WO2022202769A1 - Poly(acide amique), solution de poly(acide amique), polyimide, substrat de polyimide et produit en couches, et leurs procédés de production - Google Patents

Poly(acide amique), solution de poly(acide amique), polyimide, substrat de polyimide et produit en couches, et leurs procédés de production Download PDF

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WO2022202769A1
WO2022202769A1 PCT/JP2022/013023 JP2022013023W WO2022202769A1 WO 2022202769 A1 WO2022202769 A1 WO 2022202769A1 JP 2022013023 W JP2022013023 W JP 2022013023W WO 2022202769 A1 WO2022202769 A1 WO 2022202769A1
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polyamic acid
polyimide
mol
amount
charged
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PCT/JP2022/013023
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Japanese (ja)
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博文 中山
萌子 加藤
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株式会社カネカ
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Priority to JP2023509175A priority Critical patent/JPWO2022202769A1/ja
Priority to CN202280021912.XA priority patent/CN117043230A/zh
Priority to KR1020237034036A priority patent/KR20230160288A/ko
Publication of WO2022202769A1 publication Critical patent/WO2022202769A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds

Definitions

  • the present invention relates to polyamic acid, polyamic acid solution, polyimide, polyimide substrate and laminate, and methods for producing them.
  • Electronic devices such as displays, touch panels, and solar cells are required to be thinner, lighter, and more flexible, and resin film substrates are being used instead of glass substrates.
  • various electronic elements such as thin film transistors and transparent electrodes, are formed on the substrate, and high-temperature processes are required to form these electronic elements.
  • General aromatic polyimide has sufficient heat resistance to adapt to high-temperature processes, and its coefficient of linear thermal expansion (CTE) is also close to that of glass substrates and electronic elements. substrate material.
  • Aromatic polyimides are generally colored yellowish brown due to the formation of intramolecular conjugation and charge transfer (CT) complexes.
  • CT charge transfer
  • top-emission type organic EL devices light is taken out from the side opposite to the substrate side, and the substrate is not required to be transparent, so a general aromatic polyimide has been used.
  • transparent displays bottom-emission type organic EL, and liquid crystal displays, where the light emitted from the display element is emitted through the substrate, and in order to make smartphones and the like full-screen displays (notchless)
  • the substrate is also required to have high optical properties.
  • Patent Documents 1 and 2 It has been reported that the formation of a CT complex can be suppressed by using an aliphatic monomer in order to reduce the coloring of polyimide.
  • Patent Documents 1 and 2 it does not relate to a technique for reducing the coloring of polyimide, by imidizing polyamic acid as a polyimide precursor by adding silicone oil, the obtained polyimide film exhibits high adhesion to the substrate. is known (Patent Document 3).
  • Patent Documents 1 and 2 have high transparency and low CTE, they have an aliphatic structure and thus have a low thermal decomposition temperature and cannot be applied to high-temperature processes for forming electronic devices.
  • organic EL light-emitting elements have low moisture resistance, and moisture entering from the outside causes dark spots, leakage current, and non-lighting. If a resin is used as the substrate, it is not possible to block moisture completely. Therefore, in order to improve the barrier property of the substrate, an inorganic film such as a silicon oxide film and a silicon nitride film is used as an intermediate layer between the polyimide layers of the two-layered polyimide film, or in the two-layered polyimide film. used on membranes.
  • the adhesion of the inorganic film to the polyimide film is low, and there is a problem that peeling or lifting occurs at the interface between the inorganic film and the polyimide film during the process.
  • the present invention provides a polyimide having high heat resistance and high transparency and improved adhesion to an inorganic film, polyamic acid as a precursor thereof, a polyimide substrate and laminate, and methods for producing the same. for the purpose of providing
  • One embodiment of the present invention has the following configuration.
  • a polyamic acid that is a polyaddition reaction product of a diamine and a tetracarboxylic dianhydride, wherein the diamine comprises 1,4-phenylenediamine and 1,3-bis(3-aminopropyl)tetramethyldisiloxane , a polyamic acid in which said tetracarboxylic dianhydride comprises 3,3,4,4-biphenyltetracarboxylic dianhydride and 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride.
  • the present invention can provide polyimide having high heat resistance and high transparency and improved adhesion to inorganic films, and polyamic acid as its precursor. These are suitable as substrate materials for electronic devices.
  • a polyamic acid according to one embodiment of the present invention is a polyamic acid that is a polyaddition reaction product of a diamine and a tetracarboxylic dianhydride, wherein the diamine is 1,4-phenylenediamine and 1,3-bis (3-aminopropyl)tetramethyldisiloxane, wherein the tetracarboxylic dianhydride is 3,3,4,4-biphenyltetracarboxylic dianhydride and 9,9-bis(3,4-dicarboxy It is a polyamic acid containing phenyl)fluoric acid dianhydride.
