Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/1201—Manufacture or treatment
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
  • H10K77/10—Substrates, e.g. flexible substrates
  • H10K77/111—Flexible substrates

Definitions

• the present invention relates to a resin film, a method for producing the same, a resin composition, a display, and a method for producing the same.
• Polyimide is used as a material for various electronic devices such as semiconductors and displays due to its excellent electrical insulation, heat resistance, and mechanical properties. Recently, by using a polyimide film for a display substrate such as an organic EL display, electronic paper, or a color filter, it is possible to manufacture a shock-resistant and flexible display.
• Materials used in electronic devices are required to have high heat resistance to withstand high-temperature processes in device manufacturing. Especially in applications that require transparency, a material that can achieve both heat resistance and transparency is required.
• Patent Document 1 discloses an example of manufacturing an organic EL display using polyimide having high heat resistance as a substrate.
• Patent Document 2 discloses an example of manufacturing an electronic device such as a color filter, an organic EL display, and a touch panel by using a highly transparent polyimide as a substrate.
• Patent Document 3 reports an example in which a polyimide film is produced using an alkoxysilane-modified polyimide precursor and used for a transparent substrate application or the like.
• the polyimide resin film described in Patent Document 1 has a problem that it cannot be applied to applications requiring transparency because the light transmittance of the resin film is insufficient.
• the polyimide resin film described in Patent Document 2 and Patent Document 3 has a problem that the film laminated on the polyimide resin film is peeled off or wrinkles are generated in the laminated film in the high temperature process at the time of manufacturing an electronic device. .. Therefore, an object of the present invention is to provide a transparent resin film capable of suppressing peeling and wrinkling of the film laminated on the resin film in a high temperature process.
• the present invention is a resin film containing a resin having a repeating unit represented by the chemical formula (1), has a light transmittance of 68% or more at a wavelength of 400 nm, and has a glass transition temperature (hereinafter, appropriately referred to as Tg).
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms.
• the present invention is a resin composition containing a resin having a repeating unit represented by the chemical formula (4) and a solvent, and the thickness of 10 ⁇ m obtained by applying the resin composition and firing at 410 ° C.
• a resin composition having a light transmittance of 68% or more at a wavelength of 400 nm, a Tg of 370 ° C. or higher, and a Td 0 of 440 ° C. or higher.
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms.
• R 1 and R 2 independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion, respectively. ..
• the resin film according to the present invention is required to be transparent and capable of suppressing the phenomenon that the film laminated on the resin film is peeled off or wrinkles are generated in the laminated film in a high temperature process in manufacturing an electronic device. It can be suitably used for the purpose of use.
• the resin film according to the embodiment of the present invention is a resin film containing a resin having a repeating unit represented by the chemical formula (1), has a light transmittance of 68% or more at a wavelength of 400 nm, and has a glass transition temperature. It is a resin film having a temperature of 370 ° C. or higher and a weight reduction start temperature of 440 ° C. or higher.
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms.
• Examples of the resin having a repeating unit represented by the chemical formula (1) include a polyimide resin, a polyetherimide resin, and a polyamideimide resin.
• the resin film according to the embodiment of the present invention has a light transmittance of 68% or more at a wavelength of 400 nm, it can be suitably used for applications requiring transparency.
• the film thickness of the resin film at this time is not particularly limited as long as the light transmittance is 68% or more, but it is preferably 4 ⁇ m or more, preferably 5 ⁇ m, from the viewpoint of the mechanical properties of the resin film. It is more preferably 6 ⁇ m or more, and further preferably 6 ⁇ m or more.
• the film thickness of the resin film is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 25 ⁇ m or less.
• the film thickness of the resin film is 4 ⁇ m or more and 40 ⁇ m or less, the mechanical properties of the resin film are good. Further, from the viewpoint of further improving the light transmittance of the resin film, the film thickness is preferably 0.5 ⁇ m or more and 4 ⁇ m or less, and more preferably 1 ⁇ m or more and 3 ⁇ m or less.
• the resin film according to the embodiment of the present invention has a light transmittance of 68% or more at a wavelength of 400 nm when the film thickness is converted to 10 ⁇ m.
• the light transmittance when the film thickness is converted to 10 ⁇ m is that the absorbance is proportional to the film thickness, and the film thickness is 10 ⁇ m from the value of the light transmittance obtained by measuring a resin film of a certain film thickness. The light transmittance in a certain case is calculated.
• the resin film according to the embodiment of the present invention has a glass transition temperature Tg of 370 ° C. or higher, the resin film is deformed and wrinkles are formed on the film formed on the resin film in the high temperature process in the manufacture of electronic devices. Can be suppressed.
• Tg glass transition temperature
• Tg is more preferably 380 ° C. or higher.
• Tg in the present invention is measured using a thermomechanical analyzer.
• the sample is heated to 150 ° C. at a temperature rising rate of 5 ° C./min
• the sample is air-cooled to room temperature at a temperature decreasing rate of 5 ° C./min
• the third stage The temperature of the sample is raised at a temperature rising rate of 5 ° C./min to obtain a value.
• the weight reduction start temperature Td 0 of the resin film according to the embodiment of the present invention is 440 ° C. or higher, it is formed on the resin film due to gas generation from the resin film in a high temperature process in the manufacture of an electronic device. It is possible to suppress the occurrence of a film floating phenomenon in which the formed film is peeled off.
