WO2017111299A1 - Composition d'acide polyamique ayant une force adhésive supérieure et film de polyimide comprenant la composition - Google Patents

Composition d'acide polyamique ayant une force adhésive supérieure et film de polyimide comprenant la composition Download PDF

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WO2017111299A1
WO2017111299A1 PCT/KR2016/012828 KR2016012828W WO2017111299A1 WO 2017111299 A1 WO2017111299 A1 WO 2017111299A1 KR 2016012828 W KR2016012828 W KR 2016012828W WO 2017111299 A1 WO2017111299 A1 WO 2017111299A1
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diamine
polyamic acid
compound
reactor
added
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PCT/KR2016/012828
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English (en)
Korean (ko)
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오현석
김동연
김선영
안경일
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주식회사 두산
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Priority to JP2018533263A priority Critical patent/JP2019506478A/ja
Priority to CN201680075840.1A priority patent/CN108473677B/zh
Publication of WO2017111299A1 publication Critical patent/WO2017111299A1/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
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the present invention relates to a polyamic acid composition including a diamine monomer having a specific chemical structure and improved adhesion properties on a glass substrate, and a colorless transparent polyimide film prepared from the polyamic acid composition and applicable to a flexible display substrate or a protective film.
  • a flat panel display such as a plasma display, a liquid crystal display, an organic light emitting display, and the like use a glass substrate.
  • FPD flat panel display
  • a plasma display such as a plasma display, a liquid crystal display, an organic light emitting display, and the like use a glass substrate.
  • transparent plastic substrates are being investigated for glass substrate replacement.
  • a substrate using a polyethylene terephthalate (PET) film or a polyether sulfone (PES) film has been developed.
  • PET polyethylene terephthalate
  • PES polyether sulfone
  • the transparent plastic substrate using a polymer resin such as PET or PES has a good ductility compared to the glass substrate, but has a low heat resistance because the glass transition temperature (Tg) is low.
  • Tg glass transition temperature
  • CTE coefficient of thermal expansion
  • polyimide (PI) has excellent mechanical, chemical, and electrical properties in addition to excellent heat resistance properties, it has recently been extended to coating materials, molding materials, and composite materials including PI. Since the polyimide resin is colored in brown or yellow under the influence of a charge transfer complex (CTC) and has low transmittance in the visible light region, there is a limit in displaying high transparency like a glass substrate. Therefore, a lot of research is in progress to solve this problem.
  • a 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 produce a polyamic acid derivative, followed by ring closure dehydration at high temperature for imidization.
  • aromatic dianhydride component for producing the polyimide resin
  • pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) is used
  • the aromatic diamine component is 2, 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFDB), oxydianiline (ODA), p-phenylene diamine (p-PDA), m-methylene diamine (m-MDA) , Methylene diamine (MDA), bisaminophenylhexafluoropropane (HFDA) and the like are used.
  • PMDA pyromellitic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • TFDB 2, 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl
  • ODA oxydianiline
  • p-PDA p-phenylene diamine
  • the film is separated from the glass substrate during the TFT process.
  • the relationship between the optical properties and the thermal properties is in a trade-off relationship, it is necessary to develop a compound of a component suitable for each property, that is, a monomer for transparent PI, and thus exhibit high optical properties.
  • development of a polyamic acid composition and a polyimide film for a transparent plastic substrate having excellent adhesion to a glass substrate and having high thermal characteristics is required.
  • the present invention has been focused on the fact that the introduction of a monomer having a specific structure and a substituent improves optical properties, adhesion properties with a glass substrate, heat resistance properties, and coefficient of thermal expansion.
  • the present invention it is determined that it is effective to introduce a diamine-based monomer having a specific chemical structure and a substituent in order to obtain a polyimide resin having high transparency, high adhesion and excellent thermal properties, and to determine the content of the diamine monomer.
  • a diamine-based monomer having a specific chemical structure and a substituent in order to obtain a polyimide resin having high transparency, high adhesion and excellent thermal properties, and to determine the content of the diamine monomer.
  • the present invention is a transparent polyamic acid composition applicable to a plastic transparent substrate, a TFT substrate, a flexible printed circuit board, a flexible OLED surface lighting substrate, an electronic paper substrate material for LCD and OLED flexible display And polyimide films.
  • the present invention (a) a diamine containing a compound represented by the formula (1); (b) acid dianhydrides; And (c) an organic solvent, wherein the compound represented by Chemical Formula 1 provides a polyamic acid composition that is included in the range of 10 to 80 mol% based on 100 mol% of the total diamine.
  • A is a single bond, or , ,
  • X 1 and X 2 are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C 1 ⁇ C 6 alkyl, and C 1 ⁇ in which one or more hydrogen substituted with halogen atoms C 6, the Provided that at least one of X 1 and X 2 is a C 1 to C 6 alkyl group substituted with halogen or a halogen atom,
  • a plurality of Y's are hydrogen bondable functional groups, each independently a hydroxyl group,
  • n is an integer of 1 or 2.
  • the X 1 and X 2 may be each independently selected from F or CF 3 electron-withdrawing group (EWG).
  • the diamine is fluorinated first diamine; It may further comprise one or more selected from the group consisting of sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and alicyclic fifth diamine.
  • the content of the fluorinated first diamine, sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and cycloaliphatic fifth diamine are each 20 to 90 mol based on 100 mol% total diamine May be%.
  • the acid dianhydride may include one or more selected from the group consisting of fluorinated aromatic first acid dianhydride, alicyclic diacid dianhydride and non-fluorinated aromatic tertiary dianhydride.