  • the polyimide obtained from the polyamic acid according to the present embodiment has a siloxane bond in the resin, which increases affinity with inorganic films (for example, silicon oxide films), and is expected to improve adhesion to inorganic films.
  • inorganic films for example, silicon oxide films
  • Tg glass transition temperature
  • the ratio of 1,3-bis(3-aminopropyl)tetramethyldisiloxane when the total of all diamines is 100 mol% is 0.1 mol% to 10.0 mol%. is preferably 0.15 mol % to 1.0 mol %, and even more preferably 0.2 mol % to 0.5 mol %.
  • the polyimide obtained from the polyamic acid can have sufficient adhesion to an inorganic film (for example, a silicon oxide film) and heat resistance capable of coping with high-temperature processes.
  • the polyamic acid has a ratio of 3,3,4,4-biphenyltetracarboxylic dianhydride of 70 mol% with respect to a total of 100 mol% of all tetracarboxylic dianhydride.
  • Polyamic acid is preferably ⁇ 99 mol%, more preferably 75 mol% to 98 mol%, more preferably 75 mol% to 97 mol%, more preferably 75 mol% to 96 mol%, more preferably 75 mol % to 95 mol %, more preferably 80 mol % to 90 mol %.
  • 9,9-bis(3,4-dicarboxyphenyl)fluoric acid dianhydride suppresses the formation of a charge transfer complex, so that the polyimide obtained from the polyamic acid exhibits transparency.
  • this bulky structure inhibits packing of molecular chains, the internal stress of the polyimide obtained from the polyamic acid tends to increase.
  • the polyamic acid is 9,9-bis(3,4-dicarboxy Phenyl)fluoric acid dianhydride is preferably a polyamic acid having a proportion of 1 mol% to 30 mol%, more preferably 5 mol% to 25 mol%, and even more preferably 10 mol% to 20 mol%.
  • the polyimide obtained from the polyamic acid can suppress an increase in internal stress, and can reduce the internal stress generated when laminated with a glass substrate or the like. Therefore, it is possible to obtain a material excellent in process compatibility without warping of the laminate in the manufacturing process of the laminate using the polyimide obtained from the polyamic acid or the electronic device using the laminate.
  • the polyamic acid according to the present embodiment is other than 1,4-phenylenediamine and other diamine components than 1,3-bis(3-aminopropyl)tetramethyldisiloxane as long as it does not impair its performance.
  • diamine components include 1,4-diaminocyclohexane, 1,3-phenylenediamine, 4,4'-oxydianiline, 3,4'-oxydianiline, 2,2'-bis(tri fluoromethyl)-4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminobenzanilide, N,N'-bis(4-aminophenyl)terephthalamide, 4 , 4′-diaminodiphenylsulfone, 4-(aminophenyl) 4-aminobenzoate, m-tolidine, o-tolidine, 4,4′-bis(aminophen)
  • the polyamic acid according to the present embodiment is other than 3,3,4,4-biphenyltetracarboxylic dianhydride and 9,9-bis(3,4-dicarboxy
  • Other acid dianhydride components other than phenyl)fluoric acid dianhydride may also be included.
  • Examples of the other acid dianhydride components include pyromellitic dianhydride, 1,4-phenylenebis(trimellitate dianhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride product, 4,4'-oxyphthalic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, 2'-oxodispiro[bicyclo[2.2.1]h
  • a polyimide containing the above structure can be obtained by a known method.
  • a polyimide can be synthesized by a synthesis method involving precursors such as polyamic acid and polyimide ester, and a synthesis method not involving precursors. From the viewpoint of availability of monomers and ease of polymerization, it is preferable to synthesize polyimide by imidization of polyamic acid as a precursor.
  • a polyamic acid containing the above structure can be obtained by reacting a diamine and a tetracarboxylic dianhydride in an organic solvent.
  • a diamine is dissolved or dispersed in an organic solvent in the form of a slurry to obtain a diamine solution
  • a tetracarboxylic dianhydride is dissolved in an organic solvent or dispersed in the form of a slurry in a solution or a solid state, and the diamine It may be added into the solution.
  • a diamine may be added to the tetracarboxylic dianhydride solution.
  • the dissolution and reaction of diamine and tetracarboxylic dianhydride are preferably carried out in an inert gas atmosphere such as argon or nitrogen.
  • a polyamic acid having a plurality of constitutional units can be obtained by using a plurality of kinds of diamines and/or a plurality of kinds of tetracarboxylic dianhydrides. Also, by blending polyamic acids with different structures, it is possible to obtain a blend of polyamic acids having a plurality of structural units with different structures.
  • the organic solvent used for the polyamic acid synthesis reaction is not particularly limited.
  • the organic solvent is preferably capable of dissolving the tetracarboxylic dianhydride and diamines used, and capable of dissolving polyamic acid produced by polymerization.