• Td 0 is more preferably 450 ° C. or higher.
• Td 0 in the present invention is measured using a thermogravimetric measuring device.
• the sample is heated to 150 ° C. at a temperature rising rate of 10 ° C./min
• the sample is air-cooled to room temperature at a temperature decreasing rate of 10 ° C./min
• the third stage The temperature of the sample is raised at a temperature rising rate of 10 ° C./min to obtain a value.
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• the tetracarboxylic acid residue may be a tetravalent hydrocarbon group having 2 to 80 carbon atoms.
• A is a tetravalent organic group having 2 to 80 carbon atoms, which contains hydrogen and carbon as essential components and contains one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen. May be good.
• the number of each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen contained in this organic group is preferably in the range of 20 or less, and more preferably in the range of 10 or less. ..
• the tetracarboxylic acid that gives A is not particularly limited, and known ones can be used.
• p represents an integer of 0 to 3.
• q represents an integer of 1 to 4.
• tetracarboxylic acids can be used as raw materials for giving A as they are, or in the state of acid anhydride, active ester or active amide, and two or more of them may be used.
• A does not contain a fluorine atom in the chemical formula (1).
• A is a tetracarboxylic acid residue having a structure represented by the chemical formula (33) or a structure represented by the chemical formula (34). Alternatively, it more preferably has a 3,3', 4,4'-biphenyltetracarboxylic acid residue represented by the chemical formula (32), and has a 3,3', 4,4'-biphenyltetracarboxylic acid residue. Is particularly preferred.
• the tetracarboxylic acid that gives A enhances the applicability to the support when manufacturing the resin film and the resistance to oxygen plasma and UV ozone treatment used for cleaning when forming the element on the resin film. Therefore, silicon-containing tetracarboxylic acids such as dimethylsilanediphthalic acid and 1,3-bis (phthalic acid) tetramethyldisiloxane may be used. When these silicon-containing tetracarboxylic acids are used, it is preferable to use 1 to 30 mol% of the total tetracarboxylic acid.
• a part of hydrogen contained in the residue of the tetracarboxylic acid is a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group and an ethyl group, and a carbon such as a trifluoromethyl group. It may be substituted with a group of numbers 1 to 10, such as a fluoroalkyl group, F, Cl, Br, and I. Furthermore, if part of the hydrogen contained in the residue is replaced with an acidic group such as OH, COOH, SO 3 H, CONH 2 , SO 2 NH 2 , the solubility of the resin precursor in an alkaline aqueous solution becomes high. Since it improves, it is preferable when it is used as a photosensitive resin composition described later.
• B represents a divalent diamine residue having 2 or more carbon atoms, and the diamine residue is preferably a divalent hydrocarbon group having 2 to 80 carbon atoms.
• B is a divalent organic group having 2 to 80 carbon atoms, which contains hydrogen and carbon as essential components and contains one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen. May be good.
• the number of each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen contained in this organic group is preferably in the range of 20 or less, and more preferably in the range of 10 or less. ..
• the diamine that gives B is not particularly limited, and known diamines can be used.
• C represents an ether group, an ester group, an amide group, or a sulfonyl group.
• diamine having the structure represented by the chemical formula (31) include 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,3'-diaminodiphenyl sulfone. , 3,4'-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4-aminophenyl 4-aminobenzoate and the like.
• diamines can be used as they are, or as the corresponding trimethylsilylated diamines as diamines that give B, and two or more of these may be used.
• B does not contain a fluorine atom in the chemical formula (1).
• a and B are free of fluorine atoms.
• B in the chemical formula (1) has a diamine residue having a structure represented by the chemical formula (31), and 3,3'-. It is more preferred to have a diaminodiphenyl sulfone residue or a 4,4'-diaminodiphenyl sulfone residue. Particularly preferred is a tetracarboxylic acid residue having a structure in which A is represented by the chemical formula (33) or a structure represented by the chemical formula (34), or a 3,3', 4,4'-biphenyltetracarboxylic acid residue. B has a diamine residue having a structure represented by the chemical formula (31).
• A has a 3,3', 4,4'-biphenyltetracarboxylic acid residue and B has a 3,3'-diaminodiphenyl sulfone residue or a 4,4'-diaminodiphenyl sulfone residue.
• a and B have these structures, it is easy to obtain a resin film having excellent heat resistance and transparency.
• diamine giving B in order to enhance the coatability to the support when manufacturing the resin film and the resistance to oxygen plasma and UV ozone treatment used for cleaning when forming the element on the resin film.
• 1,3-Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-anilino) tetramethyldisiloxane and other silicon-containing diamines may be used.
• silicon-containing diamine compounds it is preferable to use 1 to 30 mol% of the total diamine compound.
• a part of hydrogen contained in the diamine compound has a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group and an ethyl group, and 1 to 10 carbon atoms such as a trifluoromethyl group. It may be substituted with a fluoroalkyl group, a group such as F, Cl, Br, I or the like. Furthermore, if a part of hydrogen contained in the diamine compound is replaced with an acidic group such as OH, COOH, SO 3 H, CONH 2 , SO 2 NH 2 , the solubility of the resin precursor in an alkaline aqueous solution becomes high. Since it improves, it is preferable when it is used as a photosensitive resin composition described later.
