WO2018038309A1 - Composition de résine précurseur de polyimide, transparente, plus stable et plus résistance à la chaleur, procédé de production d'un film de polyimide utilisant la composition, et film de polyimide ainsi obtenu - Google Patents

Composition de résine précurseur de polyimide, transparente, plus stable et plus résistance à la chaleur, procédé de production d'un film de polyimide utilisant la composition, et film de polyimide ainsi obtenu Download PDF

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WO2018038309A1
WO2018038309A1 PCT/KR2016/010435 KR2016010435W WO2018038309A1 WO 2018038309 A1 WO2018038309 A1 WO 2018038309A1 KR 2016010435 W KR2016010435 W KR 2016010435W WO 2018038309 A1 WO2018038309 A1 WO 2018038309A1
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mol
heat resistance
acid dianhydride
polyimide film
resin composition
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Korean (ko)
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강진수
김진모
안용호
오경옥
한승진
최은지
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㈜대림코퍼레이션
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Priority to JP2019532897A priority Critical patent/JP6906054B2/ja
Priority to CN201680088588.8A priority patent/CN109689732B/zh
Publication of WO2018038309A1 publication Critical patent/WO2018038309A1/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
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the present invention provides a polyimide precursor resin composition having excellent mechanical properties, high heat resistance, low coefficient of thermal expansion, but having no transparency in solution casting, and a polyimide film manufacturing method using the same, and a polyimide film prepared thereby
  • the present invention relates to a flexible display substrate material and a semiconductor material.
  • Flexible polymer materials are attracting attention as substrate materials of flexible displays, which are being spotlighted as next generation display devices.
  • the flexible device generally uses an organic light emitting diode (OLED) display, and a TFT process with a high process temperature (300 to 500 ° C) is used.
  • OLED organic light emitting diode
  • a TFT process with a high process temperature 300 to 500 ° C
  • Polymer materials that withstand such high process temperatures are extremely limited, and polyimide (PI) resin, which is a polymer having excellent heat resistance, is mainly used.
  • An organic light emitting diode (OLED) display manufactures a display by coating a resin on a glass substrate, thermosetting and filming the film, and removing the glass substrate from the glass substrate after several steps.
  • the stability of the resin at room temperature is important. If the stability of the resin is not secured, a uniform film may not be formed after curing due to agglomeration of the resin, cloudiness, etc., and eventually, product defects may occur. In addition, product defects may occur due to thermal shock due to the high temperature of the TFT deposition process during the post process. Therefore, a polyimide resin (PI) having resin stability at room temperature, high heat resistance and low coefficient of thermal expansion (CTE) is required.
  • PI polyimide resin having resin stability at room temperature, high heat resistance and low coefficient of thermal expansion (CTE)
  • Korean Patent Laid-Open Publication No. 2015-108812 discloses a polyamic acid solution and a film using the same, which can be applied as a base layer or a protective layer of a display device because of its excellent thermal properties with low thermal expansion rate and high thermal decomposition temperature. This may not be secured, and the uniform film may not be formed after curing due to agglomeration of the resin, cloudiness, and the like, and eventually, product defects may occur.
  • Korean Patent Laid-Open Publication No. 2013-35691 discloses a composition and a manufacturing method for preparing a copolymerized polyamide-imide film, but this has a limitation in the economic part of the process because it must go through a process of generating and removing by-products. .
  • the polyimide composition having high heat resistance, low coefficient of thermal expansion, and excellent mechanical strength, as well as the stability of the resin, and the manufacturing process require a relatively simple method of raising a manufacturing method.
  • Patent Document 1 Korean Patent Application Publication No. 2015-108812
  • Patent Document 2 Korean Laid-Open Patent No. 2013-35691
  • the present inventors have improved the composition of aromatic diamine and acid dianhydride compounds, and the composition of organic solvents that do not cause turbidity, in the production of polyimide films having improved heat resistance and optimum mechanical properties.
  • This invention was completed by discovering the polyimide precursor resin composition which has transparency, resin stability, high heat resistance, and a low coefficient of thermal expansion than the conventional polyimide film.