  • the content of at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride may be 10 to 100 mol% based on 100 mol% of the total acid dianhydride.
  • the ratio (a / b) of the number of moles of the diamine (a) and the acid dianhydride (b) may range from 0.7 to 1.3.
  • the present invention also provides a transparent polyimide film prepared by imidizing the above-described polyamic acid composition.
  • the transparent polyimide film may satisfy the physical property conditions of the following (i) to (vi), more specifically (i) the adhesive strength on the glass substrate according to ASTM D 3359 standard is 2B or more, (ii) the yellowness according to ASTM E 313-73 standard is 7 or less (based on the film thickness of 10 ⁇ m), (iii) the light transmittance at the wavelength of 550 nm is 89% or more, and (iv) the glass transition temperature (T g ) Is in the range of 330 to 400 ° C., (v) the coefficient of thermal expansion (CTE) by TMA measurement is in the range of 10 to 60 ppm / ° C., and (vi) the phase difference R th in the thickness direction calculated by the following formula is 10 ⁇ m in thickness. It may be from 80nm to 400nm as a reference.
  • n z is the refractive index in the thickness direction of the polyimide resin film measured with light having a wavelength of 550 nm; d is the thickness of the polyimide film.
  • the transparent imide film may be used as a substrate or a protective film for a flexible display.
  • a polyamic acid composition having excellent optical properties, thermal properties and adhesive strength with a glass substrate by adopting a diamine monomer having a specific structure and a substituent and adjusting the content thereof in a specific range.
  • the present invention provides a flexible display substrate having excellent physical properties and product reliability by imidating the polyamic acid composition having excellent optical properties, thermal properties and adhesion properties with a glass substrate and applying the same as a transparent substrate. Can be.
  • FIG. 1 is a photograph showing an adhesion evaluation result 5B of the polyimide film prepared in Example 1.
  • the transparent polyamic acid composition of the present invention is for producing a transparent polyimide film, characterized in that it comprises a compound represented by the formula (1) as a diamine (diamine) component.
  • the polyamic acid composition comprises (a) a diamine containing the compound of Formula 1; (b) acid dianhydrides; And (c) an organic solvent.
  • the diamine (a) monomer used for manufacture of the transparent polyamic acid of this invention contains the compound represented by following formula (1).
  • A is a single bond, or , ,
  • X 1 and X 2 are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C 1 ⁇ C 6 alkyl, and C 1 ⁇ in which one or more hydrogen substituted with halogen atoms C 6, the At least one of X 1 and X 2 is a C 1 to C 6 alkyl group substituted with halogen or a halogen atom,
  • a plurality of Y's are hydrogen bondable functional groups, each independently a hydroxyl group,
  • n is an integer of 1 or 2.
  • the compound of the formula (1) having at least one or more functional groups capable of forming a hydrogen bond with the glass substrate, such as a hydroxy group (-OH) is introduced into the diamine ( It is used as a diamine component.
  • the adhesion property of the polyimide film may be significantly improved through hydrogen bonding with the glass substrate.
  • the polyimide film is dark brown rather than colorless because of the Charge Transfer Complex (CTC) of ⁇ electrons present in the imide chain. Since -F, -CF 3 and the like introduced in Chemical Formula 1 are strong electron withdrawing groups, the CT-Complex does not occur through the movement between ⁇ electrons, thereby exhibiting high transparency of polyimide.
  • EWG electron-withdrawing group
  • CTC Charge Transfer Complex
  • X 1 and X 2 may be a conventional electron withdrawing group (EWG) known in the art, each independently fluorine (F) or CF 3 It is preferred.
  • EWG electron withdrawing group
  • Y may be used without limitation the conventional hydrogen bond functional groups known in the art.
  • the plurality of Y is the same or different from each other, each independently preferably a hydroxy group (-OH), more preferably two hydroxy groups are introduced.
  • A is , , or Is preferably.
  • the compound represented by Formula 1 according to the present invention may be more specific to any one of a compound group consisting of Compound 1 to Compound 12, but is not particularly limited thereto.
  • the amount of the diamine monomer represented by Chemical Formula 1 is not particularly limited, and may be, for example, in the range of 10 to 80 mol% based on 100 mol% of the total acid dianhydride, preferably 20 to 80 mol%. It can be a range.
  • the diamine compound mixed with the compound of Formula 1 may be used without particular limitation as long as the compound has a diamine structure in the molecule.
  • An example is an aromatic, alicyclic, or aliphatic compound having a diamine structure.
  • Diamines usable in the present invention include optical properties such as high transmittance, low Y.I, low haze, and the like; Thermal properties such as high glass transition temperature (High Tg) and low coefficient of thermal expansion (Low CTE); Considering the mechanical properties such as high modulus and high surface hardness, the linear structure with fluorinated substituents or sulfone based, hydroxy based, ether based, etc. Appropriate combinations of structures, including Accordingly, in the present invention, as the diamine compound, fluorinated aromatic first diamine, sulphonated second diamine, hydroxy third diamine, ether fourth diamine and alicyclic fifth diamine each having a fluorine substituent introduced therein alone. It may be used or in a form in which two or more thereof are mixed.
  • Non-limiting examples of diamine monomer (a) that can be used include oxydianiline (ODA), 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB ), 2,2'-bis (trifluoromethyl) -4,3'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,3'-Diaminobiphenyl), 2,2'-bis ( Trifluoromethyl) -5,5'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -5,5'-Diaminobiphenyl), 2,2'-bis (trifluoromethyl) -4,4 '-Diaminophenyl ether (2,2'-Bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 6-FODA), bis aminohydroxy phenyl hexafluoropropane (DBOH), bis amino
  • the fluorinated first diamine is a 2,2'-bis (trifluoromethyl) -4,4'-dia which may lead to linear polymerisation.
