WO2020040527A1 - Film de polyimide comprenant une résine de polyimide cristalline et une charge thermoconductrice, et procédé de fabrication associé - Google Patents

Film de polyimide comprenant une résine de polyimide cristalline et une charge thermoconductrice, et procédé de fabrication associé Download PDF

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WO2020040527A1
WO2020040527A1 PCT/KR2019/010587 KR2019010587W WO2020040527A1 WO 2020040527 A1 WO2020040527 A1 WO 2020040527A1 KR 2019010587 W KR2019010587 W KR 2019010587W WO 2020040527 A1 WO2020040527 A1 WO 2020040527A1
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polyimide film
polyimide
dianhydride
polyamic acid
film
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PCT/KR2019/010587
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English (en)
Korean (ko)
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김기훈
이길남
최정열
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에스케이씨코오롱피아이 주식회사
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Priority to CN201980055154.1A priority Critical patent/CN112585198B/zh
Publication of WO2020040527A1 publication Critical patent/WO2020040527A1/fr

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    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a polyimide film comprising a crystalline polyimide resin and a thermally conductive filler and a method for producing the same.
  • the polyimide (PI) resin refers to a high heat-resistant resin prepared by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, and then imidization by cyclization of the ring at a high temperature.
  • Polyimide resin is an insoluble and insoluble ultra high heat resistant resin that has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature, chemical resistance, and so on. It is used for electronic materials in a wide range of fields such as coatings, insulating films, semiconductors, and electrode protective films for TFT-LCDs.
  • the polyimide resin used in electronic devices for accumulating a large amount of information and processing and transmitting such information at high speed has to have high electrical insulation and to effectively release heat generated from electronic devices.
  • To improve the thermal conductivity is required.
  • the polyimide resin is different from other configurations, but generally has an amorphous structure, so the thermal conductivity is not high.
  • a method for improving the thermal conductivity of such a polyimide resin a method is known in which a thermally conductive filler is dispersed in a precursor solution and then a film is formed using the dispersion.
  • the polyimide film is configured to include a first polyimide resin, a second polyimide resin having a higher crystallinity and a thermally conductive filler than the first polyimide resin, thereby forming a planar surface of the polyimide film
  • a first polyimide resin a second polyimide resin having a higher crystallinity and a thermally conductive filler than the first polyimide resin, thereby forming a planar surface of the polyimide film
  • Directional thermal conductivity and thickness direction thermal conductivity can be improved.
  • the viscosity of the second polyamic acid which is a precursor of the second polyimide resin it is possible to improve the crystallinity of the polyimide film produced therefrom.
  • the present invention has a practical purpose to provide a specific embodiment thereof.
  • the present invention 100 parts by weight of the first polyimide resin,
  • the second polyimide resin is more crystalline than the first polyimide resin
  • the present invention has found that the thermal conductivity of the polyimide film is improved by the second polyimide resin and the thermally conductive filler having greater crystallinity than the first polyimide resin.
  • dianhydride is intended to include precursors or derivatives thereof, which technically may not be dianhydride, but nevertheless will react with the diamine to form a polyamic acid. This polyamic acid can be converted back to polyimide.
  • diamine 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 in turn Can be converted to mid.
  • any pair of any upper range thresholds whether or not a range is disclosed separately, or It is to be understood that this disclosure specifically discloses all ranges formed with a desired value and any lower range limit or desired value.
  • Polyimide film according to the present invention 100 parts by weight of the first polyimide resin,
  • the second polyimide resin is more crystalline than the first polyimide resin
  • the polyimide film has a crystallinity of 50% or more, a thickness direction thermal conductivity of 0.8 W / m ⁇ K or more, and a planar direction thermal conductivity of 3.2 W / m ⁇ K or more.
  • polyimide resins are amorphous polymers, and polyimide films prepared therefrom also exhibit low or no crystallinity.
  • the polyimide film comprises a second polyimide resin having a higher crystallinity than the first polyimide resin in the polyimide film so as to exhibit crystallinity.
  • the crystallinity may be at least 50%.
  • the crystallinity of the polyimide resin is greatly influenced by the composition of the monomers constituting the polyimide resin, but the crystallinity may vary depending on the polymerization method in addition to the composition.
  • the crystallinity may vary depending on the polymerization method in addition to the composition.
  • some molecular structures may be arranged in a regular state depending on the viscosity to form a degree of crystal formation.
