WO2020141710A1 - Procédé de préparation d'une composition d'acide polyamique, composition d'acide polyamique, procédé de fabrication d'un film de polyimide l'utilisant et film de polyimide fabriqué par ce procédé de fabrication - Google Patents

Procédé de préparation d'une composition d'acide polyamique, composition d'acide polyamique, procédé de fabrication d'un film de polyimide l'utilisant et film de polyimide fabriqué par ce procédé de fabrication Download PDF

Info

Publication number
WO2020141710A1
WO2020141710A1 PCT/KR2019/014970 KR2019014970W WO2020141710A1 WO 2020141710 A1 WO2020141710 A1 WO 2020141710A1 KR 2019014970 W KR2019014970 W KR 2019014970W WO 2020141710 A1 WO2020141710 A1 WO 2020141710A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamic acid
combinations
dianhydride
solvent
bis
Prior art date
Application number
PCT/KR2019/014970
Other languages
English (en)
Korean (ko)
Inventor
김진모
안용호
김상현
오경옥
최은지
Original Assignee
주식회사 대림코퍼레이션
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 대림코퍼레이션 filed Critical 주식회사 대림코퍼레이션
Priority to JP2021538708A priority Critical patent/JP7317122B2/ja
Priority to CN201980086432.XA priority patent/CN113795536A/zh
Publication of WO2020141710A1 publication Critical patent/WO2020141710A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the present invention relates to a method for preparing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced through the manufacturing method, a diamine compound in which hetero atoms and halogen atoms are introduced more accurately It relates to a method for producing a polyamic acid composition capable of improving optical properties, including an acid dianhydride compound, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced through the method.
  • the substrate material of the flexible display which is drawing attention as a next-generation display device, should be light, unbreakable, bendable, and have no form restrictions due to easy processability.
  • a polymer material that is not only lighter than a glass substrate used as a display substrate material, but also does not break, and is easy to manufacture, so that a thin film-type film can be manufactured, is attracting attention as the most suitable material for the implementation of a flexible display.
  • the difference in refractive index between the light source and the polymer capsule material causes total internal reflection when light passes through the light source and passes through the capsule material at a specific angle of incidence, thereby reducing the light extraction efficiency of the device.
  • excellent optical characteristics and high refractive index are required for application to high-tech optical devices.
  • Conventional polyimide has a low refractive index in the range of about 1.3 to 1.6, and thus, has a problem in that light extraction efficiency is deteriorated.
  • Korean Registered Patent No. 10-1704010 relates to the production of a diamine compound in which a substituent of an aromatic ring containing a hetero atom and a halogen atom is introduced, and a polyamic acid and polyimide produced thereby, having a high refractive index and a low birefringence
  • a transparent film is provided, this also has a limitation in providing a film having excellent heat resistance and shape stability while satisfying a high refractive index of 1.7 or more.
  • the present invention is to solve the above problems, the specific purpose is as follows.
  • a high heat-resistant polyimide having a high refractive index and excellent light and heat resistance through a combination of an acid dianhydride and a diamine compound containing a halogen atom and a hetero atom having a high atomic specific refractive index.
  • a diamine compound an acid dianhydride compound and one selected from the group consisting of combinations thereof, wherein the diamine compound comprises a first diamine monomer; And a second diamine monomer comprising one group selected from the group consisting of chlorine, bromine, iodine, cyanide, trifluoromethyl and combinations thereof.
  • the first diamine monomer may be one selected from the group consisting of fluorinated aromatic diamine monomers, non-fluorinated aromatic diamine monomers, and combinations thereof.
  • the first diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4,4'-oxydianiline (ODA), 4,4'-methylene Dianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA) , p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine (mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4- (4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoro propane (BAFP), 2,2-bis[4-(4-aminophenoxy)phenyl]
  • the second diamine monomer may include at least one of the following Chemical Formula 1 and Chemical Formula 2.
  • R1 includes one selected from the group consisting of chlorine, bromine, iodine, cyanide, trifluoromethyl, and combinations thereof.