  • an object of the present invention is to provide a polyimide precursor resin composition that can be used as a flexible display substrate material having transparency, resin stability, high heat resistance, and low coefficient of thermal expansion.
  • the present invention has a glass transition temperature of 300 °C or more, the thermal expansion coefficient in the range of 100 to 300 °C 25 ppm / °C or less, wavelength of 550 nm based on the thickness of the film prepared by the above method 10 ⁇ 15 ⁇ m
  • An object thereof is to provide a polyimide resin film having a transmittance of 85% or more and a yellow index (YI) of 7 or less at a wavelength of 550 nm.
  • the present invention provides a polyimide precursor resin composition
  • a polyimide precursor resin composition comprising an aromatic diamine component, an acid dianhydride compound, and an organic solvent, wherein the aromatic diamine component (A) is 2,2'-bis (trifluoromethyl) which is a fluorinated aromatic diamine monomer.
  • the dianhydride compound (B) is 4,4- (hexafluoroisopropylidene) diphthalic anhydride (6FDA) which is a fluorinated aromatic acid dianhydride and pyromellitic dianhydride (PMDA) which is a non-fluorinated aromatic acid dianhydride, or 3 ',
  • 6FDA 4,4- (hexafluoroisopropylidene) diphthalic anhydride
  • PMDA pyromellitic dianhydride
  • BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • the organic solvent (C) is gamma-butyrolactone (GBL) and N-methyl-2-pyrrolidone (NMP) Mixtures of, or gamma-butyrolactone (GBL) and 3-methoxy-N, N-dimethyl propaneami Provides (DM
  • the present invention provides a method for producing a transparent polyimide resin film, characterized in that the polyamic acid solution prepared by using the composition is heat-treated.
  • the present invention has a glass transition temperature of 300 °C or more, the thermal expansion coefficient in the range of 100 to 300 °C 25 ppm / °C or less, wavelength of 550 nm based on the thickness of the film prepared by the above method 10 ⁇ 15 ⁇ m
  • a transparent polyimide resin film having a transmittance of 85% or more and a yellow index (YI) of 550 nm at a wavelength of 7 or less is provided.
  • the resin stability is excellent at room temperature, which does not cause cloudiness during solution casting, compared to the conventional polyamic acid solution, and provides excellent mechanical properties, optical properties, and heat resistance properties during film production through thermal curing. By doing so, it can be usefully used for a flexible display substrate material, a semiconductor material and the like.
  • the present invention can secure process competitiveness because it does not go through the process of generating and removing by-products compared to the prior art when preparing a polyamic acid solution.
  • Figure 3 shows the clouding phenomenon (at room temperature stability) according to the organic solvent (100 mol% of NMP alone) of Comparative Example 3, when casting a polyamic acid solution on a glass substrate at room temperature.
  • the polyimide precursor resin composition (hereinafter referred to as the 'polyamic acid composition') of the present invention has a composition of an aromatic diamine and an acid dianhydride compound having improved heat resistance and optimum mechanical properties, and a composition of an organic solvent in which no turbidity occurs. And its usage is optimized to provide a transparent polyimide film having high heat resistance, low coefficient of thermal expansion and excellent mechanical strength.
  • the polyimide precursor composition in other words the 'polyamic acid composition' according to the present invention, means a composition used to prepare a polyamic acid solution used for preparing a polyimide film.
  • the polyamic acid composition according to the present invention comprises an aromatic diamine component (A) comprising a fluorinated aromatic diamine or an amide group or a mixture thereof, an acid containing a fluorinated aromatic acid dianhydride and a non-fluorinated aromatic acid dianhydride compound.
  • An organic solvent comprising N-methyl-2-pyrrolidone (NMP) or 3-methoxy-N, N-dimethyl propanamide (DMPA) in dianhydride compound (B), gamma-butyrolactone (GBL) C), and a polyamic acid composition comprising the reaction catalyst (D).
  • NMP N-methyl-2-pyrrolidone
  • DMPA N-dimethyl propanamide
  • B dianhydride compound
  • GBL gamma-butyrolactone
  • D polyamic acid composition comprising the reaction catalyst
  • the aromatic diamine component in the present invention is 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) which is a fluorinated aromatic diamine monomer, or N- (which is a polyamine monomer having an amide group.
  • TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl
  • N- which is a polyamine monomer having an amide group.
  • DBA 4-amino phenyl) -4-aminobenzamide
  • the fluorinated aromatic diamine monomer 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) is 30 to 100 mol% based on the total diamine compound
  • N- (4-amino phenyl) -4-aminobenzamide (DBA) is 5 to 50 mol% relative to the total diamine compound, and may further comprise a balance of non-fluorinated aromatic diamine.
  • the aromatic diamine component (A) contains a fluorinated aromatic diamine having a fluorine substituent introduced therein, it is possible to provide a polyimide film having excellent optical properties due to the charge transfer effect between the fluorine substituents in the molecular chain. have.
  • polyimide film having excellent heat resistance and low coefficient of thermal expansion due to the rigidity of the aromatic structure and the amide structure Can be provided.
  • the polyimide film has improved optical properties and thermal properties while maintaining optical properties as compared with using only fluorinated aromatic diamine. Can be prepared.
  • the fluorinated aromatic diamine is not particularly limited as long as it is an aromatic diamine containing fluorine.
  • 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,4'-Diaminobiphenyl, TFMB) bis aminohydride Bisaminohydroxyphebyl hexafluoropropane (DBOH), bis aminophenoxy phenyl hexafluoropropane (4BDAF), 2,2'-bis (trifluoromethyl) -4,3'-dia Minobiphenyl (2,2'-Bis (trifluoromethyl) -4,3'-Diaminobiphenyl), and 2,2'-bis (trifluoromethyl) -5,5'-diaminobiphenyl (2,2 ' At least one selected from the group consisting of -Bis (trifluoromethyl) -5,5'-Diaminobiphenyl)
  • TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl
  • the TFMB is 30 to 100 mol%, preferably 50 to 90 mol% based on 100 mol% of the total diamine compound, and the charge transfer effect between intermolecular fluorine substituents when used within the above range. ) May further improve the optical properties of the polyimide film.
  • the present invention may include not only fluorinated aromatic diamine monomers such as TFMB, but also non-fluorinated aromatic diamine monomers. At this time, the fluorinated aromatic diamine and non-fluorinated aromatic are used so that the total is 100 mol%.
  • the polyimide resin may include a compound having or forming an amide structure for excellent heat resistance and low coefficient of thermal expansion.
  • Compounds capable of forming such an amide structure include an acid halide and a dicarboxylic acid. Examples include p-terephthaloyl chloride (TPC), isophthaloyl dichloride (IPC), 1,3-adamantanedicarbonyl dichloride (ADC) , 5-norbornene-2,3-dicarbonyl chloride (NDC), 4,4'-benzoyl dichloride (4,4'-benzoyl dichloride, BDC), 1 1,4-naphthalene dicarboxylic acid dichloride (1,4-NaDC), 2,6-naphthalene dicarboxylic acid dichloride (2,6-naphthalene dicarboxylic acid dichloride) 6-NaDC), 1,5-naphthalene dicarboxylic acid dichloride (1,5-NaDC), ter
  • N- (4-aminophenyl) -4-aminobenzamide N- (4-aminophenyl) -4-aminobenzamide, DBA
  • DBA N- (4-aminophenyl) -4-aminobenzamide
  • the content of N- (4-amino phenyl) -4-aminobenzamide (DBA) is not particularly limited, but may be 5 to 50 mol%, preferably 5 to 20 mol% based on 100 mol% of the diamine compound. Can be.
  • the aromatic acid dianhydride compounds of the present invention comprise 20 to 80 mol% of fluorinated aromatic acid dianhydrides and 80 to 20 mol% of non-fluorinated aromatic acid dianhydride compounds.
  • the optical and heat resistance properties of the polyimide film may be simultaneously improved. Due to the fluorine substituent of the fluorinated aromatic dianhydride, a polyimide film having excellent optical properties can be produced, and a polyimide film having excellent heat resistance can be prepared due to the rigid molecular structure of the aromatic dianhydride.