  • the crystallinity of the polyimide film may vary according to the content of the second polyimide resin in the polyimide film, and also according to the viscosity of the second polyamic acid which is a precursor of the second polyimide resin.
  • the degree of crystallinity of the polyimide film produced from may vary.
  • the second polyimide resin may form a crystal
  • the crystal and the thermally conductive filler may have a structure of forming a heat transfer path in a thickness direction and / or a planar direction in the film.
  • the crystal is a structure in which a part of the polyimide chain included in the second polyimide resin is regularly arranged, for example, radially regular arrangements in the two-dimensional or three-dimensional direction from the central nucleus of the crystal
  • a structure in which the polyimide chain is regularly arranged in the form of a circle or sphere in the form of a crystal is grown, but a specific shape or form is not limited.
  • Such a crystal may be present in a myriad of numbers in the polyimide film, may include a portion of the amorphous portion between the crystalline portion and the crystalline portion, it is also possible that the amorphous portion, the crystal portion may be present separately.
  • This structure is different from the structure of a general polyimide film in which a thermally conductive filler is dispersed between amorphous polyimide resins in a polyimide film, and the crystals have a thickness as well as the planar direction of the thermally conductive filler and film in the polyimide film.
  • the heat transfer path can also be formed in the direction, and thus the planar thermal conductivity and / or thickness thermal conductivity of the polyimide film according to the present invention can be improved.
  • the second polyimide resin is unconditionally contained in the polyimide film unconditionally.
  • the above advantages may be expressed when the content of the second polyimide resin in the polyimide film is a certain level, but if it exceeds this, the advantages in terms of improving the thermal conductivity may be enhanced, but as described above in the polyimide film It is because elongation of a polyimide film may fall rapidly because too much crystal
  • the polyimide film contains an appropriate amount of the first polyimide resin and the second polyimide resin so that the mechanical properties and the thermal conductivity of the polyimide film are compatible.
  • the polyimide film of the present invention comprises 100 parts by weight of the first polyimide resin, 3 to 10 parts by weight of the second polyimide resin, and 2 to 8 parts by weight of the thermally conductive filler and the crystallinity of the polyimide film Is 50% or more, the thickness thermal conductivity is 0.8 W / m ⁇ K or more, and the planar thermal conductivity may be 3.2 W / m ⁇ K or more.
  • the polyimide film of the present invention may include 5 to 10 parts by weight of the second polyimide resin.
  • the first polyimide resin may be prepared by imidizing the first polyamic acid formed by the reaction of the first dianhydride and the first diamine.
  • the first dianhydride that may be used to prepare the first polyamic acid of the present invention may be an aromatic tetracarboxylic dianhydride.
  • the aromatic tetracarboxylic dianhydride is pyromellitic dianhydride (or PMDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone-3,4,3 ', 4'-tetracarboxylic Dianhydride (or DSDA), bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,3,3 ', 4'- benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride (or BTDA), bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, p-phenylenebis (trimelitic monoester Acid
  • dianhydrides which may be particularly preferably used as the first dianhydride in the present invention are pyromellitic dianhydride (PMDA), oxydiphthalic Anhydride (ODPA) and benzophenone tetracarboxylic dianhydride (BTDA) may be one or more selected from the group consisting of.
  • PMDA pyromellitic dianhydride
  • ODPA oxydiphthalic Anhydride
  • BTDA benzophenone tetracarboxylic dianhydride
  • the 1st diamine which can be used for manufacture of the 1st polyamic-acid solution of this invention is an aromatic diamine, classified as follows, for example.
  • 1,4-diaminobenzene or paraphenylenediamine, PDA
  • 1,3-diaminobenzene 2,4-diaminotoluene
  • 2,6-diaminotoluene 3,5-diaminobenzo Diamines having one benzene nucleus in structure, such as Ik acid (or DABA) and the like, diamines having a relatively rigid structure
  • Ik acid or DABA
  • diaminodiphenyl ethers such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (methylenediamine), 3,3'-dimethyl-4,4'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'- Diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (or
  • diamines which may be particularly preferably used as the first diamine in the present invention include phenylenediamine (PPD), 2,2-bis [4 '-( 4-aminophenoxy) phenyl] propane (BAPP) and methylenedianiline (MDA) may be one or more selected from the group consisting of.