  • R2 is chlorine, bromine, iodine, cyanide, trifluoro. Methyl, and combinations thereof.
  • the acid dianhydride compound may be one selected from the group consisting of fluorinated aromatic acid dianhydrides, non-fluorinated aromatic acid dianhydrides, and combinations thereof.
  • the fluorinated aromatic acid dianhydride is 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 6FDA)), 4,4'-(4,4'- Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride)(4,4'-(4,4'-Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride, 6-FDPDA), and combinations thereof. It may include.
  • the non-fluorinated aromatic acid dianhydride is pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (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 ( 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 tetra carboxylic anhydr
  • the second diamine monomer may include 50 to 80 mol% based on the diamine compound.
  • the viscosity of any one of the polyamic acids may be 1,000 to 10,000 cp at 23°C.
  • a polyimide film comprising any one of the polyamic acids.
  • the thickness of the polyimide film is 10 to 15 ⁇ m, a refractive index of 1.7 or more, a yellowness index (YI) of 10 or less, and a coefficient of thermal expansion (CTE) of 15 ppm/° C. or less at 100 to 250° C.
  • the transition temperature may be 300°C or higher and transmittance at a wavelength of 550 nm of 88% or higher.
  • a first diamine monomer comprising;
  • a second diamine monomer comprising one selected from the group consisting of chlorine, bromine, iodine, cyanide, trifluoromethyl and combinations thereof.
  • the solvent is selected from the group consisting of a polar solvent, a low boiling point solvent, a low absorbent solvent, a spreading solvent, and combinations thereof
  • the polar solvent is m-cresol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), diethyl acetate (DEA), 3-methoxy-N,N-dimethyl propanamide (DMPA ), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide (DML) and combinations thereof, wherein the low boiling point solvent is tetrahydrofuran (THF), trichloromethane (Chloroform, TCM) and combinations thereof, and the low absorbent solvent is gamma-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (DMPA), N,N- Di
  • the spreading solvent is ethylene glycol mono.
  • EGBE butyl ether
  • EGME ethylene glycol dimethyl ether
  • EGDE ethylene glycol diethyl ether
  • EGDPE ethylene glycol dipropyl ether
  • ESDBE ethylene glycol dibutyl ether
  • a first low-absorbent solvent mixture gamma-butyrolactone 30-70 mol% and 30-70 mol% of gamma-butyrolactone and 30-70 mol% of N-methyl-2-pyrrolidone as the low absorbent solvent
  • Second low absorbent solvent mixture comprising 30 to 70 mole% of N,N-dimethyl propinoamide, 30 to 70 mole% of gamma-butyrolactone and 30 to 70 mole of 3-methoxy-N,N-dimethyl propanamide %
  • a third low absorbent solvent mixture 100 mol% of N,N-dimethyl propinoamide or 100 mol% of 3-methoxy-N,N-dimethyl propanamide.
  • the solvent is ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof It may include one spreading solvent selected from the group consisting of.
  • the second diamine monomer may include 50 to 80 mol% based on the diamine compound.
  • the mixing may be performed for 30 to 60 minutes at a nitrogen atmosphere and a temperature of 25 to 30°C.
  • one selected from the group consisting of plasticizers, antioxidants, flame retardants, dispersants, viscosity modifiers, leveling agents, and combinations thereof may be further added to the mixture.
  • the polymerization may be performed at a temperature of 10 to 70° C. for 6 to 48 hours.
  • the diamine compound and the acid dianhydride compound constitute a solid content of the polyamic acid solution, and the content of the solid content may be 10 to 40% by weight based on the polyamic acid solution.
  • the acid dianhydride compound may include 100 to 105 molar parts based on the diamine compound.
  • any one of the polyamic acid manufacturing method coating the polyamic acid solution on a substrate to form a transparent coating layer; And heat-treating the transparent coating layer; further includes, the heat treatment is provided at a temperature of 100 to 450 °C for 30 to 120 minutes to provide a method for producing a polyimide film.
  • a polyimide film having a low coefficient of thermal expansion can be produced.
  • Example 2 dissolves TFMB, the first diamine monomer, in 19.532 g (0.061 mole) and 20.949 g (0.061 mole), the compound of Formula 3, in the second diamine monomer in a solvent, and an acid dianhydride compound.
  • Phosphorus BPDA was added in the same manner as in Example 1, except that the viscosity of the finally prepared polyamic acid solution was adjusted to 4,500 cp by adding 37.180 g (0.126 mole).
  • Example 3 dissolved 11.634g (0.036mole) of the first diamine monomer and 29.117g (0.085mole) of the compound of Formula 3, which is the second diamine monomer, in a solvent, and an acid dianhydride compound.