  • Fluorinated aromatic acid dianhydrides are aromatic acid dianhydrides having fluorine substituents introduced therein, for example, 4,4- (hexafluoroisopropylidene) diphthalic anhydride (4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) ), And 4,4- (4,4-hexafluoroisopropylidenediphenoxy) bis- (phthalic anhydride) (4,4 '-(4,4'-Hexafluoroisopropylidenediphenoxy) bis- (phthalic anhydride, 6- One or more selected from the group consisting of FDPDA) can be used, but in the present invention, 6FDA is preferably used as the fluorinated aromatic acid dianhydride.
  • the fluorinated aromatic acid dianhydride is 20 to 80 mol%, preferably 40 to 70 mol%, based on 100 mol% of the total acid dianhydride, and can realize high permeability and low yellowness of the polyimide film within the above range. have.
  • the non-fluorinated aromatic acid dianhydride is an aromatic acid dianhydride to which no fluorine substituent is introduced, and pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydrides (3,3'4,4'-biphenyltetracarboxylic acid dianhydride, BPDA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-benzophenonetetracarboxylic dianhydride , BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 2,2-bis [4-3,4-dicarboxyphenoxy] phenyl] propane anhydride (2,2- Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), 3, 3 ', 4, 4'-diphenyl sulfone tetracar
  • the non-fluorinated aromatic acid dianhydride is 80 to 20 mol%, preferably 30 to 50 mol%, based on 100 mol% of the total acid dianhydride, further improving heat resistance while maintaining the high permeability and low yellowness of the polyimide film. Can be lowered.
  • the organic solvent in the present invention is m-cresol, N-methyl-2-pyrrolidone (NMP), N, N- dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), di Polar solvents such as ethyl acetate (DEA), 3-methoxy-N, N-dimethyl propanamide (DMPA), low-boiling solvents such as tetrahydrofuran (THF), chloroform, or gamma-butyrolactone and GBL Low absorption solvents.
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • di Polar solvents such as ethyl acetate (DEA), 3-methoxy-N, N-dimethyl propanamide (DMPA), low-boiling solvents such as tetrahydrofuran (THF), chloroform, or gam
  • the organic solvent used in the present invention plays an important role in improving the clouding phenomenon, where the clouding phenomenon can be confirmed through FIGS. 1 to 3.
  • 1 shows room temperature stability (without turbidity) for 70 mol% GBL and 30 mol% NMP organic solvent when casting a polyamic acid solution on a glass substrate at room temperature
  • FIG. 2 shows 70 mol% GBL and 30 mol DMPA. It shows the room temperature stability (without cloudy phenomenon) with respect to the organic solvent of%.
  • Figure 3 shows the turbidity phenomenon for the organic solvent of 100 mol% NMP alone.
  • the amount of the organic solvent used is 30 to 70 mol% of gamma-butyrolactone (GBL) and N-methyl-2-pyrrolidone (NMP) or 3-methoxy-N, N-dimethyl propanamide (DMPA) 70 to Preference is given to using 30 mol%. More preferably, 30-50 mol of N-methyl-2-pyrrolidone (NMP) or 3-methoxy-N, N-dimethyl propanamide (DMPA) in 50-70 mol% of gamma-butyrolactone (GBL) %to be. Or 100 mol% of gamma-butyrolactone (GBL) alone.
  • the reaction catalyst of the present invention may further include at least one selected from the group consisting of trimethylamine, xylene, pyridine, and quinoline, depending on the reactivity, but is not necessarily limited thereto. Does not.
  • the polyamic acid composition may contain a small amount of additives such as a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, and a leveling agent, as necessary, within a range that does not significantly impair the object and effect of the present invention.
  • the polyamic acid solution obtained by polymerization using an aromatic diamine component, an acid dianhydride compound, an organic solvent, and a reaction catalyst which is a polyamic acid composition according to the present invention, has a solid content of 10 to 40 wt%, based on the total weight of the polyamic acid solution, Preferably it contains 10 to 25% by weight. If the solid content is less than 10% by weight there is a limit to increase the thickness of the film during film production, if the solid content is more than 40% by weight there is a limit in controlling the viscosity of the polyamic acid is formed within the above range.