• the value obtained by dividing the number of moles of the diamine residue contained in the resin by the number of moles of the tetracarboxylic acid residue is not particularly limited, but is 0.4 or more. It is preferably present, and more preferably 0.6 or more.
• the division value Ka is preferably 0.95 or less, more preferably 0.9 or less, and even more preferably 0.8 or less. When the division value Ka is 0.4 or more, the mechanical properties of the resin film are good. When the division value Ka is 0.95 or less, it is preferable because more structures represented by the chemical formula (2) described later can be contained.
• the resin preferably has a structure represented by the chemical formula (2).
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms
• Z represents an aminosilane residue having 1 to 10 carbon atoms
• R 3 represents a hydrocarbon group having 1 to 20 carbon atoms.
• n indicates 2 or 3.
• X represents a structure represented by the chemical formula (3), and the oxygen atom in the chemical formula (3) and the Si atom in the chemical formula (2) are bonded.
• the resin film containing the resin having the structure represented by the chemical formula (2) tends to have a preferably high light transmittance, Tg and Td 0.
• the structure represented by the chemical formula (2) defines the structure of the terminal of the resin having the repeating unit represented by the chemical formula (1), and the terminal of the resin is represented by the chemical formula (1).
• the unit is a tetracarboxylic acid terminal, it can be considered as a structure in which an aminosilane compound having a siloxane structure is imide-bonded to the tetracarboxylic acid structure at the terminal. Since the siloxane binding site is excellent in heat resistance and light transmittance, the light transmittance and Td 0 of the resin film are higher.
• the end of the polymer structure having the repeating unit represented by the chemical formula (1) is fixed by a siloxane bond, and the thermal motion of the resin is restricted. Therefore, it is estimated that the Tg of the resin film becomes higher.
• Z represents an aminosilane residue having 1 to 10 carbon atoms
• examples of Z include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms.
• These hydrocarbon groups may have a linear, branched or cyclic structure.
• Z is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a phenyl group.
• R 3 represents a hydrocarbon group having 1 to 20 carbon atoms.
• R 3 an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms Group etc. can be mentioned. These hydrocarbon groups may have a linear, branched or cyclic structure.
• R 3 is preferably an aromatic hydrocarbon group having an aliphatic hydrocarbon group or a C 6-20 having 1 or 2 carbon atoms, a methyl group or a phenyl group Is more preferable.
• n 2 or 3, but it is preferably 3.
• n 3
• the siloxane binding site has a three-dimensional structure, so that the Tg of the resin film is more likely to be improved.
• the value obtained by dividing the number of moles of aminosilane residues contained in the resin by the number of moles of tetracarboxylic acid residues is preferably 0.1 or more, and 0. It is more preferably 2 or more, and further preferably 0.4 or more.
• the division value Kb is preferably 1.2 or less, and more preferably 0.9 or less.
• the resin contains many structures represented by the chemical formula (2), so that the transparency and heat resistance of the resin film are more likely to be improved.
• the division value Kb is 1.2 or less, the mechanical properties of the resin film are good.
• X indicates the structure represented by the above chemical formula (3), and the oxygen atom in the chemical formula (3) and the Si atom in the chemical formula (2) are bonded.
• bond destinations that bond with Si atoms in chemical formula (3) include carbon atoms that make up R 3 in chemical formula (2), carbon atoms that make up Z in chemical formula (2), hydrogen atoms, and hydroxyl groups.
• the Si atom in the chemical formula (3) may be bonded to the Si atom in another chemical formula (2) or (3) via an oxygen atom to repeatedly have a chain or network structure of a siloxane structure.
• the Si atom in the chemical formula (3) may be a Si atom in another chemical formula (2), and a part of the Si atom of the repeating structure represented by the chemical formula (3) may be another chemical formula (2). It may be a Si atom inside.
• the structure in which the Si atom in the chemical formula (3) is a Si atom in another chemical formula (2) can be regarded as a structure in which the resins having the structure of the chemical formula (2) are crosslinked by the siloxane structure, and the resin film. Tg is more likely to be improved, which is preferable.
• the resin composition according to the embodiment of the present invention is a resin composition containing a resin having a repeating unit represented by the chemical formula (4) and a solvent, and the resin composition is applied and fired at 410 ° C.
• firing at 410 ° C means firing at 410 ° C for 30 minutes.
• the characteristics of a resin film having a thickness of 10 ⁇ m obtained by firing at 410 ° C. are usually specified at 410 ° C.
• the film thickness of about 10 um is based on the fact that a film thickness of about 10 um is mainly used in applications where mechanical properties are required (for example, a display substrate).
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms.
• R 1 and R 2 independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion, respectively. ..
• the resin composition according to the embodiment of the present invention has a light transmittance of 68% or more of the obtained resin film, the resin composition can be suitably used for applications requiring transparency.
• the Tg of the obtained resin film is 370 ° C. or higher, wrinkles occur in the film formed on the resin film in the high temperature process in the manufacture of electronic devices. Therefore, it can be suitably used for electronic device applications that pass through a high temperature process during manufacturing. Further, the higher the Tg of the resin film, the higher the process temperature for manufacturing the electronic device, which is preferable. For example, the Tg of the obtained resin film is more preferably 380 ° C. or higher.