  • PPD phenylenediamine
  • BAPP 2,2-bis [4 '-( 4-aminophenoxy) phenyl] propane
  • MDA methylenedianiline
  • the second polyimide resin may be prepared by imidizing the second polyamic acid formed by the reaction of the second dianhydride and the second diamine.
  • the second dianhydride may include biphenyltetracarboxylic dianhydride (BPDA), and the second diamine may be oxydianiline (ODA), 1,3-bis (4-aminophenoxy).
  • ODA oxydianiline
  • TPE-R 1,4-bis (3-aminophenoxy) benzene
  • TPE-Q 1,4-bis (3-aminophenoxy) benzene
  • the second diamine may be used alone or in combination of two or more as desired, but the diamine which may be particularly preferably used as the second diamine is 1,3-bis (4-aminophenoxy) benzene. (TPE-R).
  • the thermally conductive filler may include one or more selected from the group consisting of graphene, alumina, boron nitride, but is not limited thereto.
  • the thermally conductive filler may include 1 to 3 parts by weight of graphene and 1 to 5 parts by weight of alumina.
  • the desired level of thermal conductivity cannot be achieved.
  • the graphene or alumina content is above the above range, the excess graphene or alumina particles form agglomerates so that the particle agglomerates can be formed. It is not preferable because it may protrude from the surface of the film, resulting in a poor appearance, a problem that the mechanical properties of the produced polyimide film may be degraded or the film forming process itself is impossible.
  • the thermally conductive filler particle size can be appropriately adjusted to achieve the effect of the present invention, for example, the average long diameter of the graphene may be 5 to 15 ⁇ m, the average particle diameter of the alumina is 5 to 25 ⁇ m Can be.
  • the size of the graphene or alumina particles is less than the range, a desired level of thermal conductivity may not be achieved.
  • the size of the graphene or alumina particles is larger than the range, When mixed with the first polyamic acid or the second polyamic acid, the dispersibility is low, and the particles may protrude from the surface of the film, causing appearance defects.
  • the polyimide film of the present invention may have a crystallinity of 50% or more, a thickness thermal conductivity of 0.8 W / m ⁇ K or more, a planar thermal conductivity of 3.2 W / m ⁇ K or more, and an elongation of 30% or more. .
  • Preparing a precursor composition by mixing the first polyamic acid, the second polyamic acid, and the thermally conductive filler;
  • Production of the polyamic acid in the present invention is, for example,
  • the solvent is not particularly limited as long as it is an organic solvent in which the polyamic acid may be dissolved.
  • the 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, o-chloro Phenol solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), diglyme, and the like, and the like, and these may be used alone or in combination of two or more thereof.
  • amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc)
  • p-chlorophenol o-chloro Phenol solvents
  • o-chloro Phenol solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), diglyme, and the like, and the like, and these may be used alone or in
  • the solubility of the polyamic acid may be adjusted 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 solvents that can be particularly preferably used for preparing the precursor compositions of the present invention may be amide solvents N, N'-dimethylformamide and N, N'-dimethylacetamide.
  • the polymerization method is not limited only to the above examples, and any known method may be used.
  • the polymerization method may be applied to the first polyamic acid and the second polyamic acid polymerization, respectively.
  • the second polyamic acid when the solid content is 15% by weight, may have a viscosity measured at 23 ° C. from 100,000 cP to 150,000 cP.
  • the viscosity of the second polyamic acid exceeds the above range, a higher pressure must be applied by friction with the pipe when the second polyamic acid is moved through the pipe during the manufacturing process of the polyimide film, so that the process cost This may increase and the handleability may decrease.
  • the higher the viscosity the more time and cost the mixing process can take.
  • the filming process itself may be impossible due to the excessively high viscosity, and even if the filming process is possible, the elongation of the polyimide film produced therefrom may be lowered, which is not preferable.
  • the viscosity of the said second polyamic acid is less than the said range, the crystallinity of the 2nd polyimide resin contained in the polyimide film manufactured from this will fall, and the crystal and thermoelectric of a 2nd polyimide resin will fall.
  • the conductive filler cannot exert the effect of the present invention to form a heat transfer path in the film to improve the thermal conductivity.
  • the obtaining of the polyimide film may include forming a polyimide film by imidating the gel film after preparing the gel film by forming the precursor composition on a support and drying the film.
  • thermal imidation method As a specific method of such imidation, the thermal imidation method, the chemical imidation method, or the composite imidation method which uses the said thermal imidation method and the chemical imidation method together is mentioned as an example, About these the following non-limiting examples It will be described in more detail through.