  • the polyamic acid solution is an organic solvent content based on a solid content of 10 to 40wt% condition, and mixed with 95 to 100 mol% of aromatic diamine components and 100 to 105 mol% of acid dianhydride compounds 10 to 70 °C temperature conditions It is preferable to carry out for 24 to 48 hours. At this time, the reaction temperature may be fluid depending on the monomer used.
  • the acid dianhydride compound is preferably added in an excess of -5 to 5 mol% relative to the aromatic diamine component to reach the target viscosity, for reasons of proper viscosity control and storage stability.
  • the polyamic acid solution produced through this reaction preferably has a viscosity in the range of 1,000 to 7,000 cP. If the viscosity is less than 1,000 cP, there is a problem in obtaining an appropriate level of film thickness, and if it is more than 7,000 cP, there is a problem in uniform coating and effective solvent removal, so it is preferable to be within the above range.
  • the transparent polyimide film and a method of manufacturing the same are as follows.
  • the present invention provides a transparent polyimide film prepared by thermal imidating a polyamic acid solution prepared from the polyamic acid composition described above.
  • the polyamic acid solution according to the present invention is viscous, and is prepared by coating and heat-treating the glass substrate in a suitable manner during film production.
  • the coating method may be used without limitation to known conventional methods, for example, spin coating (dip coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating, spray coating (Spray coating) ), But is not limited thereto.
  • the polyamic acid composition of the present invention may be prepared into a polyimide film by heat treatment in a high temperature convection oven.
  • the heat treatment condition is carried out under a nitrogen atmosphere, it is carried out for 30 to 120 minutes at 100 ⁇ 450 °C conditions. More preferably, the film is obtained under temperature and time conditions of 100 ° C / 30min, 220 ° C / 30min, 350 ° C / 30mim. This is because of the imidization which can maximize the removal of the proper solvent and properties.
  • the transparent polyimide film of the present invention is produced using the polyamic acid composition, it exhibits high transparency and has a low coefficient of thermal expansion.
  • the film has a thickness of 10 to 15 ⁇ m, a glass transition temperature of 300 ° C. or higher and a thermal expansion coefficient of 25 ppm / ° C. or lower, preferably 15 ppm / ° C. or lower in the range of 100 to 300 ° C. It is low, the transmittance at a wavelength of 550 nm is high, at least 85%, and the yellowness index (YI) at a wavelength of 550 nm is 7 or less, preferably 5 or less.
  • the polyimide film of this invention can suppress the defect of the element on a board
  • the polyimide film of the present invention has high light transmittance and low yellowness and can be applied to a flexible display.
  • the polyimide film of the present invention can be used in various fields, and particularly displays for OLEDs, displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, flexible OLED surface-illuminated substrates, electronic species that require high transparency and heat resistance It may be provided as a substrate for a flexible display and a protective film such as a substrate material used.
  • a polyamic acid solution was prepared in the same manner as in Comparative Example 1, except that the content ratio of the organic solvent of Table 1 was used.
  • a polyamic acid solution was prepared in the same manner as in Comparative Example 1, except that the content ratio of the organic solvent of Table 1 was used.
  • the polyamic acid solution was coated on a glass plate using a bar coater and then heat treated in a high temperature convection oven.
  • the heat treatment conditions were carried out in a nitrogen atmosphere, and the final film was obtained at the temperature and time conditions of 100 °C / 30 min, 220 °C / 30 min, 350 °C / 30 min.
  • Thus obtained film was measured in the physical properties as shown in Table 2 below the results.
  • the transmittance was measured at 550 nm using a UV-Vis NIR Spectrophotometer, and the phase difference in the plane direction (R ⁇ ) and the phase difference in the thickness direction (R ⁇ ) were measured using a birefringence measuring instrument (Retarder, Otsuka RETs-100). .
  • Haze meter (TOYOSEIKI, HAZE-GARD) was measured using.
