WO2019160218A1 - Composition d'acide polyamique ayant une stabilité au stockage améliorée, procédé de fabrication de film de polyimide l'utilisant, et film de polyimide fabriqué au moyen de celle-ci - Google Patents

Composition d'acide polyamique ayant une stabilité au stockage améliorée, procédé de fabrication de film de polyimide l'utilisant, et film de polyimide fabriqué au moyen de celle-ci Download PDF

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WO2019160218A1
WO2019160218A1 PCT/KR2018/012258 KR2018012258W WO2019160218A1 WO 2019160218 A1 WO2019160218 A1 WO 2019160218A1 KR 2018012258 W KR2018012258 W KR 2018012258W WO 2019160218 A1 WO2019160218 A1 WO 2019160218A1
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polyamic acid
mol
polyimide film
viscosity
dianhydride
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PCT/KR2018/012258
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English (en)
Korean (ko)
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황인환
김주영
이익상
임현재
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에스케이씨코오롱피아이 주식회사
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Publication of WO2019160218A1 publication Critical patent/WO2019160218A1/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
    • 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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film

Definitions

  • the present invention relates to a polyamic acid composition having improved storage stability, a method for preparing a polyimide film using the same, and a polyimide film prepared therefrom.
  • Polyimide (PI) is a polymer material having thermal stability based on a rigid aromatic backbone, and has mechanical properties such as excellent strength, chemical resistance, weather resistance, and heat resistance based on the chemical stability of an imide ring.
  • polyimide has attracted attention as a high-performance polymer material applicable to a wide range of industrial fields such as electronics, telecommunications, and optics due to its excellent electrical properties such as insulation and low dielectric constant.
  • a polyimide film is prepared by applying a polyamic acid produced by a polymerization reaction of dianhydride and diamine on a support and imidizing it to prepare a film, and peeling it from the support.
  • the polyamic acid contains both an amine group and a carboxylic acid group, and in particular, the hydroxy group in the carboxylic acid group can be hydrolyzed by reacting with an adjacent amine group, so that the storage stability is known to be poor. In addition, this phenomenon is known to stand out at room temperature or more than the low temperature.
  • the viscosity during the process may change significantly, and thus the application and imidization of the polyamic acid may proceed unstable.
  • the viscosity of the polyamic acid is lowered, the mechanical and thermal properties of the polyimide film may be greatly reduced.
  • the degradation of the thermal properties of the double polyimide film can be particularly negative for the manufacture of display substrates involving high temperature processes.
  • a process temperature of 400 ° C. or higher may be formed, and even at this high temperature, even a polyimide having excellent heat resistance may be thermally decomposed.
  • the thermal properties of the mid film may be a very important factor for implementing the display substrate.
  • the alcohol-based additive is disclosed as an essential factor for the implementation of the polyimide film having not only can improve the storage stability of the polyamic acid, but also has excellent thermal and mechanical properties.
  • the alcoholic additive may replace at least a portion of the hydroxy group included in the polyamic acid with an alkoxy group having a relatively low reactivity at room temperature.
  • a polyamic acid-containing composition in which at least a portion of a hydroxy group is substituted with an alkoxy group by an alcohol-based additive may be used.
  • the imidization reaction may proceed relatively quickly due to the rapid release of the alkoxy group during the heat treatment for forming the polyimide.
  • This rapid imidization reaction may contribute to the improvement of the conversion ratio ('imidization rate') from the amic acid group to the imide group, thereby realizing a polyimide film having excellent mechanical and thermal properties.
  • the polyimide film prepared according to the above the thermal decomposition temperature is 550 °C or more, the tensile strength is 280 kgf / cm 2 or more, the thermal expansion coefficient may be 40 ppm / °C or less, the elongation may be 13% or more.
  • Such a polyimide film has an advantage of satisfying the mechanical and thermal properties required for the display substrate.
  • the present invention has a substantial object to provide a specific embodiment thereof.
  • the present invention found that the polyamic acid composition in which at least a part of the hydroxy group contained in the polyamic acid of the alcohol-based additive is substituted with an alkoxy group has excellent storage stability at room temperature.
  • the present invention also found that by using this to produce a polyimide film, it is possible to induce a faster imidization reaction, thereby realizing a polyimide film having excellent mechanical and thermal properties.
  • dianhydrides are intended to include precursors or derivatives thereof, which may technically not be dianhydrides, but nevertheless will react with diamines to form polyamic acids. 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.
  • a range of numerical values is mentioned herein, unless stated otherwise, the range is intended to include the endpoint and all integers and fractions within that range. It is intended that the scope of the invention not be limited to the particular values mentioned when defining the range.
  • the polyamic acid composition according to the present invention comprises an organic solvent and a polyamic acid, at least a part of the hydroxy group included in the polyamic acid is alcohol-decomposed reaction with an alcohol-based additive is substituted with an alkoxy group,
  • the viscosity change rate according to the following formula (1) is characterized in that more than -3% to less than + 3%.