  • organic solvent examples include urea-based solvents such as tetramethylurea and N,N-dimethylethylurea; sulfoxide or sulfone-based solvents such as dimethylsulfoxide, diphenylsulfone, and tetramethylsulfone; N,N-dimethylacetamide ( DMAC), N,N-dimethylformamide (DMF), N,N'-diethylacetamide, N-methyl-2-pyrrolidone (NMP) and other amide solvents; ⁇ -butyrolactone and other ester solvents; hexamethylphosphoric acid Amide solvents such as triamide; Halogenated alkyl solvents such as chloroform and methylene chloride; Aromatic hydrocarbon solvents such as benzene and toluene; Phenol solvents such as phenol and cresol; Ketone solvents such as cyclopentanone; , 1,3-dioxolane, 1,4-
  • organic solvents may be used in combination if necessary.
  • the organic solvent used in synthesizing the polyamic acid is preferably selected from amide solvents, ketone solvents, ester solvents and ether solvents, particularly DMF, Amide solvents such as DMAC and NMP are preferred.
  • the temperature conditions for the polyamic acid synthesis reaction are not particularly limited. From the viewpoint of suppressing a decrease in the molecular weight of the polyamic acid due to depolymerization, the reaction temperature is preferably 80° C. or lower. From the viewpoint of moderate progress of the polymerization reaction, the reaction temperature is more preferably 0 to 50°C.
  • the reaction time may be arbitrarily set within the range of 10 minutes to 30 hours.
  • a polyamic acid solution containing polyamic acid and an organic solvent is obtained by polymerizing the diamine and the tetracarboxylic dianhydride in the organic solvent.
  • This polymerization solution can be used as it is as a polyamic acid solution.
  • the concentration of polyamic acid and the viscosity of the solution may be adjusted by removing part of the solvent from the polymerization solution or by adding a solvent.
  • the solvent to be added may be different from the solvent used for polymerizing the polyamic acid.
  • a solid polyamic acid resin obtained by removing the solvent from the polymerization solution may be dissolved in a solvent to prepare a polyamic acid solution.
  • organic solvent for the polyamic acid solution one having a high solubility of polyamic acid is preferable, and the organic solvents exemplified above can be used as the organic solvent used for synthesizing the polyamic acid.
  • amide solvents such as DMF, DMAC and NMP are preferred.
  • the imidization is carried out by dehydrating and ring-closing the polyamic acid. Dehydration ring closure is accomplished by azeotropic methods using azeotropic solvents, thermal methods or chemical methods.
  • an imidization agent and/or a dehydration catalyst to the polyamic acid solution to perform chemical imidization.
  • the imidizing agent is not particularly limited, it is preferable to use a tertiary amine, and among them, a heterocyclic tertiary amine is more preferable.
  • the heterocyclic tertiary amines include pyridine, picoline, quinoline, isoquinoline, and imidazoles.
  • the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and ⁇ -valerolactone.
  • thermal imidization in which dehydration ring closure is performed by heating
  • the method of heating the polyamic acid is not particularly limited. Heat treatment may be performed. The heating time varies depending on the amount of the polyamic acid solution to be treated for dehydration ring closure and the heating temperature, but generally, it is preferable to perform heating for 1 minute to 5 hours after the treatment temperature reaches the maximum temperature.
  • An imidization agent and/or a dehydration catalyst may be added to the polyamic acid solution, and imidization may be performed by heating in the above manner.
  • the imidization reaction and the decomposition of the polyamic acid occur at the same time.
  • the method for suppressing the decomposition of the polyamic acid include esterification of the polyamic acid, silyl esterification, and increasing the reaction rate, but any method may be used. Specifically, by adding a small amount of tertiary amines such as imidazoles, the imidization rate during thermal imidization can be accelerated and a polyimide film with excellent transparency can be obtained.
  • imidazoles examples include 1H-imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2 -phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole and the like. Among them, 1,2-dimethylimidazole is preferred.
  • the content of imidazoles in the polyamic acid solution is preferably 0.005 mol to 0.100 mol, more preferably 0.010 mol to 0.080 mol, and 0.015 mol to 0, per 1.000 mol of the amide group of the polyamic acid. 0.050 mol is more preferred.
  • “Amido group of polyamic acid” means an amide group produced by polyaddition reaction of diamine and tetracarboxylic dianhydride. If the added amount of the imidazole is within the above range, improvement in transparency and low internal stress of the polyimide film can be expected.
  • the imidazole may be added to the polyamic acid solution as it is, or may be added to the polyamic acid solution as an imidazole solution.
  • the imidization of the polyamic acid into polyimide can be performed at any imidization rate of 1% to 100%, and a partially imidized polyamic acid may be synthesized.
  • the solubility in organic solvents and the viscosity of the solution tend to change.