• the obtained resin film since the obtained resin film has a Td 0 of 440 ° C. or higher, the film formed on the resin film is peeled off in a high temperature process in the manufacture of an electronic device. Since it is possible to suppress the occurrence of the phenomenon, it can be suitably used for electronic device applications that pass through a high temperature process during manufacturing. Further, the higher the Td 0 of the resin film, the higher the process temperature for manufacturing the electronic device, which is preferable. For example, the Td 0 of the obtained resin film is more preferably 450 ° C. or higher.
• the resin having the repeating unit represented by the chemical formula (4) is a resin that can be converted into the resin having the repeating unit represented by the chemical formula (1) by heat treatment, chemical treatment, or the like.
• the resin having the repeating unit represented by the chemical formula (4) and the resin having the structure represented by the chemical formula (5) described below are referred to as “precursor resin”.
• a resin composition containing a precursor resin is referred to as a "precursor resin composition”.
• the precursor resin include a polyimide precursor resin, a polyetherimide precursor resin, and a polyamideimide precursor resin.
• Specific examples and preferable examples of A in the chemical formula (4) include the above-mentioned specific examples of A in the chemical formula (1) and the structures described as preferable examples.
• Specific examples and preferable examples of B in the chemical formula (4) include the structures described as specific examples of B in the chemical formula (1) described above.
• the value obtained by dividing the number of moles of diamine residues contained in the precursor resin by the number of moles of tetracarboxylic acid residues is 0.4 or more. It is preferably 0.6 or more, and more preferably 0.6 or more.
• the division value Kc is preferably 0.9 or less, and more preferably 0.8 or less. When the division value Kc is 0.4 or more, the mechanical properties of the obtained resin film are good. When the division value Kc is 0.9 or less, it is preferable because more structures represented by the following chemical formula (5) can be contained.
• the precursor resin preferably has a structure represented by the chemical formula (5).
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms.
• R 1 and R 2 independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion, respectively. ..
• R 3 and R 4 each independently represent a hydrocarbon group having 1 to 20 carbon atoms.
• n indicates 2 or 3.
• the precursor resin composition containing the precursor resin having the structure represented by the chemical formula (5) has a light transmittance of a resin film having a thickness of 10 ⁇ m obtained by applying the resin composition and firing at 410 ° C. Tg and Td 0 tend to be higher.
• a precursor resin having a structure represented by the chemical formula (5) has a tetracarboxylic acid structure at the terminal when the terminal of the precursor resin is a tetracarboxylic acid terminal of a repeating unit represented by the chemical formula (4). It can be considered that the structure is such that an aminosilane compound having a hydrolyzable silyl group is bonded to and an amic acid is formed.
• the amic acid structure is converted to an imide structure by calcination, and the hydrolyzable silyl group is converted to a siloxane structure by calcination. That is, the structure represented by the chemical formula (5) is a structure that can be converted into the structure represented by the chemical formula (2) by heating. Therefore, the resin film obtained by firing the precursor resin composition containing the precursor resin having the structure represented by the chemical formula (5) contains the resin having the structure represented by the chemical formula (2). It is considered that the light transmittance, Tg and Td 0 of the resin film obtained by firing as shown above are higher.
• R 3 in the formula (5) include the structures described as specific examples and preferred examples of R3 in the above-mentioned chemical formula (2).
• examples of R 4 and aromatic hydrocarbon groups aliphatic hydrocarbon group and having 6 to 20 carbon atoms having 1 to 20 carbon atoms. These hydrocarbon groups may have a linear, branched or cyclic structure.
• n 2 or 3, but it is preferably 3.
• n 3 since the siloxane binding site after firing has a three-dimensional structure, the Tg of the resin film is more likely to be improved.
• aminosilane compound giving the chemical formula (5) examples include 4-aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 4-aminophenylmethyldimethoxysilane, 4-aminophenylmethyldiethoxysisilane, 3 -Aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 3-aminophenylmethyldimethoxysilane, 3-aminophenylmethyldiethoxysisilane, 2-aminophenyltrimethoxysilane, 2-aminophenyltriethoxysilane, 2 -Aminophenylmethyldimethoxysilane, 2-aminophenylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropy
• aminosilane compound selected from 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane is preferable.
• the value obtained by dividing the number of moles of aminosilane residues contained in the precursor resin by the number of moles of tetracarboxylic acid residues is preferably 0.1 or more. It is more preferably 0.2 or more, and further preferably 0.4 or more.
• the division value Kd is preferably 1.2 or less, and more preferably 0.9 or less.
• the division value Kd is 0.1 or more, the precursor resin contains many structures represented by the chemical formula (5), so that the transparency and heat resistance of the obtained resin film are more likely to be improved.
• the division value Kd is 1.2 or less, the mechanical properties of the obtained resin film are good.
• the precursor resin in addition to the repeating unit represented by the chemical formula (4) described above, the precursor resin has a repeating unit represented by the chemical formula (61), a repeating unit represented by the chemical formula (62), and a chemical formula. It may further contain at least one of the repeating units represented by (1).