  • Phosphorus BPDA was added in the same manner as in Example 1, except that the viscosity of the finally prepared polyamic acid solution was adjusted to 4,600 cp by adding 36.911 g (0.125 mole).
  • Example 4 was dissolved in a solvent of 33.156 g (0.097 mole) of the following Formula 4 as a second diamine monomer in a solvent, and 36.778 g (0.125 mole) of the acid dianhydride compound was added to the final mixture. It was carried out in the same manner as in Example 1, except that the viscosity of the polyamic acid solution prepared as 4,700cp was adjusted.
  • Example 5 dissolved TFMB, the first diamine monomer, 19.532g (0.061mole) and 20.949g (0.061mole), the compound of Formula 4, which is the second diamine monomer in a solvent, and an acid dianhydride compound.
  • Phosphorus BPDA was added in the same manner as in Example 4, except that the viscosity of the finally prepared polyamic acid solution was adjusted to 4,600 cp by adding 37.180 g (0.126 mole).
  • Example 6 dissolved 11.634g (0.036mole) of the first diamine monomer and 29.117g (0.085mole) of the compound of Formula 4, which is the second diamine monomer, in a solvent, and an acid dianhydride compound.
  • Phosphorus BPDA was added in the same manner as in Example 4, except that the viscosity of the finally prepared polyamic acid solution was adjusted to 4,600 cp by adding 36.911 g (0.125 mole).
  • the polyamic acid solutions prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were dropped on a glass plate to form a certain thickness (15 ⁇ m after heat treatment when the solution thickness was 100 ⁇ m, based on 15% solid content) using a spin coater. After standing for 30 minutes in an atmosphere with a temperature of 25°C and a humidity of 90% or more, a clouding phenomenon was observed. The level of cloudiness was evaluated by digitizing from 0 to 5 (0: no occurrence, 5: actual occurrence).
  • the polyamic acid solutions prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were coated on a glass plate using a spin coater, and then heat treated in a high temperature convection oven. The heat treatment was conducted under a nitrogen atmosphere, and a final film was obtained at 100°C/30min and 350°C/30min temperature and time conditions.
  • Table 2 below shows the results of measuring the physical properties of the polyimide films prepared in each of the following methods.
  • Transmittance was measured at 550 nm using a UV-Vis NIR Spectrophotometer (Shimadsu, UV-1800).
  • the glass transition temperature (T g ) and thermal expansion coefficient (CTE) of the film were measured using TMA 402 F3 from Netzsch.
  • the force of the tension mode was set to 0.05N, and the measurement temperature was increased from 30°C to 350°C at a rate of 5°C/min to measure the coefficient of linear thermal expansion as an average value in the range of 100 to 250°C.
  • the thermal decomposition temperature (T d , 1%) was measured using TG 209 F3 from Netzsch.
  • the diamine monomers having structures 3 and 4 can have excellent optical properties and high refractive index.
  • DMPA a low-absorption solvent, no clouding occurred in the atmosphere after curing after coating.
  • the polyamic acid solution prepared by the present invention has a film having a thickness of 10 to 15 ⁇ m, a thermal expansion coefficient in the range of 100 to 250° C. of 17 ppm or less, and a refractive index at a wavelength of 540 nm of 1.75 or more and 550 nm. It may be provided as a transparent polyimide film having a transmittance at a wavelength of 88% or more and a yellow index (Yellow Index, YI) of 8 or less.
  • YI yellow index
  • the polyimide film produced according to the present invention satisfies high refractive index, excellent light transmittance and heat resistance, and thus displays for OLEDs, displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, flexible OLED surface lighting substrates, and electronics. It can be widely applied to flexible substrates and protective films, such as substrate materials for paper.
  • first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from other components.
  • first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component.
  • Singular expressions include plural expressions unless the context clearly indicates otherwise.
  • the terms “include” or “have” are intended to indicate the presence of features, numbers, steps, actions, components, parts or combinations thereof described in the specification, one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, actions, components, parts or combinations thereof are not excluded in advance.
  • a part such as a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case of being “just above” the other part but also another part in the middle.
  • a portion of a layer, film, region, plate, or the like is said to be “under” another portion, this includes not only the case “underneath” another portion, but also another portion in the middle.