  • the viscosity and thixotropy of the solution affect the uniformity of the film thickness. Therefore, considering the stability of the process, the polyamic acid solution is applied onto the support while the imidization rate is 0% without adding an imidizing agent and a dehydration catalyst to the polyamic acid. Solvent removal and imidization are preferably carried out by heating on the support.
  • the polyamic acid and polyimide according to one embodiment of the present invention may be used as they are for producing products and members.
  • a thermosetting component, a photocurable component, a non-polymerizable binder resin, a dye, a surfactant, a leveling agent, a plasticizer, a silane coupling agent, fine particles, a sensitizer, etc. are added to the polyamic acid and the polyimide. It may be added to form a composition.
  • the mixing ratio of these optional components is preferably in the range of 0.1% by weight to 95% by weight with respect to the total solid content of the polyimide.
  • the solid content of the composition is all components other than the organic solvent, and liquid monomer components are also included in the solid content.
  • the polyimide according to one embodiment of the present invention has excellent transparency and heat resistance, it can be used as a transparent substrate such as a substitute for glass. I can expect it.
  • the electronic devices it is preferably used as a substrate for devices requiring optical transparency, such as liquid crystal display devices, organic EL elements, electronic paper, and touch panels.
  • the polyimide according to one embodiment of the present invention can also be used as a color filter, an antireflection film, an optical member such as a hologram, a building material, and a structural material.
  • Various inorganic thin films such as metal oxides and transparent electrodes may be formed on the surface of the polyimide according to one embodiment of the present invention.
  • the inorganic thin film is formed by, for example, a sputtering method, a PVD method such as a vacuum deposition method and an ion plating method, and a dry process such as a CVD method.
  • the polyimide according to one embodiment of the present invention is preferably used as a substrate of an electronic device manufactured by a batch process because it has good adhesion to a support in addition to heat resistance and transparency.
  • a polyimide film (substrate) is formed on a support, electrodes and/or electronic elements are formed thereon, and then the polyimide substrate on which the electrodes and/or electronic elements are formed is peeled off from the support.
  • An electronic device is obtained by
  • a polyimide substrate made of the polyimide described above, a laminate of the polyimide substrate and a support, and an electronic device comprising electrodes and/or electronic elements on the polyimide substrate described above. Devices are also included. Further, in one embodiment of the present invention, there is provided a method for producing a laminate of a polyimide substrate and a support, wherein the polyamic acid solution is cast on the support and imidized to form a polyimide on the support. Also included is a method of manufacturing a laminate in which a polyimide substrate is formed in the substrate.
  • the thickness of the polyimide substrate is about 1-200 ⁇ m, preferably about 5-100 ⁇ m.
  • an inorganic film such as a silicon oxide film and a silicon nitride film is formed as an intermediate layer between each polyimide layer of a two-layered polyimide film, or , can be used on a bilayered polyimide membrane.
  • the polyamic acid solution is applied on a support, dried by heating and imidized, and then the polyimide film formed on the support is subjected to CVD vapor deposition of an inorganic film. conduct. Subsequently, the polyamic acid solution is applied again on the inorganic film, dried by heating, and imidized to obtain a polyimide film (polyimide substrate) adhered and laminated on the support.
  • a polyimide substrate in which an inorganic film is used as an intermediate layer between polyimide layers of a two-layered polyimide film.
  • the support on which the polyamic acid solution is applied examples include glass substrates (glass plates); metal substrates such as SUS or metal belts; resin films such as polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate, and triacetyl cellulose. be done. In order to accommodate current batch-type device manufacturing processes, it is more preferable to use a glass substrate (glass plate) as the support.
  • the imidization of the polyamic acid begins as the solvent evaporates, and the organic solvent and the water generated by imidization (dehydration of the polyamic acid) are released from the polyamic acid solution. volatilize. At this time, part of the water and/or the organic solvent does not volatilize and stays between the support and the resin film during imidization, causing peeling at the interface between the support and the resin film. cause.
  • the water and/or organic solvent remaining at the interface between the support and the resin film is then discharged through the polyimide film in the step of heating at a high temperature, and air bubbles remain in the portion where peeling or floating occurs. do.
  • the generation of such air bubbles causes problems when forming elements on the polyimide substrate. In particular, in thinned or miniaturized devices, even minute peeling or floating has a great influence on the formation or mounting of elements.
  • Polyamic acid and polyimide according to one embodiment of the present invention having a siloxane structure in addition to adhesion to glass, has high adhesion to an inorganic film used as an intermediate layer or the like.
  • an inorganic film used as an intermediate layer or the like At the time of imidization, lifting and peeling due to retention of an organic solvent or water at the interface between the glass support and the resin film are less likely to occur. Therefore, it is possible to accurately form and mount elements on the polyimide substrate that is closely laminated on the support.
  • a polyimide film created using a polyamic acid solution according to an embodiment of the present invention can improve adhesion to an inorganic film in addition to high heat resistance and high transparency.