• A, B, R 1 and R 2 in the above chemical formulas (61) and (62), and chemical formula (1) are as described above.
• the repeating unit represented by the chemical formula (61), the repeating unit represented by the chemical formula (62), and the repeating unit represented by the chemical formula (1) are each obtained by heat-treating the repeating unit represented by the chemical formula (4).
• the structure is imide-closed by chemical treatment or the like. That is, the repeating unit represented by the chemical formula (4), the repeating unit represented by the chemical formula (61), the repeating unit represented by the chemical formula (62), and the repeating unit represented by the chemical formula (1).
• the precursor resin containing at least one of them can also be regarded as a partially imidized precursor resin.
• the imidization ratio of the polyimide precursor is a value represented by "(t + u + 2v) / (2s + 2t + 2u + 2v) x 100".
• the imidization ratio is the ratio of the number of imide-closed bonding portions "t + u + 2v” to the total number of bonding portions "2s + 2t + 2u + 2v” in the bonding portion of the polyimide precursor (reaction portion between the tetracarboxylic acid dianhydride and the diamine compound). Shown.
• the imidization ratio of the precursor resin is preferably 5 to 30%.
• the imidization ratio is more preferably 10% or more, and further preferably 13% or more. Further, it is more preferably 27% or less, and further preferably 25% or less.
• the imidization ratio of the precursor resin is measured as follows. First, the 1 H-NMR spectrum of the precursor resin is measured. Table in each Subsequently, the integral value of the peak of the 1 H amide groups and (the epsilon), the chemical formula contained in the precursor resin (4), formula (61) or formula (62), and the chemical formula (1) the molar ratio of respective repeating units is 100: 0: when was 0, obtains the integral value of peaks of the 1 H amide groups (and ⁇ to) and. That is, obtaining the integrated value of the peaks of the 1 H amide groups when the precursor resin is assumed to be a state of complete amide acid resins which are not imidized. Using these ⁇ and ⁇ , the imidization ratio can be calculated by the following equation.
• Imidization rate ( ⁇ - ⁇ ) / ⁇ ⁇ 100
• ⁇ can be obtained by the following equation.
• alpha is the chemical formula (4), formula (61), formula (62), and the chemical formula (1) in the integral value of the peak of all of the 1 H or certain of the 1 H contained in A and B in be.
• ⁇ is the number of hydrogen atoms targeted when ⁇ was calculated.
• the measurement sample of 1 H-NMR is preferably the precursor resin alone, but may contain other resin components and solvents. However, the peak of the 1 H contained in the other components, it is preferable that does not overlap with the peaks of the 1 H as an index for calculating the imidization ratio.
• the solvent contained in the precursor resin composition can be used without particular limitation as long as it dissolves the precursor resin.
• solvents include, for example, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-.
• Aprotonic polar solvents such as N, N-dimethylpropionamide, N, N-dimethylisobutylamide, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, dimethylsulfoxide, tetrahydrofuran, dioxane , Ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether and other ethers, acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone and other ketones, Ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, 3-methyl-3-methoxybutyl acetate, ethylene glycol ethyl
• the precursor resin composition may contain the silane compound (h).
• the silane compound (h) is preferably a compound having a structure represented by the chemical formula (7).
• R 5 and R 6 each independently represent a hydrocarbon group having 1 to 20 carbon atoms. m indicates 3 or 4.
• the silane compound (h) condenses during firing of the precursor resin composition to form a siloxane bond. Therefore, since the siloxane portion is formed in the resin film obtained by firing, the light transmittance of the resin film can be further improved.
• the precursor resin composition contains a precursor resin having a structure represented by the chemical formula (5)
• the silane compound (h) and the hydrolyzable silyl group in the chemical formula (5) are condensed during firing. Since a siloxane bond is formed, phase separation between the resin contained in the resin film and the siloxane site is suppressed, and a resin film having more excellent light transmittance can be easily obtained.
• examples of R 6, and aromatic hydrocarbon groups aliphatic hydrocarbon group and having 6 to 20 carbon atoms having 1 to 20 carbon atoms. These hydrocarbon groups may have a linear, branched or cyclic structure.
• Examples of the compound having the structure represented by the chemical formula (7) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and ethyltri. Examples thereof include methoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
• the content of the silane compound (h) is preferably 15 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the precursor resin composition.
• the content of the silane compound (h) is 15 parts by mass or more, the light transmittance of the resin film is likely to be improved. If it is 100 parts by mass or less, a resin film having good mechanical properties can be easily obtained.
• the precursor resin composition is, if necessary, a photoacid generator (a), a thermal cross-linking agent (b), a thermal acid generator (c), a compound containing a phenolic hydroxyl group (d), and an adhesion improver. It may contain at least one additive selected from (e), surfactant (f), and inorganic particles (g). Specific examples of these additives include those described in International Publication No. 2017/099183.
• the concentration of the precursor resin in the precursor resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the precursor resin composition. Further, 50% by mass or less is preferable, and 40% by mass or less is more preferable.
• the viscosity of the precursor resin composition is preferably 20 to 20,000 mPa ⁇ s, more preferably 50 to 10,000 mPa ⁇ s.
• Method for producing precursor resin composition Next, a method for producing the precursor resin composition will be described.