  • variable includes all values within the stated range including the described endpoints of the range.
  • a range of “5 to 10” includes values of 5, 6, 7, 8, 9, and 10, as well as any subrange of 6 to 10, 7 to 10, 6 to 9, 7 to 9, and the like. It will be understood to include, and include any value between integers pertinent to the stated range of ranges such as 5.5, 6.5, 7.5, 5.5 to 8.5 and 6.5 to 9, and the like.
  • the range of “10% to 30%” is 10% to 15%, 12% to 10%, 11%, 12%, 13%, etc. and all integers including up to 30% It will be understood that it includes any subranges such as 18%, 20% to 30%, etc., and includes any value between valid integers within the scope of the stated range, such as 10.5%, 15.5%, 25.5%, and the like.
  • the present invention relates to a method for producing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced through the method, the polyamic acid composition and a polyimide film and polya comprising the same It will be described by dividing it into a method for producing a mixed acid composition and a polyimide film.
  • the polyamic acid of the present invention includes one selected from the group consisting of diamine compounds, acid dianhydride compounds, and combinations thereof, wherein the diamine compounds include a first diamine monomer; And a second diamine monomer.
  • the diamine compound of the present invention is characterized by comprising a first diamine monomer and a second diamine monomer.
  • the first diamine monomer includes one selected from the group consisting of fluorinated aromatic diamine monomers, non-fluorinated aromatic diamine monomers, and combinations thereof.
  • the fluorinated aromatic diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]- 1,1,1,3,3,3-hexafluoro propane (BAFP), 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane (BAMF), 2,2'-bis( 3-Aminophenyl)-hexafluoropropane (BAPF), 3,5-diaminobenzotrifluoroide (DABF), 2,2'-bis(trifluoromethyl)-4,4'-diaminodi It is preferred to use one selected from the group consisting of phenyl ether (BTDE), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHH) and combinations thereof.
  • BAFP 2,2'-bis(3-amino-4-hydroxyphen
  • the non-fluorinated aromatic diamine monomers are 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p -Methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine ( mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and combinations thereof. desirable.
  • ODA 4,4'-oxydianiline
  • MDA 4,4'-methylenedianiline
  • pPDA p-phenylenediamine
  • mPDA
  • the second diamine monomer includes at least one of the following Chemical Formula 1 and Chemical Formula 2.
  • R1 in Formula 1 includes one selected from the group consisting of chlorine, bromine, iodine, cyanide, trifluoromethyl and combinations thereof
  • R2 in Formula 2 is chlorine, bromine, iodine, cyanide, trifluor Romethyl and combinations thereof.
  • the second diamine monomer is characterized in that it contains 50 to 80 mol% based on the total diamine compound. At this time, if it is less than 50 mol%, there is a limit in improving the refractive index property, and if it is more than 80 mol%, there is a limit due to deterioration of optical properties.
  • the acid dianhydride compound of the present invention is characterized by including one selected from the group consisting of fluorinated aromatic acid dianhydrides, non-fluorinated aromatic acid dianhydrides, and combinations thereof.
  • the fluorinated aromatic acid dianhydride is an aromatic acid dianhydride in which a fluorine substituent is introduced, for example, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(Hexafluoroisopropylidene) diphthalic anhydride, 6FDA )), 4,4'-(4,4'-hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride)(4,4'-(4,4'-Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride, 6-FDPDA) and combinations thereof.
  • a fluorine substituent for example, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(Hexafluoroisopropylidene) diphthalic anhydride, 6FDA )
  • the non-fluorinated aromatic acid dianhydride is an aromatic acid dianhydride in which a fluorine substituent is not introduced, for example pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxyl Acid dianhydride (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
  • the acid dianhydride is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4'- Hexafluoroisopropylidenediphenoxy)bis-(phthalic anhydride), cyclobutanetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bicyclo[2.2.
  • the viscosity of the polyamic acid of the present invention comprising the diamine compound and the acid dianhydride compound is characterized by 1,000 to 10,000 cp at 23°C. At this time, when the viscosity of the polyamic acid is less than 1,000 cp, it may be difficult to obtain an appropriate level of film thickness when preparing the polyimide film, and when it is more than 10,000 cp, there is a problem that uniform coating and effective solvent removal cannot be achieved.