  • Preference is given to using minobiphenyl (2,2'-TFDB).
  • the hydroxy tertiary diamine is 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane (2,2-Bis (3-amino-4-methylphenyl) -hexafluoropropane, BIS-AT- AF) is preferred.
  • BIS-AT- AF 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane
  • BIS-AT- AF 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane
  • the content of the fluorinated first diamine, sulfonated second diamine, hydroxy third diamine, ether fourth diamine, alicyclic fifth diamine, and the like are not particularly limited. It may be 20 to 90 mol% based on 100 mol% total diamine, preferably in the range of 20 to 80 mol%.
  • Acid dianhydride (b) monomers used in the preparation of the transparent polyamic acid of the present invention can be used without limitation, acid dianhydrides such as fluorinated, non-fluorinated, alicyclic and the like known in the art having an acid dianhydride structure in the molecule.
  • acid dianhydrides such as fluorinated, non-fluorinated, alicyclic and the like known in the art having an acid dianhydride structure in the molecule.
  • the fluorinated first acid dianhydride, alicyclic diacid dianhydride, and non-fluorinated triacid dianhydride may be used alone or in a mixed form of two or more thereof.
  • the fluorinated first acid dianhydride monomer is not particularly limited as long as it is an aromatic acid dianhydride into which a fluorine substituent is introduced.
  • fluorinated first dianhydrides examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydrid, 6-FDA), 4- (trifluoromethyl) pyromellitic dianhydride (4- (trifluoromethyl) pyromellitic dianhydride, 4-TFPMDA). These may be used alone or in combination of two or more thereof.
  • 6-FDA is a very suitable compound for clearing due to its very high property of limiting the formation of change transfer complexes (CTCs) between and within molecular chains.
  • the alicyclic diacid dianhydride that can be used in the present invention is not particularly limited as long as it is a compound having an acid dianhydride structure having an alicyclic ring instead of an aromatic ring in the compound.
  • Examples of the alicyclic second dianhydride usable in the present invention include cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA) , Bicyclo [2,2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BCDA), or mixtures of one or more thereof, but are not particularly limited thereto. .
  • CBDA cyclobutane tetracarboxylic dianhydride
  • CPDA 1,2,3,4-cyclopentane tetracarboxylic dianhydride
  • BCDA Bicyclo [2,2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride
  • the non-fluorinated tertiary acid dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic acid dianhydride to which a fluorine substituent is not introduced.
  • Non-limiting examples of non-fluorinated tertiary dianhydride monomers that can be used include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (3, 3 ′, 4,4′-Biphenyl tetracarboxylic acid dianhydride (BPDA), benzophenone tetracarboxylic dianhydride (BTDA), oxydiphthalic dianhydride (ODPA), and the like. These may be used alone or in combination of two or more thereof.
  • PMDA pyromellitic dianhydride
  • BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • BTDA benzophenone tetracarboxylic dianhydride
  • ODPA oxydiphthalic dianhydride
  • the content of at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride is not particularly limited. In one example, they may each range from 10 to 100 mole percent, based on 100 mole percent total acid dianhydride, preferably in the range from 10 to 90 mole percent, more preferably 20 to 80 mole percent.
  • the fluorinated first acid dianhydride and the non-fluorinated third acid dianhydride are mixed as the acid dianhydride (b)
  • their use ratio may be 40 to 90:10 to 60 mol% ratio.
  • the ratio thereof when the fluorinated first acid dianhydride and alicyclic second acid dianhydride are mixed as the acid dianhydride (b), the ratio thereof may be 30 to 80:20 to 70 mol%. have.
  • the ratio (a / b) of the number of moles of the diamine component (a) to the number of moles of the dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2. And more preferably 0.9 to 1.1.
  • the solvent (c) for solution polymerization of the aforementioned monomers included in the polyamic acid composition of the present invention may use any organic solvent known in the art without limitation.
  • solvents examples include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • acetone diethyl
  • polar solvents selected from acetate, and dimethyl phthalate (DMP) can be used.
  • a low boiling point solution such as tetrahydrofuran (THF), chloroform or a solvent such as ⁇ -butyrolactone may be used.
  • the content of the solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the solvent for polymerization (the first solvent) is preferably 50 to 95% by weight based on the total weight of the polyamic acid composition. More preferably 70 to 90% by weight.
  • the acid dianhydride and the diamine described above can be added to an organic solvent and reacted to produce a transparent polyamic acid composition.
  • the diamine of Formula 1 at least one or more diamine components of the first to fifth diamine, and acid dianhydride, diamine (a) and acid dianhydride (b) to improve the glass transition temperature and yellowness Transparent polyamic acid compositions can be formed with an equivalent ratio of approximately 1: 1.
  • the composition of the polyamic acid composition is not particularly limited, and for example, based on 100% by weight of the total weight of the polyamic acid composition, 2.5 to 25.0% by weight of the acid dianhydride, 2.5 to 25.0% by weight of diamine, and the remaining amount to satisfy 100% by weight of the composition It may be configured to include an organic solvent of.
  • the content of the organic solvent may be 70 to 90% by weight.
  • the acid dianhydride may be in the range of 30 to 70% by weight, diamine 30 to 70% by weight, but is not particularly limited thereto.