• the precursor resin a silane compound (h), a photoacid generator (a), a thermal cross-linking agent (b), a thermal acid generator (c), and a phenolic hydroxyl group, if necessary, are used.
• the compound (d) containing the above, the adhesion improver (e), the surfactant (f), the inorganic particles (g) and the like are dissolved or dispersed in a solvent. Thereby, a varnish which is one of the precursor resin compositions can be obtained.
• the precursor resin having the repeating unit represented by the chemical formula (4) can be polymerized by a known method. For example, it can be obtained by polymerizing a tetracarboxylic acid or a corresponding acid dianhydride, an active ester, an active amide or the like as an acid component and a diamine or a corresponding trimethylsilylated diamine or the like as a diamine component in a reaction solvent. .. Further, in the precursor resin, the carboxy group forms a salt with an alkali metal ion, an ammonium ion, and an imidazolium ion, or is esterified with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms. It may be an esterified product.
• the reaction solvent for example, the solvent described as a specific example of the solvent contained in the precursor resin composition described above can be used alone or in combination of two or more.
• the amount of the reaction solvent used is preferably adjusted so that the total amount of the tetracarboxylic acid and the diamine compound is 0.1 to 50% by mass of the total amount of the reaction solution.
• the reaction temperature is preferably ⁇ 20 ° C. to 150 ° C., more preferably 0 to 100 ° C.
• the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.
• precursor resin having the structure represented by the chemical formula (5) is produced by the method described below.
• Manufacturing method 1 In the first production method, the tetracarboxylic acid dianhydride is reacted with the aminosilane compound in the first step to produce the compound represented by the chemical formula (9), and the chemical formula (9) is produced in the second step. ) Is reacted with a diamine compound and a tetracarboxylic acid dianhydride to produce a precursor resin having a structure represented by the chemical formula (5).
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms.
• R 3 and R 4 each independently represent a hydrocarbon group having 1 to 20 carbon atoms.
• n indicates 2 or 3.
• Manufacturing method 2 In the second production method, in the first step, the diamine compound is reacted with the tetracarboxylic acid dianhydride to produce a precursor resin having a repeating unit represented by the chemical formula (4), and in the second step, This is a production method in which a resin having a structure represented by the chemical formula (10) is reacted with an aminosilane compound to produce a precursor resin having a structure represented by the chemical formula (5).
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms
• R 2 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion.
• precursor resin having the structure represented by the chemical formula (5) may be produced by using the production methods 1 and 2 in combination.
• the corresponding acid dianhydride, active ester, active amide and the like can also be used as the tetracarboxylic dian.
• the diamine compound the corresponding trimethylsilylated diamine or the like can also be used.
• the carboxy group of the obtained resin is a salt formed of an alkali metal ion, an ammonium ion or an imidazolium ion, it is esterified with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms. It may be an esterified product.
• the obtained precursor resin solution may be used as it is as the precursor resin composition according to the embodiment of the present invention.
• the desired precursor resin composition can be obtained without isolating the precursor resin by using the same solvent as the one used for the precursor resin composition as the reaction solvent or by adding the solvent after the reaction is completed. Can be obtained.
• the obtained precursor resin a part of the repeating unit of amic acid may be further imidized or esterified.
• the precursor resin solution obtained by polymerizing the precursor resin may be used as it is in the next reaction, or the precursor resin may be isolated and then used in the next reaction.
• the precursor resin in the esterification reaction and imidization reaction of the precursor resin, can be simply obtained by using the same solvent as the reaction solvent used in the precursor resin composition or by adding a solvent after the reaction is completed.
• the desired precursor resin composition can be obtained without separation.
• This method for producing a resin film is an example of a method for producing a resin film according to an embodiment of the present invention from the precursor resin composition described above.
• a varnish which is one of the precursor resin compositions according to the embodiment of the present invention, is applied onto the support.
• the support include wafer substrates such as silicon and gallium arsenic, glass substrates such as sapphire glass, soda lime glass, and non-alkali glass, metal substrates such as stainless steel and copper, metal foils, and ceramic substrates.
• wafer substrates such as silicon and gallium arsenic
• glass substrates such as sapphire glass, soda lime glass, and non-alkali glass
• metal substrates such as stainless steel and copper, metal foils, and ceramic substrates.
• non-alkali glass is preferable from the viewpoint of surface smoothness and dimensional stability during heating.
• Examples of the varnish coating method include a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, and the like, and these may be combined.
• the resin film is used as a display substrate, it is necessary to apply it on a large-sized support, and therefore the slit application method is particularly preferably used.
• a drying method vacuum drying, heat drying, or a combination thereof can be used.
• a method of vacuum drying for example, a support in which a coating film is formed is placed in a vacuum chamber, and the coating film is dried by reducing the pressure in the vacuum chamber.
• a method of heat-drying a method of drying a coating film using a hot plate, an oven, infrared rays and the like can be mentioned.
• a hot plate is used, the support on which the coating film is formed is held and the coating film is heated and dried directly on the plate or on a jig such as a proxy pin installed on the plate.
• the heating temperature varies depending on the type and purpose of the solvent used for the varnish, and it is preferable to heat the varnish in the range of room temperature to 180 ° C. for 1 minute to several hours.