  • polyamic acid (which is the same expression as the polyamic acid solution) is prepared.
  • the polyamic acid production method comprises the steps of preparing a mixture by mixing a diamine compound and a solvent; And preparing a polyamic acid solution by adding and polymerizing an acid dianhydride compound to the mixture.
  • the diamine compound may include a first diamine monomer including one selected from the group consisting of fluorinated aromatic diamine monomers, non-fluorinated aromatic diamine monomers, and combinations thereof; And a second diamine monomer comprising one selected from the group consisting of chlorine, bromine, iodine, cyanide, trifluoromethyl, and combinations thereof.
  • the fluorinated aromatic diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]- It is preferred to use one selected from the group consisting of 1,1,1,3,3,3-hexafluoro propane (BAFP) and combinations thereof.
  • TFMB 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl
  • BAFP 1,1,1,3,3,3-hexafluoro propane
  • the non-fluorinated aromatic diamine monomers are 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p -Methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine ( mXDA), 4,4'-diaminodiphenylsulfone (DDS), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and combinations thereof. desirable.
  • ODA 4,4'-oxydianiline
  • MDA 4,4'-methylenedianiline
  • pPDA p-phenylenediamine
  • mPDA
  • the second diamine monomer specifically includes one monomer selected from the group consisting of the following Chemical Formula 1, Chemical Formula 2, and combinations thereof.
  • R1 in Formula 1 includes one selected from the group consisting of chlorine, bromine, iodine, cyanide, trifluoromethyl and combinations thereof
  • R2 in Formula 2 is chlorine, bromine, iodine, cyanide, trifluor Romethyl and combinations thereof.
  • the mixing is conducted for 30 to 60 minutes at a temperature of 25 to 30°C under a nitrogen atmosphere.
  • the second diamine monomer is preferably adjusted to 30 to 80 mol%, preferably 50 to 80 mol%, based on the entire diamine compound.
  • the solvent in which the diamine compound is added may be selected from the group consisting of a polar solvent, a low boiling point solvent, a low absorbent solvent, a spreading solvent, and combinations thereof.
  • a polar solvent a low boiling point solvent
  • a low absorbent solvent a low absorbent solvent
  • a spreading solvent a more specific example will be described below. (However, in the case of a solvent containing two or more characteristics among the solvents listed below, it may be described in duplicate.)
  • the polar solvent is m-cresol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl acetate ( DEA), 3-methoxy-N,N-dimethyl propanamide (DMPA), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide (DML) and combinations thereof Can.
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylacetamide
  • DMSO dimethyl sulfoxide
  • DEA diethyl acetate
  • DMPA 3-methoxy-N,N-dimethyl propanamide
  • DPA N,N-dimethyl propinoamide
  • DML N,N-dimethyllactamide
  • the low boiling point solvent may be selected from the group consisting of tetrahydrofuran (THF), trichloromethane (chloroform, TCM) and combinations thereof.
  • THF tetrahydrofuran
  • chloroform chloroform
  • the low boiling point solvent has a high volatility, so it is easy to remove the solvent when producing the film, which makes it possible to improve the physical properties of the produced film.
  • the low absorbent solvent is gamma-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (DMPA), N,N-dimethyl propinoamide (DPA), N,N-dimethyllactamide ( DML), N-methyl-2-pyrrolidone (NMP), and combinations thereof.
  • GBL gamma-butyrolactone
  • DMPA 3-methoxy-N,N-dimethylpropanamide
  • DPA N,N-dimethyl propinoamide
  • DML N,N-dimethyllactamide
  • NMP N-methyl-2-pyrrolidone
  • the low-absorbent solvent plays an important role in improving the cloudiness by minimizing water absorption during film production.
  • gamma-butyrolactone (GBL) and N-methyl-2-pi First low absorbent solvent mixture of lollidon (NMP), gamma-butyrolactone (GBL) and second low absorbent solvent mixture of N,N-dimethyl propinoamide (DPA), gamma-butyrolactone (GBL) and Choose a third low absorbent solvent mixture of 3-methoxy-N,N-dimethyl propanamide (DMPA), or 3-methoxy-N,N-dimethyl propanamide (DMPA) and N,N-dimethyl propino It is preferred to select amides (DPA) each independently.
  • N,N-dimethyl propinoamide alone or 3-methoxy-N,N-dimethyl propanamide is selected alone as the low-absorbent solvent, it is preferable to use 100 mol% alone without adding another solvent.