  • Such transparent polyamic acid compositions of the present invention may have a viscosity in the range of about 1,000 to 200,000 cps, preferably about 5,000 to 50,000 cps.
  • the viscosity of the polyamic acid solution falls within the above-described range, the thickness of the polyamic acid solution may be easily adjusted when the solution is coated, and the coating surface may be uniformly exhibited.
  • the polyamic acid solution of the present invention may contain a small amount of additives such as plasticizers, antioxidants, flame retardants, dispersants, viscosity regulators, leveling agents and the like within the range that does not significantly impair the object and effect of the present invention if necessary. .
  • the present invention provides a polyimide film prepared by imidizing and heat treating the polyamic acid solution described above at high temperature.
  • the polyimide resin is a polymer material containing an imide ring, and is excellent in heat resistance, chemical resistance, abrasion resistance, and electrical properties.
  • the polyimide resin may be in the form of a random copolymer or a block copolymer.
  • a polyimide resin film in order to apply a polyimide resin film to a flexible display, it should basically have characteristics such as high transparency, low thermal expansion coefficient, and high glass transition temperature. More specifically, a light transmittance of 550 nm is 89% or more at a film thickness of 10 ⁇ m, a yellowness value of 550 nm is 7 or less, a glass transition temperature (Tg) of 300 ° C. or more is required. In addition, in order to secure reliability during the TFT deposition process, an adhesive force is required in which the polyimide on the support (glass substrate) does not peel off from the glass substrate during the process.
  • the polyimide film of the present invention prepared by imidizing the polyamic acid composition described above has high transparency and low yellowness, high adhesion to a glass substrate, low coefficient of thermal expansion, and high glass transition temperature (Tg). More specifically, the polyimide film has a physical property of the following (i) to (vi), for example, (i) the adhesive strength on the glass substrate according to the ASTM D 3359 standard 2B or more, (ii) ASTM E 313-73 standard Yellowness by 7 or less (based on 10 ⁇ m), (iii) light transmittance at wavelength 550 nm is 89% or more, (iv) glass transition temperature (T g ) is in the range of 330 to 400 °C, (v) The coefficient of thermal expansion (CTE) by TMA measurement is in the range of 10 to 60 ppm / ° C., and (vi) the phase difference R th in the thickness direction calculated by the following formula may be 80 nm to 400 nm based on a thickness of 10
  • n z is the refractive index in the thickness direction of the polyimide resin film measured with light having a wavelength of 550 nm; d is the thickness of the polyimide film.
  • the polyimide film according to the present invention may be prepared by exothermic solution polymerization of a transparent polyamic acid solution according to conventional methods known in the art.
  • the transparent polyamic acid composition may be prepared by coating (casting) the support and inducing an imide cyclization reaction (Imidazation) for 0.5 to 8 hours while gradually raising the temperature in the range of 30 to 350 ° C. It is preferable to react in inert atmosphere, such as argon and nitrogen at this time.
  • the coating method may be used without limitation conventional methods known in the art, for example, spin coating (dip coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating (Slot die coating) ) And at least one method selected from the group consisting of spray coating.
  • the colorless transparent polyimide layer may be coated at least once with a transparent polyamic acid composition such that the thickness of the colorless and transparent polyimide layer is several hundreds of micrometers.
  • the imidization method applied to the step of casting and imidizing the polymerized polyamic acid on a support is thermal imidization, chemical imidization, or thermal imidization and chemical
  • the imidization method can be used in combination.
  • the thermal imidization method is a method of casting a polyamic acid solution on a support and heating it for 1 to 10 hours while gradually raising the temperature in a temperature range of 30 to 400 ° C. to obtain a polyimide film.
  • the chemical imidization method is a method of introducing an imidization catalyst represented by a dehydrating agent represented by an acid anhydride such as acetic anhydride and amines such as isoquinoline, ⁇ -picolin and pyridine into a polyamic acid solution.
  • an imidization catalyst represented by a dehydrating agent represented by an acid anhydride such as acetic anhydride and amines such as isoquinoline, ⁇ -picolin and pyridine
  • the heating conditions of the polyamic acid solution may vary depending on the kind of the polyamic acid solution, the thickness of the polyimide film to be produced, and the like.
  • the polyimide film can be obtained after partially curing and drying by heating at 150 to 250 ° C. to activate the dehydrating agent and the imidization catalyst.
  • the thickness of the polyimide film thus formed is not particularly limited and may be appropriately adjusted according to the field to be applied. For example, it may be in the range of 10 to 150 ⁇ m, preferably in the range of 10 to 80 ⁇ m.
  • the transparent polyimide film manufactured as described above may be used in various fields, and particularly, displays for organic EL devices (OLEDs), displays for liquid crystal devices, TFT substrates, flexible printed circuit boards that require high transparency and heat resistance.
  • OLEDs organic EL devices
  • the present invention can be used as a flexible display substrate and / or a protective film such as a flexible OLED surface-illuminated substrate and a substrate material for electronic paper.
  • a 500 mL three-neck round bottom flask was used as the reactor, and 145.9 g of N, N -dimethylacetamide (hereinafter referred to as DMAc) was charged to the reactor while passing nitrogen at a flow rate of 50 mL / min, and the temperature of the reactor was increased to 40 ° C. After raising the temperature, Compound 2 and 4-aminophenylsulfone (hereinafter referred to as 4,4'-DDS) were added to 20.0 g (41.1 wt%) and 3.53 g (7.3 wt%), respectively, and stirred for 1 hour, thereby stirring Compound 2 and 4,4'-DDS was completely dissolved.