  • the thermal imidization method is a method of excluding an chemical catalyst and inducing an imidization reaction with a heat source such as a hot air or an infrared dryer.
  • the gel film may be heat-treated to obtain a polyimide film.
  • a gel film can be understood as a film intermediate which has self-support at an intermediate stage with respect to the conversion from polyamic acid to polyimide.
  • the precursor composition is cast in the form of a film on a support such as glass plate, aluminum foil, endless stainless belt, or stainless drum, and then the precursor composition on the support 50 °C to 200 °C, Specifically, the drying may be performed at a variable temperature ranging from 80 ° C to 150 ° C.
  • a process of stretching the gel film may be performed to adjust the thickness and size of the polyimide film obtained in the subsequent heat treatment process and to improve orientation, and the stretching may be performed in the machine transport direction (MD) and the machine transport direction. It may be performed in at least one direction of the transverse direction (TD) with respect to.
  • MD machine transport direction
  • TD transverse direction
  • the gel film thus obtained is fixed in a tenter and then heat-treated at a variable temperature in the range of 50 ° C to 500 ° C, specifically 150 ° C to 500 ° C, to remove water, residual solvents, and the like remaining in the gel film. Nearly all amic acid groups can be imidated to obtain the polyimide film of the present invention.
  • 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 cure the polyimide film, and may remain in the obtained polyimide film. This may be done under a predetermined tension to relieve stress.
  • the chemical imidization method is a method of promoting imidization of an amic acid group by adding a dehydrating agent and / or an imidizing agent to the precursor composition.
  • the term "dehydrating agent” refers to a substance that promotes a ring-closure reaction through dehydration to polyamic acid, and includes, but is not limited to, aliphatic acid anhydrides, aromatic acid anhydrides, and N, N '. -Dialkylcarbodiimide, halogenated lower aliphatic, halogenated lower patty acid anhydride, aryl phosphonic dihalide, thionyl halide and the like. Of these, aliphatic acid anhydrides may be preferred in view of ease of availability and cost, and non-limiting examples thereof include acetic anhydride (AA), propion acid anhydride, and lactic acid anhydride. These etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • imidizing agent means a substance having an effect of promoting a ring closure reaction to polyamic acid, and may be an imine-based component such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine. Can be. Of these, heterocyclic tertiary amines may be preferable in view of reactivity as a catalyst. Non-limiting examples of heterocyclic tertiary amines include quinoline, isoquinoline, ⁇ -picolin (BP), pyridine, and the like, and these may be used alone or in combination of two or more thereof.
  • imine-based component such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine.
  • heterocyclic tertiary amines may be preferable in view of reactivity as a catalyst.
  • Non-limiting examples of heterocyclic tertiary amines include quinoline, iso
  • the addition amount of a dehydrating agent exists in the range of 0.5-5 mol with respect to 1 mol of amic acid groups in polyamic acid, and it is especially preferable to exist in the range of 1.0 mol-4 mol.
  • the addition amount of the imidizing agent is preferably in the range of 0.05 mol to 2 mol, and particularly preferably in the range of 0.2 mol to 1 mol with respect to 1 mol of the amic acid group in the polyamic acid.
  • the dehydrating agent and the imidating agent are less than the above range, chemical imidization is insufficient, cracks may be formed in the polyimide film to be produced, and the mechanical strength of the film may be lowered.
  • the imidization may proceed excessively rapidly, and in this case, it is difficult to cast in the form of a film or the produced polyimide film may exhibit brittle characteristics, which is not preferable. not.
  • the composite imidation method which further performs the thermal imidation method can be used for manufacture of a polyimide film.
  • the complex imidization method includes a chemical imidization method of adding a dehydrating agent and / or an imidizing agent to the precursor composition at a low temperature; And a thermal imidization process of drying the precursor composition to form a gel film and heat treating the gel film.
  • the type and amount of the dehydrating agent and the imidizing agent may be appropriately selected according to the above-described chemical imidization method.
  • the precursor composition containing the dehydrating agent and / or the imidizing agent is cast in a film form on a support such as a glass plate, an aluminum foil, an endless stainless belt, or a stainless drum, and then onto the support.
  • the precursor composition is dried at a variable temperature ranging from 50 ° C. to 200 ° C., in particular 80 ° C. to 200 ° C.