  • a 1st viscosity is a viscosity measured immediately after manufacture of a polyamic-acid composition
  • a 2nd viscosity is the viscosity measured when 10 days passed after storing a polyamic-acid composition at normal temperature.
  • the change in viscosity means that the polyamic acid has been modified, and the degree of change in viscosity can be understood as an index indicating the degree of polyamic acid modification.
  • the polyamic acid of the present invention is excellent in storage stability at room temperature because the rate of change of viscosity is not large as less than ⁇ 3% despite storage for 10 days at room temperature. This may be due to the alkoxy group at room temperature having a relatively low room temperature reactivity compared to the hydroxy group.
  • the first viscosity may be 10,000 cP or less, specifically 7,500 cP or less, and more specifically 7,200 cP or less.
  • the polyamic acid composition having such a first viscosity has an advantage of easy handling in terms of fluidity, and may be advantageous for film formation.
  • the polyamic acid composition may be prepared by adding at least 0.07 mol% to less than 1.5 mol% of an alcoholic additive based on 100 mol% of the amic acid group of the polyamic acid, and in detail, based on 100 mol% of the diamine monomer. , 0.1 mol% or more and 1 mol% or less.
  • the polyamic acid composition is prepared by adding an alcohol-based additive to exceed the above range, it may be difficult to prepare a polyimide film having desired physical properties, and when it is below the above range, improvement in storage stability may be insignificant. , Not preferred.
  • the alcohol additive may be one or more selected from the group consisting of methanol, ethanol, n-propanol, isopropyl alcohol, benzyl alcohol, ethoxyethanol and butoxyethanol, but is not limited thereto.
  • the polyamic acid may be produced by polymerizing one or more dianhydride monomers and one or more diamine monomers in an organic solvent.
  • the dianhydride monomers that may be used to prepare the polyamic acid of the present invention may be aromatic tetracarboxylic dianhydrides.
  • the aromatic tetracarboxylic dianhydride is pyromellitic dianhydride (or PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (or BPDA), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (or a-BPDA), 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 (
  • dianhydride monomers which may be particularly preferably used in the present invention are pyromellitic dianhydride (PMDA), 3,3 ', 4,4 At least one selected from the group consisting of '-biphenyltetracarboxylic dianhydride (s-BPDA) and 2,3,3', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) Can be.
  • PMDA pyromellitic dianhydride
  • s-BPDA '-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3', 4'-biphenyltetracarboxylic dianhydride
  • Diamine monomers that can be used in the production of the polyamic acid of the present invention are aromatic diamines, and are classified as follows.
  • 1,4-diaminobenzene or paraphenylenediamine, PDA, PPD
  • 1,3-diaminobenzene 2,4-diaminotoluene
  • 2,6-diaminotoluene 3,5-dia Diamines having one benzene nucleus in structure, such as minobenzoic acid (or DABA) and the like, diamines having a relatively rigid structure
  • Diamines having one benzene nucleus in structure such as minobenzoic acid (or DABA) and the like, diamines having a relatively rigid structure
  • diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether (or oxydianiline, ODA), 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenylmethane (Methylenediamine), 3,3'-dimethyl-4,4'-diaminobiphenyl, 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'-di
  • PPD 1,4-diaminobenzene
  • MPD 1,3-diaminobenzene
  • DABA 3,5-diaminobenzoic acid
  • the diamine monomer and the dianhydride monomer may be added in substantially equimolar, and in detail, based on 100 mol% of the diamine monomer, the amount of the dianhydride monomer added is 99 mol% to 101.
  • the amount of the dianhydride monomer may be 99 mol% to 99.9 mol% based on 100 mol% of the diamine monomer.
  • the polymerization is terminated before reaching a desired molecular weight, or a plurality of low molecular weight oligomers are generated to implement a polyamic acid capable of forming a polyimide film. it's difficult.
  • step (b) at least a part of the hydroxy group included in the polyamic acid is reacted with the alcoholic additive to be substituted with an alkoxy group;
  • the hydroxy group and the alkoxy group may each react with the amine group to form a plurality of imide groups, wherein the alkoxy group serves as a good leaving group, This is the point where the reaction can be promoted.
  • the alkoxy group is less reactive than a hydroxy group at room temperature, and thus is preferable for polyamic acid in terms of storage stability.
  • the alkoxy group can act as an excellent leaving group to promote the imidization reaction of polyamic acid, It can serve as a significant advantage for both mymic acid and polyimide films.
  • a polyimide film having a high imidation ratio can be realized from these advantages.
  • the advantages of the production method of the present invention can be sufficiently expected.
  • Preparation of the polyamic acid solution in the present invention is, for example,
  • the polymerization method is not limited only to the above examples, of course, any known method may be used.
  • the dianhydride monomer may be appropriately selected from the examples described above, and specifically, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) may be preferably used.
  • PMDA pyromellitic dianhydride
  • s-BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride
  • the dianhydride monomer may be appropriately selected from the examples described above, and specifically, 1,4-diaminobenzene (PPD), 1,3-diaminobenzene (MPD), 2,4-diaminotoluene, At least one selected from the group consisting of 2,6-diaminotoluene and 3,5-diaminobenzoic acid (DABA) can be preferably used.
  • PPD 1,4-diaminobenzene
  • MPD 1,3-diaminobenzene
  • DABA 3,5-diaminobenzoic acid
  • the alcoholic additive may be at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropyl alcohol, benzyl alcohol, ethoxyethanol and butoxyethanol, but the scope of the present invention is not limited thereto. .