  • Examples of the spreading solvent include ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene glycol diethyl ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and these. Combination of can use one selected from the group.
  • EGBE ethylene glycol monobutyl ether
  • EGME ethylene glycol dimethyl ether
  • EGDE ethylene glycol diethyl ether
  • EGDPE ethylene glycol dipropyl ether
  • ESDBE ethylene glycol dibutyl ether
  • ethylene glycol monobutyl ether may be used in an amount of 10 to 40 mol%, preferably 10 to 30 mol%.
  • the acid dianhydride compound to be added may include one selected from the group consisting of fluorinated aromatic acid dianhydrides, non-fluorinated aromatic acid dianhydrides, and combinations thereof, and specific examples are omitted because they are already overlapped with those described in the polyamic acid composition. Do it.
  • the diamine compound and the acid dianhydride compound constitute a solid content in a polyamic acid solution
  • the content of the solid content is preferably 10 to 40% by weight based on the polyamic acid solution. More preferably, the solid content is contained 10 to 25% by weight.
  • the content of the solid content is less than 10% by weight, there is a limit to increase the thickness of the film when preparing the polyimide film, and when the content of the solid content is more than 40% by weight, there is a problem that there is a limit in controlling the viscosity of the polyamic acid solution.
  • the diamine compound and the acid dianhydride compound constituting the solid content the diamine compound is contained in 95 to 100 mol%, and the acid dianhydride compound is contained in 100 to 105 mol parts (parts by mole weight).
  • the polymerization it is preferably carried out at a temperature of 10 to 70 °C for 6 to 48 hours.
  • a catalyst may be further added to increase reactivity other than the acid dianhydride.
  • the catalyst used at this time is not contrary to the object of the present invention and can be used without particular limitation as long as it can improve reactivity in a range that does not significantly impair the effect.
  • it may be selected from the group consisting of trimethylamine, xylene, pyridine, quinoline, and combinations thereof.
  • it in addition to the catalyst, it may further include any one selected from the group consisting of plasticizers, antioxidants, flame retardants, dispersants, viscosity modifiers, leveling agents and combinations thereof, which also significantly remarks the objects and effects of the present invention. It can be selected and used as needed within a range that does not damage.
  • the prepared polyamic acid solution may be coated on a substrate to form a transparent coating layer, and the transparent coating layer may be heat treated to produce the polyimide film of the present invention.
  • the polyamic acid solution of the present invention having a specific viscosity is coated on a prepared substrate such as glass, and the method of coating used is not particularly limited. Examples include spin coating, dip coating, solvent casting, slot die coating, spray coating, and combinations thereof.
  • the heat treatment may be carried out in a convection manner through a general oven, the heat treatment conditions are performed for 30 minutes to 120 minutes at 100 to 450 °C.
  • the heat treatment may be performed under temperature and time conditions for 30 minutes at 100°C and 30 minutes at 350°C. This is a condition capable of maximizing the properties of the polyimide film of the present invention used as an optical film at the same time as removal of a suitable solvent.
  • the polyamic acid composition of the present invention is excellent in heat resistance, optical properties, and refractive index properties by optimizing the composition of the novel specific diamine compound and acid dianhydride and the solvent (organic solvent) that does not cause cloudiness and their usage. It is a feature to provide a polyimide film having transparency. Specifically, the polyimide film of the present invention is to be manufactured through a method of manufacturing the polyimide film, wherein the polyimide film has a thickness of 10 to 15 ⁇ m, a refractive index of 1.7 or more, and a yellowness index (YI) of 10 or less.
  • YI yellowness index
  • the glass transition temperature of 300 °C or more and shows a transmittance of 85% or more at a wavelength of 550nm is characterized by having a high transparency.
  • the transmittance of the polyimide film of the present invention more preferably shows 88% or more, and the yellowness may have a value of 8 or less.
  • the polyimide film of the present invention can be used in various fields, and is particularly useful for flexible devices, tablet PCs, wearable devices, and flexible OLED lighting substrate materials that require a high-efficiency light source that requires high transparency and high refractive index characteristics. Can be.