  • chemical converting agents and / or imidating agents can act as catalysts so that amic acid groups can be rapidly converted to imide groups.
  • a process of stretching the gel film may be performed to adjust the thickness and size of the polyimide film obtained in the subsequent heat treatment process and to improve orientation, and the stretching may be performed in the machine transport direction (MD) and the machine transport direction. It may be performed in at least one direction of the transverse direction (TD) with respect to.
  • MD machine transport direction
  • TD transverse direction
  • the gel film thus obtained is fixed in a tenter and then heat treated at a variable temperature ranging from 50 ° C. to 600 ° C., specifically 150 ° C. to 500 ° C. to remove water, catalyst, residual solvent, etc. remaining in the gel film, Nearly all remaining amic acid groups can be imidated to obtain the polyimide film of the present invention.
  • the dehydrating agent and / or the imidating agent may act as a catalyst, thereby rapidly converting the amic acid group into the imide group, thereby enabling 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 cure the polyimide film, and may remain in the obtained polyimide film. This may be done under a predetermined tension to relieve stress.
  • the present invention can also provide an electronic device including the polyimide film.
  • the precursor composition was bubbled through a high speed rotation of at least 1,500 rpm. Thereafter, the degassed polyimide precursor composition was applied to the glass substrate using a spin coater. After drying for 30 minutes in a nitrogen atmosphere and at a temperature of 120 °C to prepare a gel film, the gel film is heated to 450 °C at a rate of 2 °C / min, heat treatment at 450 °C 60 minutes, up to 30 °C Cooling at a rate of 2 ° C./min gave a polyimide film. Thereafter, the polyimide film was peeled off from the glass substrate by dipping in distilled water.
  • the polyimide film prepared contained 100 parts by weight of the first polyimide resin, 3 parts by weight of the second polyimide resin, 1 part by weight of graphene and 5 parts by weight of alumina and had a thickness of 15 ⁇ m.
  • the thickness of the produced polyimide film was measured using an Anritsu Electric Film thickness tester.
  • a polyimide film was prepared in the same manner as in Example 1, except that the viscosity of the second polyamic acid solution was changed as in Table 1 below.
  • Preparation Example 3 a polyimide film was prepared in the same manner as in Example 1, except that the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • Preparation Example 2 except that the viscosity of the second polyamic acid solution was changed as shown in Table 1, and in Preparation Example 3, the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • a polyimide film was prepared in the same manner as in Example 1.
  • Preparation Example 3 a polyimide film was prepared in the same manner as in Example 1, except that the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • Preparation Example 2 except that the viscosity of the second polyamic acid solution was changed as shown in Table 1, and in Preparation Example 3, the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • a polyimide film was prepared in the same manner as in Example 1.
  • a polyimide film was prepared in the same manner as in Example 1 except that 30.51 g of ODA was added instead of TPE-R.
  • a polyimide film was prepared in the same manner as in Example 1, except that no second polyamic acid was added.
  • Preparation Example 3 a polyimide film was prepared in the same manner as in Example 1, except that the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • Preparation Example 3 a polyimide film was prepared in the same manner as in Example 1, except that the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • a polyimide film was prepared in the same manner as in Example 1, except that the viscosity of the second polyamic acid solution was changed as in Table 1 below.
  • Preparation Example 2 except that the viscosity of the second polyamic acid solution was changed as shown in Table 1, and in Preparation Example 3, the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • a polyimide film was prepared in the same manner as in Example 1.
  • Preparation Example 2 except that the viscosity of the second polyamic acid solution was changed as shown in Table 1, and in Preparation Example 3, the amount of the polyamic acid solution was changed to have a content of the polyimide resin of Table 1 below.
  • a polyimide film was prepared in the same manner as in Example 1.
  • a polyimide film was prepared in the same manner as in Example 1 except that a second polyamic acid was prepared using 29.40 g of MDA instead of TPE-R and 44.63 g of ODPA instead of BPDA. Prepared.