  • the polyimide film (polyimide substrate) adhered and laminated on the support preferably has a 90° peel strength from the support of 0.08 N/cm to 5.00 N/cm, more preferably 0.09 N/cm. It is more preferably ⁇ 4.00 N/cm, and even more preferably 0.10 N/cm ⁇ 3.50 N/cm.
  • the 90° peel strength can be measured by the method described in Examples below.
  • the transparency of the polyimide or the polyimide film is required to have a high transmittance in the entire wavelength range of visible light in applications such as displays.
  • the yellowness index (YI) of the polyimide or the polyimide film is preferably 20 or less, more preferably 18 or less. YI can be measured according to JIS K7373-2006.
  • a polyimide film having such high transparency can be used as a transparent substrate such as a substitute for glass.
  • the internal stress generated between the polyimide substrate and the support is preferably 30 MPa or less, preferably 25 MPa or less, and more preferably 20 MPa or less.
  • the internal stress generated between the polyimide substrate and the support can be measured by the method described in Examples below.
  • the internal stress is 30 MPa or less, the laminate does not warp during the manufacturing process of the electronic device, so that the polyimide substrate has an advantage of being excellent in process adaptability.
  • An embodiment of the present invention may have the following configuration.
  • a polyamic acid that is a polyaddition reaction product of a diamine and a tetracarboxylic dianhydride, wherein the diamine comprises 1,4-phenylenediamine and 1,3-bis(3-aminopropyl)tetramethyldisiloxane , a polyamic acid in which said tetracarboxylic dianhydride comprises 3,3,4,4-biphenyltetracarboxylic dianhydride and 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride.
  • a method for producing a laminate of a polyimide substrate and a support wherein the polyamic acid solution according to any one of 4) to 6) is cast on the support and imidized, thereby forming the polyamic acid solution on the support.
  • a method for manufacturing a laminate comprising forming a polyimide substrate.
  • An electronic device comprising electrodes and/or electronic elements on the polyimide substrate according to 10) or 11).
  • Peel strength A laminate of a glass plate (non-alkali glass) and a polyimide film, and a laminate of a glass plate and a polyimide film on which a silicon oxide film (inorganic film) is formed, according to the ASTM D1876-01 standard. , 90° peel strength from a glass plate and a glass plate on which a silicon oxide film (inorganic film) was formed were measured.
  • a cut of 10 mm width is made in the polyimide film with a cutter knife, and a tensile tester (Strograph VES1D) manufactured by Toyo Seiki Co., Ltd. is used, under conditions of 23 ° C. and 55% RH, a tensile speed of 50 mm / min, a peel length of 50 mm and a peel length of 90.
  • a peel test was carried out, and the average value of the peel strength was taken as the peel strength.
  • the laminate of the glass plate (non-alkali glass) and the polyimide film was produced in the same manner as in [Preparation of polyimide film] described later. Further, the laminate of the glass plate on which the silicon oxide film (inorganic film) is formed and the polyimide film is described later [ Preparation of Polyimide Film].
  • the glass plate on which the silicon oxide film (inorganic film) was formed was produced by CVD vapor deposition of the silicon oxide film on the glass plate.
  • the polyamic acid solution prepared in the examples and comparative examples was applied with a spin coater on Corning non-alkali glass (thickness 0.7 mm, 100 mm ⁇ 100 mm) whose amount of warpage had been measured in advance.
  • the polyamic acid solution-coated glass plate was baked in the air at 120° C. for 30 minutes and in a nitrogen atmosphere at 430° C. for 30 minutes to obtain a laminate of the glass substrate and the polyimide film having a thickness of 10 ⁇ m. rice field.
  • the amount of warpage of the laminated body of the glass substrate and the polyimide film was measured using a thin film stress measuring device FLX-2320-S manufactured by Tencor Corporation, and the warpage occurred between the glass substrate and the polyimide film at 25 ° C. in a nitrogen atmosphere. The internal stress was evaluated. In order to avoid water absorption of the polyimide film, the laminate of the glass substrate and the polyimide film was measured immediately after baking or after being dried at 120° C. for 10 minutes.
  • Yellowness index (YI) of polyimide film Using a UV-visible near-infrared spectrophotometer (V-650) manufactured by JASCO Corporation, the light transmittance of the polyimide film at 200-800 nm is measured, and from the formula described in JIS K 7373, yellow is used as an indicator of yellowness. An index (YI) was calculated.
  • V-650 UV-visible near-infrared spectrophotometer
  • PAM-E 1,3-bis(3-aminopropyl)tetramethyldisiloxane
  • PDA 1,4-phenylenediamine
  • DMI 1,2-dimethylimidazole
  • Example 2 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 8.68 g, the amount of BPAF charged was changed to 2.55 g, the amount of PAM-E charged was changed to 0.013 g, and the amount of PDA charged was changed to 3.76 g. to obtain a polyamic acid solution.