Landscapes

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

Abstract

La présente invention concerne un procédé de préparation d'une composition d'acide polyamique, une composition d'acide polyamique, un procédé de fabrication d'un film de polyimide l'utilisant et un film de polyimide fabriqué par ce procédé de fabrication et, plus précisément, un composé de diamine dans lequel sont introduits un hétéroatome et un atome d'halogène, un procédé de préparation d'une composition d'acide polyamique qui comprend un composé de dianhydride d'acide et est ainsi capable d'améliorer les propriétés optiques, une composition d'acide polyamique, un procédé de fabrication d'un film de polyimide l'utilisant et un film de polyimide fabriqué par ce procédé de fabrication.
PCT/KR2019/014970 2019-01-02 2019-11-06 Procédé de préparation d'une composition d'acide polyamique, composition d'acide polyamique, procédé de fabrication d'un film de polyimide l'utilisant et film de polyimide fabriqué par ce procédé de fabrication WO2020141710A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021538708A JP7317122B2 (ja) 2019-01-02 2019-11-06 ポリアミド酸組成物の製造方法、ポリアミド酸組成物、これを用いたポリイミドフィルムの製造方法及びその製造方法によって製造されたポリイミドフィルム
CN201980086432.XA CN113795536A (zh) 2019-01-02 2019-11-06 聚酰胺酸组合物及其制备方法、聚酰亚胺膜的制备方法及由此制备的聚酰亚胺膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020190000242A KR102260540B1 (ko) 2019-01-02 2019-01-02 폴리아믹산 조성물의 제조방법, 폴리아믹산 조성물, 이를 이용한 폴리이미드 필름의 제조방법 및 그 제조방법을 통해 제조된 폴리이미드 필름.
KR10-2019-0000242 2019-01-02

Publications (1)

Publication Number Publication Date
WO2020141710A1 true WO2020141710A1 (fr) 2020-07-09

Family

ID=71406850

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/014970 WO2020141710A1 (fr) 2019-01-02 2019-11-06 Procédé de préparation d'une composition d'acide polyamique, composition d'acide polyamique, procédé de fabrication d'un film de polyimide l'utilisant et film de polyimide fabriqué par ce procédé de fabrication

Country Status (4)

Country Link
JP (1) JP7317122B2 (fr)
KR (1) KR102260540B1 (fr)
CN (1) CN113795536A (fr)
WO (1) WO2020141710A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120862A1 (fr) * 2021-12-22 2023-06-29 주식회사 엘지화학 Film de résine à base de polyimide, substrat pour dispositif d'affichage l'utilisant, et dispositif optique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000066216A (ko) * 1999-04-14 2000-11-15 윤종용 광통신용 폴리이미드
KR20170076101A (ko) * 2015-12-24 2017-07-04 주식회사 두산 신규 구조의 디아민 모노머를 적용한 폴리아믹산 용액 및 이를 포함하는 폴리이미드 필름
KR20170079896A (ko) * 2015-12-31 2017-07-10 주식회사 동진쎄미켐 폴리이미드고분자 조성물, 이의 제조 방법 및 이를 이용한 폴리이미드 필름의 제조 방법
KR20180093203A (ko) * 2017-02-10 2018-08-21 삼성디스플레이 주식회사 폴리아믹산, 폴리이미드 필름 및 폴리이미드 필름의 제조 방법
KR101912738B1 (ko) * 2017-05-23 2018-10-30 주식회사 대림코퍼레이션 광 특성 및 위상 지연 특성이 우수한 고투명성을 갖는 폴리이미드 전구체 수지 조성물, 이를 이용한 폴리이미드 필름 제조방법, 및 이에 의해 제조된 폴리이미드 필름

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59157319A (ja) * 1983-02-22 1984-09-06 Agency Of Ind Science & Technol 高弾性率の全芳香族ポリイミド成型物の製造法
CN1388904A (zh) 2000-08-09 2003-01-01 三井化学株式会社 聚酰亚胺树脂光学元件
JP2006249116A (ja) 2005-03-08 2006-09-21 Fuji Photo Film Co Ltd ポリイミドおよびそれを用いた光学フィルム
KR101704010B1 (ko) 2015-08-27 2017-02-07 부산대학교 산학협력단 신규한 디아민 화합물, 이를 이용한 폴리아믹산 및 폴리이미드
CN105399950B (zh) 2015-12-18 2018-03-09 吉林大学 一种含氰基的聚酰亚胺树脂及其在制备覆铜箔方面的应用
CN107936247B (zh) 2017-11-24 2020-04-17 山东省科学院新材料研究所 一种难溶盐与聚酰亚胺气凝胶复合光催化剂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000066216A (ko) * 1999-04-14 2000-11-15 윤종용 광통신용 폴리이미드
KR20170076101A (ko) * 2015-12-24 2017-07-04 주식회사 두산 신규 구조의 디아민 모노머를 적용한 폴리아믹산 용액 및 이를 포함하는 폴리이미드 필름
KR20170079896A (ko) * 2015-12-31 2017-07-10 주식회사 동진쎄미켐 폴리이미드고분자 조성물, 이의 제조 방법 및 이를 이용한 폴리이미드 필름의 제조 방법
KR20180093203A (ko) * 2017-02-10 2018-08-21 삼성디스플레이 주식회사 폴리아믹산, 폴리이미드 필름 및 폴리이미드 필름의 제조 방법
KR101912738B1 (ko) * 2017-05-23 2018-10-30 주식회사 대림코퍼레이션 광 특성 및 위상 지연 특성이 우수한 고투명성을 갖는 폴리이미드 전구체 수지 조성물, 이를 이용한 폴리이미드 필름 제조방법, 및 이에 의해 제조된 폴리이미드 필름