  • Example 1 One 5 3 BPDA; TPE-R 130,000 Example 2 One 5 3 BPDA; TPE-R 150,000 Example 3 One 5 5 BPDA; TPE-R 130,000 Example 4 One 5 5 BPDA; TPE-R 150,000 Example 5 One 5 10 BPDA; TPE-R 130,000 Example 6 One 5 10 BPDA; TPE-R 150,000 Example 7 One 5 3 BPDA; ODA 130,000 Comparative Example 1 One 5 - - - Comparative Example 2 One 5 One BPDA; TPE-R 130,000 Comparative Example 3 One 5 13 BPDA; TPE-R 130,000 Comparative Example 4 One 5 3 BPDA; TPE-R 80,000 Comparative Example 5 One 5 3 BPDA; TPE-R 170,000 Comparative Example 6 One 5 3 BPDA; TPE-R 200,000
  • X c is the degree of crystallinity (%)
  • I a is the area of amorphous scattering
  • I c is the area of crystalline scattering peaks.
  • the crystallinity of the polyimide film is included by including 3 to 10 parts by weight of the second polyimide resin with respect to 100 parts by weight of the first polyimide resin. It can be confirmed that 50% or more are satisfied.
  • Comparative Examples 1 and 2 in which the content of the second polyimide resin is lower than the range of the present invention it can be seen that the crystallinity is lower than the polyimide film of the examples, the viscosity is lower than the range of the present invention in the manufacturing process Comparative Example 4 in which the second polyamic acid was added, Comparative Example 7 in which the second polyamic acid without the crystalline monomer was added, it was also confirmed that the crystallinity is lower than the polyimide film of the examples.
  • the crystallinity of the polyimide film varies according to the content of the second polyimide resin included in the polyimide film, and in the case of using a second polyamic acid having a relatively low viscosity in the manufacturing process, the polyimide film Although manufactured to include the same amount of the second polyimide resin, it can be seen that the crystallinity of the polyimide film is different.
  • each polyimide film was cut into a width of 10 mm and a length of 40 mm, followed by Instron 5564 UTM equipment of Instron. Elongation was measured using ASTM D-882 method, and the results are shown in Table 3 below.
  • the thermal conductivity in the planar direction is 3.2 W / m ⁇ K or more
  • the thermal conductivity in the thickness direction is 0.8 W / m ⁇ K or more
  • the elongation is 30%. It can be confirmed that the above are satisfied.
  • Comparative Examples 1 and 2 in which the content of the second polyimide resin is lower than the range of the present invention, and Comparative Example 4 in which a second polyamic acid having a viscosity lower than the range of the present invention are used in the preparation process are used.
  • Comparative Example 7 in which a second polyamic acid was added it was confirmed that the thermal conductivity, in particular, the thermal conductivity in the thickness direction was less than 0.8 W / m ⁇ K.
  • the polyimide film according to the present invention includes a first polyimide resin, a second polyimide resin having a higher crystallinity than the first polyimide resin, and a thermally conductive filler, so that the crystals and the thermal conductivity of the second polyimide resin are By forming the heat transfer path in the film in the thickness direction and / or the planar direction in the film, the planar thermal conductivity and the thickness direction thermal conductivity of the polyimide film can be improved.

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

Abstract

L'invention concerne un film de polyimide comprenant : 100 parties en poids d'une première résine de polyimide ; de 3 à 10 parties en poids d'une deuxième résine de polyimide ; et de 2 à 8 parties en poids d'une charge thermoconductrice, la deuxième résine de polyimide présentant une cristallinité supérieure à celle de la première résine de polyimide, et le film de polyimide présentant un degré de cristallisation de 50 % ou supérieur, une conductivité thermique de 0,8 W/m•K ou supérieure dans le sens de l'épaisseur et une conductivité thermique de 3,2 W/m•K ou supérieure dans le sens du plan.
PCT/KR2019/010587 2018-08-24 2019-08-20 Film de polyimide comprenant une résine de polyimide cristalline et une charge thermoconductrice, et procédé de fabrication associé WO2020040527A1 (fr)

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KR102447652B1 (ko) * 2020-11-24 2022-09-28 피아이첨단소재 주식회사 유전특성이 개선된 폴리이미드 필름 및 그 제조방법

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KR20070059582A (ko) * 2005-12-07 2007-06-12 마이크로코즘 테크놀리지 씨오.,엘티디 폴리아믹산 조성물 및 이를 이용하여 제조된 적층체
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KR20150113472A (ko) * 2014-03-31 2015-10-08 코오롱인더스트리 주식회사 폴리이미드 수지 및 이를 이용한 필름

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CN116496528B (zh) * 2023-06-25 2023-09-22 苏州尊尔光电科技有限公司 一种高强度导热复合聚酰亚胺薄膜及制备方法

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