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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • 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
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  • 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
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  • 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
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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  • 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
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
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  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells

Definitions

• the present invention relates to a polyamic acid solution composition capable of obtaining a polyimide having excellent transparency and having a linear expansion coefficient (CTE), particularly a linear expansion coefficient controlled at a relatively low temperature.
• CTE linear expansion coefficient
• Polyimides obtained from tetracarboxylic dianhydrides and diamines are widely used in the electrical and electronics industries because of their excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance.
• polyimide has poor solubility in an organic solvent, usually, a solution composition (polyamic acid solution composition) in which a polyimide precursor polyamic acid is dissolved in a solvent is applied onto a substrate surface, for example, and then A polyimide is obtained by heating at a high temperature to cause dehydration ring closure (imidization).
• polyimide generally tends to be colored yellowish brown due to intramolecular conjugation or formation of a charge transfer complex, and improvement in transparency is required depending on the application.
• Patent Document 1 discloses a polyimide excellent in light transmittance obtained from cyclopentane-1,2,3,4-tetracarboxylic dianhydride, which is an alicyclic tetracarboxylic dianhydride, and an aromatic diamine. Is disclosed. However, polyimides using alicyclic tetracarboxylic dianhydrides and / or alicyclic diamines as monomer components tend to be inferior in heat resistance and chemical resistance compared to aromatic polyimides.
• Patent Document 2 discloses a polyimide having a fluorene skeleton and excellent in translucency.
• the polyimide having this fluorene skeleton may not always have sufficient transparency.
• polyimides having a fluorene skeleton tend to have a relatively high linear expansion coefficient.
• Patent Document 3 includes 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3.
• Aromatic dianhydride components including 4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-bis Selected from (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-bis (3-aminophenoxy) diphenylsulfone, bis (3-aminophenyl) sulfone and bis (4-aminophenyl) sulfone
• a polyimide having excellent transparency obtained from an aromatic diamine component containing one or more of them is disclosed. However, this polyimide does not necessarily have a sufficiently low linear expansion coefficient, and the linear expansion
• Patent Document 4 a polyamic acid prepared such that the molecular chain terminal is an acid anhydride and a compound having a substituent capable of binding to a polymer such as 3-aminopropyltriethoxysilane (coupling)
• a polyimide / silica hybrid material obtained by reacting with (reagent) and then reacting by adding tetraethoxysilane (heat imidization / conversion to silica) is disclosed.
• the aminopropyl group may be thermally decomposed during thermal imidization, and the transmittance of the resulting polyimide may be reduced.
• An object of the present invention is to provide a polyamic acid solution composition which is excellent in transparency and can obtain a polyimide whose linear expansion coefficient, particularly a linear expansion coefficient at a high temperature, is controlled to be relatively low.
• the present invention relates to the following matters.
• a tetracarboxylic acid component containing a fluorine atom-containing tetracarboxylic dianhydride in an amount of 50 mol% or more and a diamine component containing a fluorine atom-containing diamine in an amount of 50 mol% or more are reacted in a solvent.
• Colloidal silica is dispersed in an organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component.
• a polyamic acid solution composition obtained by adding a colloidal solution. Item 2.
• the polyamic acid solution composition according to Item 1 wherein the amount of silica added is 5 to 70 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. . 3.
• Item 3 The polyamic acid solution composition according to any one of Items 1 to 2, wherein the silica has a particle size of 1 to 60 nm.
• the polyimide obtained by heat-treating the polyamic acid solution composition has a light transmittance at a wavelength of 400 nm of a film having a thickness of 10 ⁇ m of 70% or more, and a linear expansion coefficient of 300 to 400 ° C. is 350 ppm / ° C. or less.
• Item 4. The polyamic acid solution composition according to any one of Items 1 to 3, wherein 5.
• Item 5. The polyamic acid solution composition according to item 4, wherein the polyimide obtained by heat-treating the polyamic acid solution composition has a linear expansion coefficient at 300 to 400 ° C of 250 ppm / ° C or less.
• the tetracarboxylic dianhydride containing a fluorine atom is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
• the diamine containing a fluorine atom is 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl and / or 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoro.