  • DMAc N, N -dimethylacetamide
  • Example 1 190.2 g of DMAc was charged to a reactor, and the temperature of the reactor was raised to 40 ° C., followed by compound 7 and 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane (hereinafter referred to as BIS-AT- 20.0 g (31.5 wt%) and 6.5 g (10.2 wt%), respectively, were added and stirred for 1 hour to completely dissolve Compound 7 and BIS-AT-AF. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 31.7 g (49.9 wt%) of 6FDA was added, followed by stirring for 2 hours.
  • BIS-AT- 20.0 g 31.5 wt%)
  • 6.5 g (10.2 wt%)
  • BPDA 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 127.3 g of DMAc was charged to a reactor, and the temperature of the reactor was raised to 40 ° C., followed by 20.0 g of Compound 11 and 2,2′-bis (trifluoromethyl) benzidine (hereinafter referred to as TFDB). 47.1 wt%), 4.4 g (10.3 wt%) were added and stirred for 1 hour to completely dissolve Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 14.1 g (33.2 wt) of BPDA was added, followed by stirring for 2 hours.
  • TFDB 2,2′-bis (trifluoromethyl) benzidine
  • CBDA cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 147.1 g of DMAc was charged into a reactor, and the temperature of the reactor was raised to 40 ° C., followed by adding 20.0 g (40.7 wt%) and 4.6 g (9.4 wt%) of Compound 2 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 2 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 18.9 g (38.5 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, after adding 5.6 g (11.4 wt%) of CBDA, 49.0 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 37,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 169.9 g of DMAc was charged into the reactor, and the temperature of the reactor was increased to 40 ° C., followed by 18.0 g (31.8 wt%) and 8.5 g (15 wt%) of Compound 2 and 4,4′-DDS, respectively. Was added and stirred for 1 hour to completely dissolve compound 2 and 4,4'-DDS. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 15.1 g (26.7 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, after adding 15.0 g (26.5 wt%) of BPDA, 56.6 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 26,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 166.8 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 16.0 g (28.8 wt%) and 13.8 g (24.8 wt%) of Compound 7 and BIS-AT-AF were added. Addition and stirring for 1 hour completely dissolved Compound 7 and BIS-AT-AF. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 19.6 g (35.3 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, 6.2 g (11.1 wt%) of PMDA was added, and then 55.6 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 25,000 cP at 20% solids was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 159.1 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 21.0 g (39.6 wt%) and 12.2 g (23 wt%) were added to Compound 11 and TFDB, respectively, and stirred for 1 hour. Compound 11 and TFDB were dissolved completely. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 10.4 g (19.6 wt%) of PMDA was added, followed by stirring for 2 hours. Finally, after adding 9.4 g (17.7 wt%) of CBDA, 53.0 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 31,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 157.2 g of DMAc was charged into a reactor, and the temperature of the reactor was raised to 40 ° C., and then 15.0 g (28.6 wt%) and 9.1 g (17.4 wt%) were added to Compound 2 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 2 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 25.2 g (48.1 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, after adding 3.1 g (5.9 wt%) of PMDA, 52.4 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 32,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 155.8 g of DMAc was charged into the reactor, and the temperature of the reactor was increased to 40 ° C., followed by 12.5 g (24.1 wt%) and 13.2 g (25.4 wt%) of Compound 2 and 4,4′-DDS, respectively. Was added and stirred for 1 hour to completely dissolve Compound 2 and 4,4'-DDS. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 15.8 g (30.4 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, after adding 10.4 g (20 wt%) of CBDA, 51.9 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 24,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 161.5 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 10.5 g (19.5 wt%) and 20.4 g (37.8 wt%) of Compound 7 and BIS-AT-AF were added. Addition and stirring for 1 hour completely dissolved Compound 7 and BIS-AT-AF. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 13.8 g (25.6 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 9.2 g (17.1 wt%) of CBDA, 53.8 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 12,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 153.7 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 10.5 g (20.5 wt%) and 13.8 g (26.9 wt%) were added to Compound 11 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 22.3 g (43.5 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, 4.7 g (9.2 wt%) of PMDA was added, and then 51.2 g of DMAc was added thereto and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 19,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 155.5 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 12.5 g (24.1 wt%) and 16.3 g (31.4 wt%) were added to Compound 5 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 5 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 17.5 g (33.7 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 5.6 g (10.8 wt%) of PMDA, 51.8 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 37,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 155.9 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., and then 10.0 g (19.3 wt%) and 13.6 g (26.2 wt%) were added to Compound 2 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 2 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 25.2 g (48.6 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 3.1 g (6 wt%) of PMDA, 52.0 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 36,000 cP at 20% solids was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 160.8 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by 15.0 g (27.9 wt%) and 15.9 g (29.6 wt%) of Compound 2 and 4,4′-DDS, respectively. Was added and stirred for 1 hour to completely dissolve Compound 2 and 4,4'-DDS. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 18.6 g (34.6 wt%) of PMDA was added, followed by stirring for 2 hours. Finally, after adding 4.2 g (7.8 wt%) of 6FDA, 53.6 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 11,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 161.1 g of DMAc was charged into a reactor, and the temperature of the reactor was raised to 40 ° C., and then 5.0 g (9.3 wt%) and 25.9 g (48.2 wt%) of Compound 7 and BIS-AT-AF were added. Addition and stirring for 1 hour completely dissolved Compound 7 and BIS-AT-AF. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 13.1 g (24.4 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 9.7 g (18.1 wt%) of PMDA, 53.7 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 13,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 165.7 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by adding 6.0 g (10.9 wt%) and 21.0 g (38 wt%) of Compound 11 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 21.8 g (39.5 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, after adding 6.4 g (11.6 wt%) of CBDA, 55.2 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 17,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 153.3 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 5.5 g (10.8 wt%) and 19.1 g (37.4 wt%) of Compound 5 and TFDB were added thereto for 1 hour. Stirring completely dissolved Compound 5 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 13.3 g (26 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 13.2 g (25.8 wt%) of BPDA, 51.1 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 23,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 154.5 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., followed by adding 5.0 g (9.7 wt%) and 18.2 g (35.3 wt%) of Compound 2 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 2 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 25.2 g (48.9 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 3.1 g (6 wt%) of PMDA, 51.5 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 28,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 In Example 1, 157.8 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., followed by 3.4 g (6.5 wt%) and 3.5 g (6.7 g) of Compound 2, 11 and 4,4′-DDS, respectively. wt%), and 19.2 g (36.5 wt%) were added and stirred for 1 hour to completely dissolve Compound 2, Compound 11 and 4,4'-DDS. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 22.7 g (43.2 wt%) of BPDA was added, followed by stirring for 2 hours.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 160.9 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., followed by compound 2, compound 7, and BIS-AT-AF, respectively, 3.1 g (5.8 wt%) and 2.5 g (4.7 wt%). %), And 25.5 g (47.6 wt%) were added and stirred for 1 hour to completely dissolve Compound 2, Compound 7 and BIS-AT-AF. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 12.9 g (24.1 wt%) of BPDA was added, followed by stirring for 2 hours.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 158.3 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., followed by 2.4 g (4.6 wt%), 3.1 g (5.9 wt%) of Compound 7, Compound 11, and TFDB, respectively. 21.9 g (41.6 wt%) was added and stirred for 1 hour to completely dissolve Compound 7, Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 15.2 g (28.8 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 10.1 g (19.2 wt%) of CBDA, 52.8 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 11,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 157.2 g of DMAc was charged to a reactor, and the temperature of the reactor was raised to 40 ° C., followed by 6.5 g (12.4 wt%), 6.8 g (13 wt%) of Compound 2, 5, and TFDB, respectively. 11.8 g (22.5 wt%) was added and stirred for 1 hour to completely dissolve Compound 2, Compound 5 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 23.0 g (43.9 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, 4.3 g (8.2 wt%) of CBDA was added, and then 52.4 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 13,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • Example 1 160.0 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by compound 2.7, compound 7, and TFDB, respectively, 2.7 g (5.1 wt%), 2.1 g (3.9 wt%), and 19.6 g (36.8 wt%) was added and stirred for 1 hour to completely dissolve Compound 2, Compound 7 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 23.8 g (44.7 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 5.0 g (9.4 wt%) of PMDA, 53.3 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 16,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 159.9 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by 3.8 g (7.1 wt%) and 24.1 g (45.2 wt%) of Compound 2 and 4,4′-DDS, respectively. Was added and stirred for 1 hour to completely dissolve Compound 2 and 4,4'-DDS. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 12.7 g (23.8 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 12.7 g (23.8 wt%) of CBDA, 53.3 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 14,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 161.5 g of DMAc was charged into a reactor, and the temperature of the reactor was raised to 40 ° C., and then 2.4 g (4.5 wt%) and 27.9 g (51.8 wt%) of Compound 7 and BIS-AT-AF were respectively added. Addition and stirring for 1 hour completely dissolved Compound 7 and BIS-AT-AF. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 20.2 g (37.5 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, 3.4 g (6.3 wt%) of CBDA was added, and then 53.8 g of DMAc was added thereto and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 9,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 159.3 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 2.8 g (5.3 wt%) and 22.0 g (41.5 wt%) were added to Compound 11 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 23.7 g (44.7 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 4.5 g (8.5 wt%) of CBDA, 53.1 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 17,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 154.3 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by addition of 2.7 g (5.3 wt%) and 21.1 g (41.1 wt%) of Compound 5 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 5 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 22.8 g (44.4 wt%) of 6FDA was added thereto, followed by stirring for 2 hours. Finally, after adding 4.8 g (9.3 wt%) of PMDA, 51.4 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 15,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 157.3 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 2.5 g (4.8 wt%) and 20.5 g (39.1 wt%) were added to Compound 2 and TFDB, respectively, for 1 hour. Stirring completely dissolved Compound 2 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 25.2 g (48.1 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, 4.2 g (8 wt%) of BPDA was added, and then 52.4 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 31,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 159.6 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., followed by 5.1 g (9.6 wt%), 5.3 g (10.0 wt%) of Compound 2, 11 and TFDB, respectively. 13.9 g (26.1 wt%) was added and stirred for 1 hour to completely dissolve Compound 2, Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 25.7 g (48.3 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, 3.2 g (6.0 wt%) of PMDA was added, and then 53.2 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 15,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 157.9 g of DMAc was charged to a reactor, and the temperature of the reactor was raised to 40 ° C., followed by 5.3 g (10.1 wt%), 6.9 g (13.1 wt%), of Compound 7, Compound 11, and TFDB, respectively. 