  • the amount of the dianhydride monomer may be 99 mol% to 99.9 mol%, and the amount of the alcohol-based additive may be 0.1 mol% to 1 mol%.
  • the polymerization is terminated before the desired molecular weight is reached, or a plurality of low molecular weight oligomers are generated to form a polyimide film with the polyamic acid prepared therefrom. Problems you can't do can happen.
  • the alcohol-based additive When the alcohol-based additive is added in the above range, it may be difficult to manufacture a polyimide film having the desired physical properties, if the alcohol-based additive is below the range, the improvement of the storage stability of the polyamic acid solution may be insignificant, Not desirable
  • the polyimide film may be prepared through thermal imidization.
  • the said thermal imidation method is a method of removing an chemical catalyst and inducing an imidation reaction with heat sources, such as a hot air and an infrared dryer.
  • the alkoxylation reaction occurs by introducing an alcoholic additive
  • at least a part of the added alcoholic additive may remain unreacted, and water is generated as a by-product of the alkoxylation reaction. May remain in the acid solution. Water remaining in the polyamic acid solution may lose the function of the anhydride catalyst used as the chemical catalyst in the imidization process. Therefore, even if a chemical catalyst is used, there is a possibility that the imidization reaction does not proceed effectively.
  • the thermal imidation method without using the chemical catalyst may be preferable for the implementation of the polyimide film intended in the present invention.
  • the thermal imidization method may include the step (d), wherein the gel film is heat-treated at a variable temperature ranging from 50 ° C. to 600 ° C. in the step (d) to present an amic acid group present in the gel film. It can imidize.
  • amic acid (about 0.1 mol% to 10 mol%) may be imidized in the process (c) of forming the gel film, and for this purpose, in the process (c), the range of 50 ° C. to 200 ° C. It is possible to dry the polyamic acid composition at variable temperatures, which may also fall within the scope of the thermal imidization method.
  • the polyimide film of the present invention prepared according to the above production method the thermal decomposition temperature (Td) is 550 °C or more, the thermal expansion coefficient is 40 ppm / °C or less, elongation is 13% or more, tensile strength 280 kgf / cm 2 or more.
  • the present invention also provides an electronic device including the polyimide film, and the electronic device may be an electronic device including a flexible circuit board or a display substrate.
  • Viscosity was measured by measuring Brookfield viscometer (RVDV-II + P) twice at 50 rpm using 7 scandals at 25 ° C.
  • a polyamic acid composition was prepared in the same manner as in Example 1 and the first viscosity was measured.
  • the measured viscosity was about 6,900 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 1 and the first viscosity was measured.
  • the measured viscosity was 6,970 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 1 except that n-propanol was added in the molar ratio shown in Table 1 instead of methanol, and the first viscosity was measured. The measured viscosity was 6,950 cP.
  • PPD, BPDA and PMDA were added to NMP in a molar ratio shown in Table 1 while maintaining the reaction system at 25 ° C. to prepare a polyamic acid solution.
  • Methanol was added to the polyamic acid solution thus prepared in the molar ratio shown in Table 1 to prepare a polyamic acid composition, and the first viscosity was measured. The measured viscosity was about 5,300 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 5 and the first viscosity was measured.
  • the measured viscosity was about 5,150 cP.
  • PPD and BPDA were added to NMP in a molar ratio shown in Table 1 while maintaining the inside of the reaction system at 25 ° C to polymerize to prepare a polyamic acid solution, and the first viscosity was measured.
  • the measured viscosity was about 7,100 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 1 and the first viscosity was measured.
  • the measured viscosity was about 6,780 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 1 and the viscosity was measured.
  • the viscosity measured was about 6,950 cP.
  • Ethanol was used instead of methanol, except for changing the molar ratio of BPDA and ethanol as shown in Table 1 below, a polyamic acid composition was prepared in the same manner as in Example 1, and the first viscosity was measured. The measured viscosity was 7,050 cP.
  • N-propanol was used instead of methanol, and the polyamic acid composition was prepared in the same manner as in Example 1 except that the molar ratio of BPDA and n-propanol was changed as shown in Table 1 below, and the first viscosity was measured. The measured viscosity was 7,000 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 5 and the viscosity was measured.
  • the measured viscosity was about 5,400 cP.
  • a polyamic acid composition was prepared in the same manner as in Example 5 and the viscosity was measured.
  • the measured viscosity was about 5,010 cP.
  • Example 1 100 - 99.9 0.1 - - 7,100
  • Example 2 100 - 99 One - - 6,900
  • Example 3 100 - 99.9 - 0.1 - 6,970
  • Example 4 100 - 99.9 - - 0.1 6,950
  • Example 5 100 50 49.9 0.1 - - 5,300
  • Example 6 100 50 49 One - - 5,150
  • Comparative Example 1 100 - 100 - - - - 7,100
  • Comparative Example 2 100 - 98.5 1.5 - - 6,780
  • Comparative Example 5 100 - 99.95 - - 0.05 - 5,400
  • Example 7 100 50 48.5 1.5 - - 5,010
  • the polyamic acid composition prepared in Examples 1 to 6 and Comparative Examples 1 to 7 was left at room temperature for 10 days. Thereafter, the second viscosity was measured by the viscosity measuring method described in Example 1, and the viscosity change rate was calculated according to the following formula (1) and shown in Table 2 below.
  • Second viscosity (cP) % Viscosity change Example 1 7,100 7,210 + 1.55% Example 2 6,900 7,070 + 2.46% Example 3 6,970 7,100 + 1.86% Example 4 6,950 7,100 + 2.16% Example 5 5,150 5,250 + 1.32% Example 6 5,300 5,420 + 2.26% Comparative Example 1 7,100 8,030 + 13.10% Comparative Example 2 6,780 6,120 -10.78% Comparative Example 3 6,950 7,670 + 10.36% Comparative Example 4 7,050 7,850 + 11.35% Comparative Example 5 7,000 7,890 + 12.71% Comparative Example 6 5,400 6,030 + 11.67% Comparative Example 7 5,010 4,520 -10.84%