  • Example 3 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 8.68 g, the amount of BPAF charged was changed to 2.55 g, the amount of PAM-E charged was changed to 0.017 g, and the amount of PDA charged was changed to 3.76 g. to obtain a polyamic acid solution.
  • Example 4 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 8.69 g, the amount of BPAF charged was changed to 2.55 g, the amount of PAM-E charged was changed to 0.026 g, and the amount of PDA charged was changed to 3.74 g. to obtain a polyamic acid solution.
  • Example 5 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 8.68 g, the amount of BPAF charged was changed to 2.55 g, the amount of PAM-E charged was changed to 0.043 g, and the amount of PDA charged was changed to 3.73 g. to obtain a polyamic acid solution.
  • Example 6 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 8.67 g, the amount of BPAF charged was changed to 2.54 g, the amount of PAM-E charged was changed to 0.086 g, and the amount of PDA charged was changed to 3.70 g. to obtain a polyamic acid solution.
  • Example 7 The charged amount of BPDA was changed to 10.085 g, the charged amount of BPAF was changed to 0.993 g, the charged amount of PAM-E was changed to 0.018 g, and the charged amount of PDA was changed to 3.904 g, and 1,2-dimethylimidazole was added.
  • a polyamic acid solution was obtained in the same manner as in Example 1, except that there was no polyamic acid.
  • Example 8> The same procedure as in Example 7 was repeated except that the amount of BPDA charged was changed to 9.370 g, the amount of BPAF charged to 1.784 g, the amount of PAM-E charged to 0.018 g, and the amount of PDA charged to 3.829 g. to obtain a polyamic acid solution.
  • Example 9 The same procedure as in Example 1 was repeated except that the amount of BPDA charged was changed to 9.366 g, the amount of BPAF charged to 1.784 g, the amount of PAM-E charged to 0.026 g, and the amount of PDA charged to 3.823 g. to obtain a polyamic acid solution.
  • Example 10 The procedure of Example 7 was repeated except that the amount of BPDA charged was changed to 8.681 g, the amount of BPAF charged was changed to 2.546 g, the amount of PAM-E charged was changed to 0.017 g, and the amount of PDA charged was changed to 3.756 g. to obtain a polyamic acid solution.
  • Example 11 The same procedure as in Example 7 was repeated except that the amount of BPDA charged was changed to 8.629 g, the amount of BPAF charged was changed to 2.551 g, the amount of PAM-E charged was changed to 0.043 g, and the amount of PDA charged was changed to 3.766 g. to obtain a polyamic acid solution.
  • Example 12 The same procedure as in Example 7 was repeated except that the amount of BPDA charged was changed to 8.018 g, the amount of BPAF charged to 3.279 g, the amount of PAM-E charged to 0.017 g, and the amount of PDA charged to 3.686 g. to obtain a polyamic acid solution.
  • Example 13> The same procedure as in Example 1 was repeated except that the amount of BPDA charged was changed to 8.015 g, the amount of BPAF charged was changed to 3.278 g, the amount of PAM-E charged was changed to 0.025 g, and the amount of PDA charged was changed to 3.681 g. to obtain a polyamic acid solution.
  • Example 14 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 7.543 g, the amount of BPAF charged was changed to 3.871 g, the amount of PAM-E charged was changed to 0.025 g, and the amount of PDA charged was changed to 3.651 g. to obtain a polyamic acid solution.
  • Example 15 The procedure of Example 1 was repeated except that the amount of BPDA charged was changed to 8.587 g, the amount of BPAF charged was changed to 2.549 g, the amount of PAM-E charged was changed to 0.173 g, and the amount of PDA charged was changed to 3.692 g. to obtain a polyamic acid solution.
  • Example 16 Polyamic acid was prepared in the same manner as in Example 1, except that the amount of BPDA charged was changed to 4.548 g, the amount of BPAF charged was changed to 7.087 g, the amount of PDA charged was changed to 3.342 g, and PAM-E was changed to 0.023 g. A solution was obtained.
  • ⁇ Comparative Example 1> 8.70 g of BPDA, 2.55 g of BPAF, and 85.0 g of NMP were charged into a 300 mL glass separable flask equipped with a stirrer equipped with a stainless steel stirring blade and a nitrogen inlet tube, and stirred at room temperature (23 ° C.) to dissolve. rice field. After 30 minutes had passed, 3.75 g of PDA was added to this solution and stirred at room temperature for 5 hours to obtain a polyamic acid solution. Further, 1,2-dimethylimidazole was added to and dissolved in this solution so as to be 1% by weight with respect to polyamic acid (resin content).
  • Comparative Example 2 The same as in Comparative Example 1 except that the amount of BPDA charged was changed to 9.478 g, the amount of BPAF charged was changed to 1.641 g, and the amount of PDA charged was changed to 3.881 g, and 1,2-dimethylimidazole was not added. to obtain a polyamic acid solution.