• a pattern can be formed from the dried coating film by the method described below.
• chemical rays are irradiated and exposed through a mask having a desired pattern on the coating film.
• Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps can be used. preferable.
• the coating film has positive photosensitivity, the exposed portion of the coating film dissolves in the developer.
• the coating film has a negative photosensitive property, the exposed portion of the coating film is cured and insolubilized in a developing solution.
• a developing solution is used to remove the exposed part in the case of the positive type and the non-exposed part in the case of the negative type to form a desired pattern on the coating film.
• an aqueous solution of an alkaline compound such as tetramethylammonium is preferable in both the positive type and the negative type.
• a polar solvent such as N-methyl-2-pyrrolidone, alcohols, esters, ketones and the like may be added alone or in combination of a plurality of kinds to these alkaline aqueous solutions.
• a heating process is performed in which the coating film on the support is heat-treated to produce a resin film.
• the coating film is heat-treated at 370 ° C. or higher and 600 ° C. or lower, preferably 400 ° C. or higher and 490 ° C. or lower, more preferably 410 ° C. or higher and 470 ° C. or lower, and the coating film is fired.
• the heating temperature (calcination temperature) of the coating film in the heating step is 370 ° C. or higher, imidization proceeds sufficiently and a resin film having excellent mechanical properties can be obtained.
• the heating temperature is 400 ° C. or higher, a resin film having excellent heat resistance can be obtained.
• the heating temperature is 490 ° C. or lower, thermal decomposition of the resin is suppressed, and a resin film having a high transmittance can be obtained.
• the resin film obtained through the above coating step and heating step can be used by peeling from the support, or can be used as it is without peeling from the support.
• Examples of the peeling method include a mechanical peeling method, a method of immersing in water, a method of immersing in a chemical solution such as hydrochloric acid or hydrofluoric acid, and a laser beam in the wavelength range from ultraviolet light to infrared light with a resin film and a support.
• a method of irradiating the interface of the above can be mentioned.
• peeling is performed after the device is formed on the resin film, it is necessary to perform the peeling without damaging the device, so that peeling using an ultraviolet laser is preferable.
• a mold release agent may be applied to the support or a sacrificial layer may be formed before the resin composition is applied to the support.
• the release agent include silicone-based, fluorine-based, aromatic polymer-based, and alkoxysilane-based.
• the sacrificial layer include a metal film, a metal oxide film, an amorphous silicon film, and the like.
• the resin film according to the embodiment of the present invention is suitably used for display substrates such as organic EL display substrates, color filter substrates, touch panel substrates, electronic paper substrates, and ⁇ LED display substrates, and is particularly flexible display substrates. It is preferably used for.
• flexible printed substrates, substrates for solar cells, surface protective films and interlayer insulating films for semiconductor elements, insulating layers and spacer layers for organic electroluminescence elements (organic EL elements), flattening films for thin film transistor substrates, and insulating layers for organic transistors. Used as a binder for electrodes of lithium ion secondary batteries, an adhesive for semiconductors, and the like.
• the display according to the embodiment of the present invention includes the resin film according to the embodiment of the present invention.
• An example of a configuration of a display according to an embodiment of the present invention includes a resin film and a display element formed on the resin film.
• the resin film is the resin film according to the embodiment of the present invention and functions as a display substrate.
• a display element is formed on the resin film.
• a film manufacturing step of manufacturing a resin film on a support by the above-mentioned resin film manufacturing method, a step of forming a display element on the resin film, and a resin film being formed from the support. Includes a peeling step for peeling.
• the resin film according to the embodiment of the present invention is manufactured on the support according to the above-mentioned method for manufacturing the resin film.
• an inorganic film may be provided on the resin film.
• the inorganic film By providing the inorganic film, it is possible to prevent moisture and oxygen from passing through the resin film from the outside and causing deterioration of the display element.
• the inorganic film include silicon oxide (SiOx), silicon nitride (SiNy), and silicon oxynitride (SiOxNy). These can be used as a single layer or in a laminated manner of a plurality of types.
• the method for forming these inorganic films is preferably performed by using a vapor deposition method such as a chemical vapor deposition method (CVD) or a physical vapor deposition method (PVD).
• CVD chemical vapor deposition method
• PVD physical vapor deposition method
• These inorganic films can also be used by alternately laminating a plurality of layers of a resin film and an inorganic film.
• the resin film laminated with the inorganic film is preferably the resin film according to the embodiment of the present invention. Further, another resin film may be formed on the support, and the inorganic film and the resin film according to the embodiment of the present invention may be alternately laminated on the resin film.
• a display element corresponding to the target display is formed on the obtained resin film or a laminate of the resin film and the inorganic film.
• the organic EL element is formed as a target display element by forming the TFT, the first electrode, the light emitting element, the second electrode, and the sealing film, which are the display elements, in this order. ..
• the display is a liquid crystal display
• a liquid crystal cell is used by using a first substrate on which the TFT, the first electrode, and the first alignment film, which are image driving elements, are formed, and a second substrate on which the second electrode and the second alignment film are formed.
• a liquid crystal display element is formed as a target display element by forming the liquid crystal display element.
• a color filter element is formed as a target display element by forming a black matrix as needed and then forming colored pixels such as red, green, and blue.