  • the glass transition temperature (T ⁇ ) and the coefficient of thermal expansion (CTE) of the film were measured using TMA 402 F3 from Netzsch. Force in the tension mode was set to 0.05 N, and the measured temperature was elevated to 350 ° C. at a rate of 5 / min at 30 ° C., and the coefficient of linear thermal expansion was measured as an average value in the range of 100 to 300 ° C. Pyrolysis temperature (T ⁇ , 1%) was measured using TG 209 F3 by Netzsch.
  • Instron's UTM was used to measure the mechanical properties of the film.
  • the film specimen was measured while pulling the specimen at a speed of 50 mm / min with a width of 10 mm and a gap between the grips set to 100 mm.
  • Example 1 As shown in Table 1, in the case of Example 1 using the organic solvent GBL and NMP in a predetermined ratio of 70:30 (mol%), when the solution is left at room temperature after casting the solution on the glass plate does not have a cloudy phenomenon and stability You can see that.
  • TFMB 24.320g (0.076mole) as a diamine monomer was dissolved in 86.7g of NMP and 117.3g of GBL as an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour. Thereafter, 6FDA 17.110 g (0.038 mole) and PMDA 5.035 g (0.038 mol), which were dianhydride monomers, were added thereto, followed by polymerization for 24 hours, followed by further addition of GBL 85.0 g to prepare a polyamic acid solution (reaction temperature: 30). The solids were then maintained at 15% by weight relative to the total weight of the reaction solvent.) The viscosity was 6,600 cP as measured by a viscometer (Brookfield DV2T, SC4-27).
  • the polyamic acid solution prepared according to the present invention has a film thickness of 10 to 15 ⁇ m, a glass transition temperature of 300 ° C. or more, a thermal expansion coefficient of 25 ppm / ° C. or less, and a wavelength of 550 nm in a range of 100 to 300 ° C. It can be provided as a transparent polyimide film having a transmittance at 85% or more and a yellow index (YI) at 550 nm wavelength of 7 or less.
  • YI yellow index
  • the polyimide film prepared according to the present invention satisfies transparency, resin stability, high heat resistance, low coefficient of thermal expansion and mechanical properties, and thus displays for OLEDs, displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, and flexible OLEDs. It can be widely applied to substrates for flexible displays, such as surface lighting substrates, substrate materials for electronic paper, and protective films.

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Abstract

La présente invention concerne une composition de résine précurseur d'acide polyamique transparente qui ne provoque pas de phénomène de trouble blanc pendant la coulée en solution tout en ayant d'excellentes propriétés mécaniques, une résistance à la chaleur élevée et un faible coefficient de dilatation thermique par optimisation de diamine aromatique et de dianhydride d'acide pour améliorer la résistance à la chaleur et les propriétés mécaniques, et un solvant organique dans lequel un phénomène de turbidité blanche ne se produit pas ; l'invention concerne aussi un procédé de production d'un film de polyimide utilisant la composition ; et un film de polyimide ainsi obtenu.
PCT/KR2016/010435 2016-08-23 2016-09-20 Composition de résine précurseur de polyimide, transparente, plus stable et plus résistance à la chaleur, procédé de production d'un film de polyimide utilisant la composition, et film de polyimide ainsi obtenu WO2018038309A1 (fr)

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CN201680088588.8A CN109689732B (zh) 2016-08-23 2016-09-20 聚酰亚胺前体树脂组合物、由该组合物制造聚酰亚胺膜的方法及由该方法制造的聚酰亚胺膜

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CN110922753A (zh) * 2018-09-20 2020-03-27 住友化学株式会社 光学膜形成用组合物
WO2020262450A1 (fr) * 2019-06-27 2020-12-30 日鉄ケミカル＆マテリアル株式会社 Film de résine, stratifié plaqué de métal et procédé pour sa production
CN112300388A (zh) * 2020-11-03 2021-02-02 深圳市道尔顿电子材料有限公司 聚酰亚胺前驱体溶液及其制备方法、聚酰亚胺及其制备方法、聚酰亚胺薄膜及其制备方法
CN113150548A (zh) * 2021-06-02 2021-07-23 中国地质大学（北京） 一种含酚酞基阻燃透明型聚酰亚胺薄膜及其制备方法和应用

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