Also Published As

Publication number Publication date
JP7317122B2 (ja) 2023-07-28
KR102260540B1 (ko) 2021-06-08
KR20200084481A (ko) 2020-07-13
JP2022516281A (ja) 2022-02-25
CN113795536A (zh) 2021-12-14

Similar Documents

Publication Publication Date Title
WO2018038309A1 (fr) 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
WO2017179877A1 (fr) Film de polyamide-imide incolore et transparent et son procédé de fabrication
WO2017111289A1 (fr) Composition de poly(acide amique) à laquelle sont appliqués des monomères alicycliques et film de polyimide transparent l'utilisant
WO2018056573A1 (fr) Solution de précurseur de polyamide et procédé pour sa production
WO2017209413A1 (fr) Polyamide-imide transparent haute résistance et son procédé de préparation
WO2017188630A1 (fr) Polyamide-imide transparent de haute résistance et son procédé de fabrication
WO2018117551A1 (fr) Film de polyimide transparent
WO2015099478A1 (fr) Résine de polyamide-imide transparente et film utilisant celle-ci
WO2020091432A1 (fr) Composition de précurseur de polyimide pour améliorer l'adhésivité d'un film de polyimide et film de polyimide fabriqué à partir de celle-ci
WO2020138645A1 (fr) Composition d'acide polyamique et film de polyimide transparent l'utilisant
WO2017204462A1 (fr) Polyamide-imide, procédé de préparation du polyamide-imide, et film de polyamide-imide utilisant le polyamide-imide
WO2019160218A1 (fr) Composition d'acide polyamique ayant une stabilité au stockage améliorée, procédé de fabrication de film de polyimide l'utilisant, et film de polyimide fabriqué au moyen de celle-ci
WO2018216853A1 (fr) Procédé de fabrication d'une résine d'acide polyamique présentant une propriété de séparation laser facile et une grande résistance à la chaleur, et film de polyimide fabriqué par utilisation de cette dernière
WO2016140559A1 (fr) Composition de film polyimide pour substrat souple de dispositif optoélectronique
WO2016108631A1 (fr) Précurseur de polyamide-imide, film de polyamide-imide et dispositif d'affichage le comprenant
WO2018147611A1 (fr) Procédé de production d'un film de polyamide-imide
WO2020141713A1 (fr) Procédé de préparation d'une composition d'acide polyamique contenant un nouveau composé dicarbonylé, composition d'acide polyamique, procédé de fabrication d'un film de polyamide-imide l'utilisant et film de polyamide-imide produit par le même procédé de fabrication
WO2019132515A1 (fr) Procédé de préparation d'acide polyamique, et acide polyamique, résine de polyimide et film de polyimide ainsi fabriqués
WO2020159174A1 (fr) Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, chacun utilisant celui-ci
WO2018216852A1 (fr) Composition de résine précurseur de polyimide ayant des caractéristiques lumineuses et des caractéristiques de retard de phase et une transparence élevée excellentes, procédé de fabrication de film de polyimide l'utilisant, et film de polyimide ainsi fabriqué
WO2020101225A1 (fr) Composition de précurseur de polyimide contenant un composé à base de dianhydride réticulable et un antioxydant, et film de polyimide produit à partir de celle-ci
WO2020141710A1 (fr) Procédé de préparation d'une composition d'acide polyamique, composition d'acide polyamique, procédé de fabrication d'un film de polyimide l'utilisant et film de polyimide fabriqué par ce procédé de fabrication
WO2020209625A1 (fr) Copolymère séquencé de polyamide-imide, son procédé de préparation et film polyamide-imide le comprenant
WO2020040527A1 (fr) Film de polyimide comprenant une résine de polyimide cristalline et une charge thermoconductrice, et procédé de fabrication associé
WO2020022564A1 (fr) Composition de précurseur de polyimide comprenant de l'acide carboxylique aromatique et film de polyimide fabriqué à l'aide de celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19907289

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021538708

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19907289

Country of ref document: EP

Kind code of ref document: A1