  • the polyamic-acid composition of this invention is excellent in storage stability at normal temperature.
  • Comparative Example 1 in which no alcohol-based additive was added, a marked decrease in viscosity of the polyamic acid was caused. It is expected that the hydroxyl group in the polyamic acid of Comparative Example 1 promotes a modification reaction such as hydrolysis, and accordingly, the viscosity greatly changes as shown in Table 2.
  • the polyimide precursor composition of Example 1 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 in a nitrogen atmosphere and at a temperature of 120 °C for 30 minutes, the temperature was raised to 450 °C at a rate of 2 °C / min, heat treatment at 450 °C for 60 minutes, cooled to 30 °C at a rate of 2 °C / min A polyimide film was prepared. After dipping in distilled water, the polyimide film was peeled off the glass substrate. The thickness of the produced polyimide film was 15.1 ⁇ m.
  • the thickness of the prepared polyimide film was measured using an Anritsu Electric Film thickness tester.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Example 2 was used.
  • a polyimide film having a thickness of 15.5 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Example 3 was used.
  • a polyimide film having a thickness of 15.4 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Example 4 was used.
  • a polyimide film having a thickness of 14.8 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Example 5 was used.
  • a polyimide film having a thickness of 14.6 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Example 6 was used.
  • a polyimide film having a thickness of 15.3 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 1 was used.
  • a polyimide film having a thickness of 15.7 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 2 was used.
  • a polyimide film having a thickness of 15.5 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 3 was used.
  • a polyimide film having a thickness of 15.5 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 4 was used.
  • a polyimide film having a thickness of 15.4 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 5 was used.
  • a polyimide film having a thickness of 15.3 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 6 was used.
  • a polyimide film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 7, except that the polyamic acid composition of Comparative Example 7 was used.
  • Pyrolysis temperature was measured using a Perkin Elmer TGA measuring device.
  • the polyimide film was cut into 3 mm x 3 mm, placed on a pre-treated and weighed fan, insulated at 110 ° C. for 30 minutes, cooled to room temperature, and heated again at 600 ° C. per 5 ° C. to reduce the weight.
  • the pyrolysis temperature was calculated when the weight loss ratio was 1% of the weight of the polyimide film initially loaded.
  • Tensile strength was measured by the method according to KS6518.
  • the TA company thermomechanical analyzer Q400 model was used, and the polyimide film was cut into a width of 2 mm and a length of 10 mm, and then subjected to a tension of 0.05 N in a nitrogen atmosphere at 500 ° C. After the temperature was raised to °C and cooled again at a rate of 10 °C / min was measured the slope of 100 °C 400 °C section.
  • Example 7 and Comparative Example 8 in which the monomer composition is similar.
  • the polyimide film of Example 7 was prepared from the polyamic acid composition in which the alcohol-based additive was added to the polyamic acid, and it can be seen that the polyimide film has a relatively excellent thermal decomposition temperature and tensile strength.
  • the polyimide film of Comparative Example 8 was prepared from a polyamic acid without an alcohol-based additive, it can be seen that it has a significantly lower thermal decomposition temperature and tensile strength than Example 7.
  • the alkoxy group may react at a faster reaction rate with an adjacent amine group. This is expected to be due to the alkoxy group belonging to a relatively better leaving group compared to the hydroxy group at the temperature formulated for imidization.
  • the thermal expansion coefficient of the polyimide film may be preferably 15 ppm / ° C., specifically 10 ppm / ° C. or less, in terms of dimensional stability at high temperature. It is important that the dimension does not change even at a high temperature process of more than °C, it may be desirable to have a thermal expansion coefficient of 10 ppm / °C or less.
  • the thermal expansion coefficient of 8 ppm / °C or less it can be seen that the dimensional stability at high temperature, such characteristics are required in various electronic fields, such as display substrates or flexible circuits It can be used preferably.
  • the coefficient of thermal expansion was remarkably high, which can be expected to be difficult to apply to the above-described electronic field due to poor dimensional stability at high temperature.
  • the film when the film is a good product, it is represented as 'O', and it is represented as 'X' when it is judged to be defective because it has no self-supporting or brittle characteristics.
  • a feature of the polyamic acid composition according to the present invention is that at least a part of the hydroxy group included in the polyamic acid is substituted with an alkoxy group by adding an alcoholic additive.
  • the alkoxy group has a relatively low reactivity at room temperature and does not cause denaturation of the polyamic acid. Accordingly, the polyamic acid composition has an advantage of improving room temperature storage stability.
  • the alkoxy group can also inhibit hydrolysis even in the process of raising the temperature to imidize the polyamic acid, which can advantageously act to implement a polyimide film having better physical properties than in the absence of the alkoxy group.
  • the polyimide film prepared according to the above the thermal decomposition temperature is 550 °C or more, the tensile strength is 280 kgf / cm 2 or more, it can have excellent thermal and mechanical properties required for the display substrate.