  • Example 4 A polyamic acid solution was prepared in the same manner as in Example 1, except that the amount of BPDA charged was changed to 10.950 g, the amount of BPAF charged to 0 g, the amount of PDA charged to 4.023 g, and the amount of PAM-E changed to 0.028 g. Obtained.
  • ⁇ Comparative Example 8> 4.166 g of trans-1,4-cyclohexanediamine (CHDA), 0.046 g of PAM-E and 85 g of NMP were charged into a 300 mL glass separable flask equipped with a stirrer equipped with stainless steel stirring blades and a nitrogen inlet tube, and the mixture was heated to room temperature. Dissolved by stirring at (23° C.). After 30 minutes, 10.788 g of BPDA was added, heated at 80° C. for 30 minutes, cooled to room temperature, and stirred for 5 hours to obtain a polyamic acid solution. Further, 1,2-dimethylimidazole was added to and dissolved in this solution so as to be 1% by weight with respect to polyamic acid (resin content).
  • CHDA trans-1,4-cyclohexanediamine
  • PAM-E 0.046 g of PAM-E and 85 g of NMP were charged into a 300 mL glass separable flask equipped with a
  • NMP was added to each of the polyamic acid solutions obtained in the above examples and comparative examples to dilute the polyamic acid concentration to 10.0% by weight.
  • the diluted polyamic acid solution was cast on a 10 mm ⁇ 10 mm square non-alkali glass plate (Corning Eagle XG, thickness 0.7 mm) so that the thickness after drying was 10 ⁇ m. did.
  • imidization was performed by heating at 430° C. for 30 minutes in a nitrogen atmosphere to form a polyimide film having a thickness of 10 ⁇ m.
  • a laminate with the glass plate was obtained.
  • the polyimide film was peeled off from the glass substrate of the obtained laminate, and the characteristics were evaluated.
  • Table 1 shows the composition of the polyamic acid solution of each example and comparative example, and the evaluation results of the polyimide film.
  • the composition in Table 1 represents the total of tetracarboxylic dianhydride and diamine as 100 mol % (unit: mol %).
  • the amount of 1,2-dimethylimidazole (DMI) added is the amount (unit: parts by weight) added to 100 parts by weight of polyamic acid (resin content).
  • Stress represents internal stress generated between the polyimide film and the support.
  • "-" in the table indicates that no measurement was performed.
  • a polyamic acid that is a polyaddition reaction product of a diamine and a tetracarboxylic dianhydride, wherein the diamine is 1,4-phenylenediamine and 1,3-bis(3-aminopropyl ) tetramethyldisiloxane, wherein said tetracarboxylic dianhydride is 3,3,4,4-biphenyltetracarboxylic dianhydride and 9,9-bis(3,4-dicarboxyphenyl)fluoric acid dianhydride
  • the resulting polyimide films have the properties shown below.
  • - Adhesion to glass is 0.10 N/cm or more - Adhesion to SiO2 is 0.05 N/cm or more - YI is 20 or less
  • 3,000 mol% of all tetracarboxylic dianhydrides total 100 mol%.
  • the ratio of 3′,4,4′-biphenyltetracarboxylic dianhydride is 70 to 99 mol%, and the ratio of 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride is 1 to 30 mol%.
  • the resulting polyimide film has the following characteristics. have.
  • Adhesion to glass is 0.10 N/cm or more ⁇ Adhesion to SiO2 is 0.05 N/cm or more ⁇ Internal stress is 30 MPa or less ⁇ YI is 20 or less Total of all tetracarboxylic dianhydrides is 100 mol%
  • the ratio of 3,3′,4,4′-biphenyltetracarboxylic dianhydride is 50 mol%
  • the ratio of 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride is 50 mol%. It was found that the polyimide film of Example 16 had excellent adhesion to glass and a silicon oxide film and had a small YI value, but had a higher internal stress than those of other Examples.
  • the polyimide films of Comparative Examples 1 to 3 which do not use 1,3-bis(3-aminopropyl)tetramethyldisiloxane as a monomer, have low internal stress and high transparency, but have poor adhesion to glass and silicon oxide films. It was small, and many floats occurred between the SiOx or glass substrate and the polyimide film after the heating test.
  • the polyimide film of Comparative Example 4 which does not use 9,9-bis(3,4-dicarboxyphenyl)fluoric acid dianhydride as a monomer, has excellent adhesion to glass and silicon oxide films, and SiOx or There is no floating between the glass substrate and the polyimide film, and the internal stress is small, but the YI value is large and the transparency is low.
  • the polyimide film of Comparative Example 5 containing 0.05 phr of 3-aminopropyltriethoxysilane (APS) without using 1,3-bis(3-aminopropyl)tetramethyldisiloxane as a monomer has low internal stress and transparency. However, the adhesiveness to the glass and the silicon oxide film was low, and a large amount of floating occurred between the SiOx or glass substrate and the polyimide film after the heating test.