18.2 g (34.6 wt%) was added and stirred for 1 hour to completely dissolve Compound 7, Compound 11 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., after which 11.1 g (21.1 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 11.1 g (21.1 wt%) of CBDA, 52.6 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 16,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 155.7 g of DMAc was charged to a reactor, and the temperature of the reactor was raised to 40 ° C., followed by 5.3 g (10.2 wt%), 5.5 g (10.6 wt%) of Compound 2, 5, and TFDB, respectively. 14.5 g (27.9 wt%) was added and stirred for 1 hour to completely dissolve Compound 2, Compound 5 and TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 20.1 g (38.7 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 6.6 g (12.7 wt%) of PMDA, 51.9 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 8,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 158.7 g of DMAc was charged to the reactor, and the temperature of the reactor was raised to 40 ° C., and then 26.0 g (49.1 wt%) of TFDB was added and stirred for 1 hour to completely dissolve the TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 18.0 g (34 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 8.9 g (16.8 wt%) of PMDA, 52.9 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 110,000 cP at 20% solids was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 158.9 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 30.0 g (56.6 wt%) of TFDB was added and stirred for 1 hour to completely dissolve the TFDB. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 13.8 g (26 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 9.2 g (17.4 wt%) of CBDA, 53.0 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 190,000 cP at 20% solids was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 161.0 g of DMAc was charged to a reactor, and the temperature of the reactor was increased to 40 ° C., followed by adding 23.0 g (42.8 wt%) of 4,4′-DDS and stirring for 1 hour to 4,4′-DDS. Completely dissolved. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 20.6 g (38.4 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 10.1 g (18.8 wt%) of PMDA, 53.7 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 74,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 158.0 g of DMAc was charged into a reactor, and the temperature of the reactor was increased to 40 ° C., followed by adding 26.5 g (50.3 wt%) of 4,4′-DDS and stirring for 1 hour to 4,4′-DDS. Completely dissolved. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 15.7 g (29.8 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, 10.5 g (19.9 wt%) of CBDA was added, and then 52.7 g of DMAc was added thereto and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 81,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 157.9 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by adding 27.5 g (52.2 wt%) of BIS-AT-AF and stirring for 1 hour to completely remove BIS-AT-AF. Dissolved. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 16.9 g (32.1 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, 8.3 g (15.7 wt%) of PMDA was added, and then 52.6 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 45,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 161.0 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., and then 32.0 g (59.6 wt%) of BIS-AT-AF was added thereto, followed by stirring for 1 hour to completely remove BIS-AT-AF. Dissolved. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 13.0 g (24.2 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 8.7 g (16.2 wt%) of CBDA, 53.7 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 56,000 cP at 20% solids was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 159.2 g of DMAc was charged to a reactor, and the temperature of the reactor was raised to 40 ° C., followed by 20.0 g (37.7 wt%) of 4,4′-oxydianiline (hereinafter referred to as 4,4′-ODA). Was added and stirred for 1 hour to completely dissolve the 4,4'-ODA. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 22.2 g (41.8 wt%) of 6FDA was added, followed by stirring for 2 hours. Finally, after adding 10.9 g (20.5 wt%) of PMDA, 53.1 g of DMAc was added and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 44,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • 4,4′-ODA 4,4′-oxydianiline
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • Example 1 153.5 g of DMAc was charged into the reactor, and the temperature of the reactor was raised to 40 ° C., followed by adding 23.0 g (44.9 wt%) of 4,4′-ODA and stirring for 1 hour to 4,4′-ODA. Completely dissolved. Thereafter, the temperature of the reactor was cooled and maintained at 30 ° C., and then 16.9 g (33 wt%) of BPDA was added, followed by stirring for 2 hours. Finally, after adding 11.3 g (22.1 wt%) of CBDA, 51.2 g of DMAc was added again and reacted at 30 ° C. for 24 hours. After the reaction was completed, a polyamic acid solution having a viscosity of about 53,000 cP at a solid content of 20% was obtained through a glass filter having a pore size of 1 ⁇ m through a pressure reduction device.
  • a transparent polyimide film was prepared in the same manner as in Example 1 using the prepared polyamic acid solution.
  • compositions of the polyamic acid compositions prepared in Examples 1 to 31 and Comparative Examples 1 to 8 are as shown in Tables 1 and 2 below.
  • Y.I Yellow Index: Yellowness was measured by ASTM E313-73 standard using a UV spectrometer (KONICA MINOLTA CM-3700d).
  • Retardation (R th ) Vertical retardation was measured by measuring at an incidence angle of 45 degrees using RETS-100 (OTSUKA ELECTRONICS). More specifically, the sample size was mounted on the sample holder in a square shape of 5 cm square each, and fixed to 550 nm using a monochromator, the thickness retardation (R th ) was measured at 45 ° incident angle.
  • RETS-100 OTSUKA ELECTRONICS
  • n x is the largest refractive index of the in-plane refractive index
  • n y is the refractive index perpendicular to n x of the in-plane refractive index
  • n z is a vertical refractive index
  • d is the thickness of the polyimide film to 10 ⁇ m The calculated value.
  • Glass transition temperature was measured in the range of 30 ⁇ 400 °C using DMA (TA Instrument, model name: Q800).
  • Adhesion evaluation evaluated using ASTM D 3359.
  • the transparent polyamic acid resin was coated on the glass substrate to a thickness of 15 ⁇ m or less, followed by drying and ring closure reaction.
  • the surface of the formed polyimide thin film was cut with a knife, and the adhesive measuring tape was attached to the cut surface. Then, the peeling state of the polyimide adhesive surface was confirmed.
  • 5B is 0% of the polyimide stripped
  • 4B is 5% or less of the polyimide stripped
  • 3B is 5-15% of the polyimide stripped
  • 2B is the percentage of polyimide stripped 15-35%
  • 1B show the case where the percentage of peeled polyimide is 35-65%
  • 0B is the percentage of the peeled polyimide is more than 65%, respectively.