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Abstract

La présente invention concerne une composition d'acide polyamique ayant une excellente stabilité au stockage, un procédé de fabrication d'un film de polyimide l'utilisant, et un film de polyimide, la composition d'acide polyamique comprenant un solvant organique et de l'acide polyamique, au moins une partie des groupes hydroxyle de l'acide polyamique ayant été substituée par un groupe alcoxy au moyen d'une réaction d'alcoolyse avec un additif alcoolique.
PCT/KR2018/012258 2018-02-19 2018-10-17 Composition d'acide polyamique ayant une stabilité au stockage améliorée, procédé de fabrication de film de polyimide l'utilisant, et film de polyimide fabriqué au moyen de celle-ci WO2019160218A1 (fr)

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KR1020180019367A KR101949316B1 (ko) 2018-02-19 2018-02-19 저장 안정성이 향상된 폴리아믹산 조성물, 이를 이용한 폴리이미드 필름의 제조방법 및 이로 제조된 폴리이미드 필름
KR10-2018-0019367 2018-02-19

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KR102097406B1 (ko) * 2019-05-10 2020-04-07 에스케이씨코오롱피아이 주식회사 폴리이미드 전구체 조성물, 이의 제조 방법 및 폴리이미드
KR102125686B1 (ko) * 2019-05-24 2020-06-23 피아이첨단소재 주식회사 폴리아믹산 조성물, 및 이의 제조 방법
EP4368662A1 (fr) * 2022-11-14 2024-05-15 SK microworks Co., Ltd. Film à base de polyamide-imide, son procédé de préparation, et fenêtre de couverture et dispositif d'affichage le comprenant

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