• the touch panel element is formed as a target display element by forming the wiring layer and the insulating layer.
• a display containing the resin film of the present invention can be obtained.
• the method of peeling at the interface between the support and the resin film include a method using a laser, a mechanical peeling method, and a method of etching the support.
• the support such as a glass substrate can be peeled off without damaging the element by irradiating the support with the laser from the side where the element is not formed.
• a primer layer for facilitating peeling may be provided between the support and the support.
• Imidization rate ( ⁇ - ⁇ ) / ⁇ ⁇ 100
• ⁇ ⁇ / ⁇ ⁇ 2
• ⁇ the number of hydrogen atoms targeted when ⁇ was obtained.
• a laminate of a resin film and a glass substrate was prepared for each resin film obtained in each example, and the prepared laminate was subjected to a resin at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). The light transmittance of the film was measured.
• Tg Tg of resin film
• the temperature of the sample was raised to 150 ° C. at a temperature rising rate of 5 ° C./min, whereby the adsorbed water of this sample was removed.
• the sample was air-cooled to room temperature at a temperature reduction rate of 5 ° C./min.
• the temperature of the sample was raised at a temperature rising rate of 5 ° C./min, and the Tg of the sample was measured.
• Td 0 Measurement of Td 0 of resin film
• Td 0 was measured using a thermogravimetric measuring device (manufactured by Shimadzu Corporation, TGA-50).
• TGA-50 thermogravimetric measuring device
• the temperature of the sample was raised to 150 ° C. at a temperature rising rate of 10 ° C./min, whereby the adsorbed water of this sample was removed.
• the sample was air-cooled to room temperature at a temperature reduction rate of 10 ° C./min.
• Td 0 of the sample was measured at a heating rate of 10 ° C./min.
• the laminate composed of the resin film and the glass substrate obtained in each example is subjected to heat treatment at 425 ° C. or 450 ° C. for 30 minutes after forming a SiO film having a thickness of 50 nm on the resin film by CVD. rice field. Then, the presence or absence of wrinkles in the SiO film on the resin film was derived by visual observation and observation with an optical microscope. Those with wrinkles at 425 ° C. were evaluated as "C”, those with wrinkles only at 450 ° C. were evaluated as "B”, and those without wrinkles were evaluated as "A".
• the laminate composed of the resin film and the glass substrate obtained in each example was subjected to heat treatment at 450 ° C. for 120 minutes after forming a SiO film having a thickness of 50 nm on the resin film by CVD. Then, the number of film floats in which the SiO film floats from the resin film was derived by visual observation and observation with an optical microscope. The evaluation range was the entire surface (length 350 mm ⁇ width 300 mm), and the observation magnification was 50 times.
• Table 1 shows the composition of each resin composition (varnish) obtained in Synthesis Examples 1 to 19.
• Example 1 Using the resin composition (varnish) obtained in Synthesis Example 1, the rate of change in viscosity of the resin precursor composition was measured by the method of the first item, and the resin precursor was imidized by the method of the second item. The rate was measured.
• the resin composition of Synthesis Example 1 was placed on a non-alkali glass substrate (AN-100, manufactured by Asahi Glass Co., Ltd.) having a length of 350 mm, a width of 300 mm, and a thickness of 0.5 mm.
• An object (varnish) was applied to an area 5 mm inside from the edge of the glass substrate.
• the same apparatus was used to perform heating vacuum drying at a temperature of 40 ° C.
• the glass substrate was irradiated with a laser (wavelength: 308 nm) from the side where the resin film was not formed, and peeled off at the interface with the resin film.
• Tg was measured by the method of the fourth item
• Td 0 was measured by the method of the fifth item
• the tensile elongation and the maximum tensile stress were measured by the method of the sixth item.
• the wrinkle evaluation was carried out by the method of the above 7th item, and the film floating evaluation was carried out by the method of the 8th item.
• Examples 2 to 11, Comparative Examples 1 to 9 In Examples 2 to 11, Comparative Examples 1 to 6, and Comparative Examples 8 to 9, the same evaluations as in Example 1 were carried out using the resin compositions (varnishes) of Synthesis Examples 2 to 19 shown in Table 1. went.
• Comparative Example 7 the same evaluation as in Example 1 was performed except that the heating conditions were changed from 410 ° C to 350 ° C.
• Table 2 shows the evaluation results of Examples 1 to 11 and Comparative Examples 1 to 9.
• Example 12 A resin film was prepared in the same manner as in Example 1 except that the film thickness of 10 ⁇ m in Example 1 was changed to 2 ⁇ m.
• the light transmittance of the resin film was measured by the method of the third item, Tg was measured by the method of the fourth item, and Td 0 was measured by the method of the fifth item.
• the light transmittance was 83%, Tg was 378 ° C, and Td 0 was 450 ° C.
• a resin film was formed on the glass substrate by the same method as in Example 1. Subsequently, a SiO film having a thickness of 50 nm was formed on the resin film by CVD, and then a resin film having a film thickness of 2 um was formed on the SiO film by the same method.
• wrinkle evaluation was carried out by the method of the above 7th item, and film floating evaluation was carried out by the method of the 8th item. The result of the wrinkle evaluation was "A", and the result of the film floating evaluation was 0, showing good results.

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