  • FIG. 1 is a photograph which shows the polyimide film of Example 1 whose adhesive force evaluation result is 5B
  • FIG. 2 is a photograph which shows the polyimide film of Comparative Examples 1-8 whose adhesive force evaluation result is 0B.
  • the polyimide film of the present invention can be seen that the optical, thermal, adhesive properties of the conventional polyimide film is improved, the polyimide film as a colorless transparent flexible display plastic substrate to replace the LCD glass substrate in flat panel display manufacturing It was confirmed that it can be usefully applied.

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Abstract

La présente invention concerne : une composition d'acide polyamique comprenant un composé ayant une structure chimique particulière comme composant diamine; et un polyimide préparé à partir de la composition. La composition d'acide polyamique selon la présente invention manifeste d'excellentes caractéristiques optiques, une grande force d'adhésion à un substrat en verre et des caractéristiques thermiques élevées; le film de polyimide utilisant ladite composition peut donc être utilisé en tant que matériau pour un écran souple.
PCT/KR2016/012828 2015-12-24 2016-11-09 Composition d'acide polyamique ayant une force adhésive supérieure et film de polyimide comprenant la composition WO2017111299A1 (fr)

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CN201680075840.1A CN108473677B (zh) 2015-12-24 2016-11-09 粘接力提高了的聚酰胺酸组合物及包含其的聚酰亚胺膜

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KR20200021411A (ko) * 2018-08-20 2020-02-28 주식회사 엘지화학 폴리이미드 전구체 조성물, 이를 이용하여 제조된 폴리이미드 필름 및 플렉서블 디바이스
JP2020084123A (ja) * 2018-11-30 2020-06-04 株式会社リコー 硬化型組成物、組成物収容容器、２次元又は３次元の像の形成方法及び形成装置、硬化物、構造体、並びに成形加工品
CN114854196A (zh) * 2021-02-05 2022-08-05 株式会社斗山 聚酰亚胺膜
KR20220144510A (ko) 2021-04-20 2022-10-27 에스케이이노베이션 주식회사 신규한 디아자스피로 화합물 및 이의 용도
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KR102551047B1 (ko) 2019-02-01 2023-07-04 주식회사 엘지화학 폴리이미드 필름, 이를 이용한 플렉서블 기판 및 플렉서블 기판을 포함하는 플렉서블 디스플레이
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WO2019073972A1 (fr) * 2017-10-11 2019-04-18 株式会社カネカ Résine de polyimide ainsi que procédé de fabrication de celle-ci, solution de polyimide, et film de polyimide ainsi que procédé de fabrication de celui-ci
JP2019094369A (ja) * 2017-11-17 2019-06-20 大日本印刷株式会社 ポリイミドフィルム、ポリイミド前駆体、ポリイミドフィルムの製造方法、及び表示装置用部材
JP7039947B2 (ja) 2017-11-17 2022-03-23 大日本印刷株式会社 ポリイミドフィルム、ポリイミド前駆体、ポリイミドフィルムの製造方法、及び表示装置用部材
CN109897180A (zh) * 2017-12-08 2019-06-18 株式会社斗山 聚酰胺酸溶液、利用其的透明聚酰亚胺树脂膜及透明基板
CN109897180B (zh) * 2017-12-08 2021-08-03 株式会社斗山 聚酰胺酸溶液、利用其的透明聚酰亚胺树脂膜及透明基板
JPWO2019142866A1 (ja) * 2018-01-17 2020-09-17 旭化成株式会社 ポリイミド前駆体樹脂組成物
WO2019142866A1 (fr) * 2018-01-17 2019-07-25 旭化成株式会社 Composition de résine précurseur de polyimide
KR20200021411A (ko) * 2018-08-20 2020-02-28 주식회사 엘지화학 폴리이미드 전구체 조성물, 이를 이용하여 제조된 폴리이미드 필름 및 플렉서블 디바이스
KR20200021412A (ko) * 2018-08-20 2020-02-28 주식회사 엘지화학 폴리이미드 전구체 조성물, 그 제조 방법 및 이를 이용한 폴리이미드 필름
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WO2020040495A1 (fr) * 2018-08-20 2020-02-27 주식회사 엘지화학 Composition de précurseur de polyimide, son procédé de préparation et film de polyimide l'utilisant
KR102289812B1 (ko) 2018-08-20 2021-08-13 주식회사 엘지화학 폴리이미드 전구체 조성물, 이를 이용하여 제조된 폴리이미드 필름 및 플렉서블 디바이스
JP2020084123A (ja) * 2018-11-30 2020-06-04 株式会社リコー 硬化型組成物、組成物収容容器、２次元又は３次元の像の形成方法及び形成装置、硬化物、構造体、並びに成形加工品
JP7298141B2 (ja) 2018-11-30 2023-06-27 株式会社リコー 硬化型組成物、組成物収容容器、２次元又は３次元の像の形成方法及び形成装置、硬化物、構造体、並びに成形加工品
US11937457B2 (en) 2020-11-23 2024-03-19 Samsung Display Co., Ltd. Display device
CN114854196A (zh) * 2021-02-05 2022-08-05 株式会社斗山 聚酰亚胺膜
CN114854196B (zh) * 2021-02-05 2024-05-28 株式会社斗山 聚酰亚胺膜
KR20220144510A (ko) 2021-04-20 2022-10-27 에스케이이노베이션 주식회사 신규한 디아자스피로 화합물 및 이의 용도

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