  • a polyimide obtained by introducing 1,3-bis(3-aminopropyl)tetramethyldisiloxane into a polyamic acid composed of 1,4-phenylenediamine has excellent heat resistance and adhesion to glass and silicon oxide films. was confirmed to be high and to be highly transparent.
  • the ratio of 3,3′,4,4′-biphenyltetracarboxylic dianhydride is 70 to 99 mol% with respect to the total 100 mol% of all tetracarboxylic dianhydrides, 9,9-bis(3,4 -dicarboxyphenyl)fluoric acid dianhydride is 1 to 30 mol%, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane is added to polyamic acid using 1,4-phenylenediamine as a diamine. It was confirmed that the polyimide obtained by introducing has excellent heat resistance, high adhesion to glass and silicon oxide film, low internal stress with inorganic substrates, and high transparency.
  • the present invention is not limited to the above-described embodiments, but can be modified in various ways within the scope of the claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. is also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Le but de la présente invention est de fournir : un polyimide qui présente une résistance élevée à la chaleur et une transparence élevée et qui présente une adhérence améliorée à des films inorganiques ; un poly(acide amique) qui est un précurseur du polyimide ; un substrat de polyimide et un produit en couches ; et leurs procédés de production.　Ce qui précède peut être atteint par : un poly(acide amique) qui est un produit d'une réaction de polyaddition entre une diamine et un dianhydride d'acide tétracarboxylique, la diamine comprenant de la 1,4-phénylènediamine et du 1,3-bis(3-aminopropyl)tétraméthyldisiloxane et le dianhydride d'acide tétracarboxylique comprend le dianhydride d'acide 3,3,4,4-biphényltétracarboxylique et le dianhydride d'acide 9,9-bis(3,4-dicarboxyphényl)fluorène ; et un polyimide et un substrat de polyimide obtenu à partir du poly(acide amique).
PCT/JP2022/013023 2021-03-23 2022-03-22 Poly(acide amique), solution de poly(acide amique), polyimide, substrat de polyimide et produit en couches, et leurs procédés de production WO2022202769A1 (fr)

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JPH07179604A (ja) * 1993-12-24 1995-07-18 Nitto Denko Corp ポリイミド前駆体およびポリイミド、並びにネガ型感光性材料およびネガ型パターン形成方法
JP2012077285A (ja) * 2010-09-07 2012-04-19 Jfe Chemical Corp ポリイミドおよびポリイミドフィルム
JP2018168370A (ja) * 2017-03-29 2018-11-01 荒川化学工業株式会社 ポリイミド、接着剤、フィルム状接着材、接着層、接着シート、樹脂付銅箔、銅張積層板、プリント配線板、並びに多層配線板及びその製造方法
WO2019188306A1 (fr) * 2018-03-28 2019-10-03 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide, et film polyimide
WO2019188380A1 (fr) * 2018-03-30 2019-10-03 株式会社カネカ Polyamide-acide et son procédé de production, solution de polyamide-acide, polyimide, film de polyimide, corps multicouche et son procédé de production, et dispositif flexible et son procédé de production

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Publication number Priority date Publication date Assignee Title
JP5903789B2 (ja) 2010-07-22 2016-04-13 宇部興産株式会社 共重合ポリイミド前駆体及び共重合ポリイミド
JP5660249B1 (ja) 2013-06-26 2015-01-28 東レ株式会社 ポリイミド前駆体、ポリイミド、それを用いたフレキシブル基板、カラーフィルタおよびその製造方法、ならびにフレキシブル表示デバイス
JP6420064B2 (ja) 2014-06-03 2018-11-07 旭化成株式会社 ポリイミド前駆体組成物及びポリイミドフィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07179604A (ja) * 1993-12-24 1995-07-18 Nitto Denko Corp ポリイミド前駆体およびポリイミド、並びにネガ型感光性材料およびネガ型パターン形成方法
JP2012077285A (ja) * 2010-09-07 2012-04-19 Jfe Chemical Corp ポリイミドおよびポリイミドフィルム
JP2018168370A (ja) * 2017-03-29 2018-11-01 荒川化学工業株式会社 ポリイミド、接着剤、フィルム状接着材、接着層、接着シート、樹脂付銅箔、銅張積層板、プリント配線板、並びに多層配線板及びその製造方法
WO2019188306A1 (fr) * 2018-03-28 2019-10-03 三菱瓦斯化学株式会社 Résine polyimide, vernis polyimide, et film polyimide
WO2019188380A1 (fr) * 2018-03-30 2019-10-03 株式会社カネカ Polyamide-acide et son procédé de production, solution de polyamide-acide, polyimide, film de polyimide, corps multicouche et son procédé de production, et dispositif flexible et son procédé de production

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