• Item 6 The polyamic acid solution composition according to any one of Items 1 to 5, which is propane.
• Producing a polyamic acid solution In the obtained polyamic acid solution, colloidal silica is dispersed in an organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component.
• a method for producing a polyamic acid solution composition comprising the steps of adding and mixing a colloidal solution.
• a method of manufacturing a flexible device which is a display device or a light receiving device, The step of applying the polyamic acid solution composition according to any one of Items 1 to 6 on a carrier substrate and heat-treating it to form a solid polyimide resin film, and the step of forming a circuit on the polyimide resin film And the manufacturing method of the flexible device characterized by including the process of peeling the polyimide resin film in which the said circuit was formed in the surface from the said carrier substrate.
• a flexible device which is a display device or a light receiving device manufactured by the method for manufacturing a flexible device according to Item 10.
• a polyamic acid solution composition capable of obtaining a polyimide having excellent transparency and a linear expansion coefficient, particularly a linear expansion coefficient at a high temperature (for example, a linear expansion coefficient of 300 to 400 ° C.) controlled to be relatively low. Can be provided.
• the polyimide obtained from the polyamic acid solution composition of the present invention that is, the polyimide of the present invention has high transparency and a linear expansion coefficient, particularly a linear expansion coefficient at a high temperature (for example, a linear expansion coefficient of 300 to 400 ° C.). Is controlled low.
• the polyimide of the present invention can be suitably used for an electric device, an electronic device, and an optical device.
• a display device such as a liquid crystal display, an EL display, and electronic paper, a touch panel, a solar cell, a substrate for an LED lighting device, or It can be suitably used as a protective film.
• it can be suitably used as a substrate for flexible devices such as display devices such as liquid crystal displays, organic EL displays and electronic paper, and light receiving devices such as light receiving elements of thin film solar cells.
• the polyamic acid in the polyamic acid solution composition of the present invention contains a tetracarboxylic dianhydride containing a fluorine atom in an amount of 50 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, particularly preferably 90.
• the tetracarboxylic acid component contained in an amount of at least mol% and the diamine containing a fluorine atom in an amount of at least 50 mol%, preferably at least 75 mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%. It is obtained from the diamine component contained.
• the tetracarboxylic acid component includes tetracarboxylic acid and tetracarboxylic acid derivatives such as tetracarboxylic dianhydride.
• the polyamic acid of the present invention comprises a repeating unit represented by the following chemical formula (1).
• a in chemical formula (1) is a chemical structure derived from a tetracarboxylic acid component, which is a tetravalent group obtained by removing a carboxyl group from tetracarboxylic acid
• B is a chemical structure derived from a diamine component.
• a divalent group obtained by removing an amino group from a diamine provided that 50 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more of A is a fluorine atom.
• Examples of the tetracarboxylic dianhydride containing a fluorine atom used in the present invention include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) represented by the following formula (2).
• the tetracarboxylic dianhydride containing a fluorine atom may use 1 type, or may use 2 or more types.
• Examples of the diamine containing a fluorine atom used in the present invention include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFMB) represented by the following formula (3): 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) represented by the following formula (4), 2,3,5,6-tetrafluoro-1,4-diaminobenzene, 2,4,5,6-tetrafluoro-1,3-diaminobenzene, 2,3,5,6-tetrafluoro-1,4-benzene (dimethanamine), 2,2′-difluoro- (1,1 ′ -Biphenyl) -4,4'-diamine, 2,2 ', 6,6'-tetrafluoro- (1,1'-biphenyl) -4,4'-diamine, 4,4'-diaminooct
• 1 type may be used for the diamine containing a fluorine atom, or 2 or more types may be used for it.
• the polyamic acid of the present invention may be obtained by using other tetracarboxylic acid components and / or other diamine components as long as the characteristics of the present invention are not impaired.
• 50 mol% or less preferably 25 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less is one or more other tetracarboxylic acid components.
• 50 mol% or less preferably 25 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less is one or more other diamines. It may be a component.
• tetracarboxylic acid components examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and dicyclohexyl.
• CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
• 1,2,4,5-cyclohexanetetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride
• dicyclohexyl examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and dicyclohexyl.
• Examples of other diamine components that can be used include trans-1,4-cyclohexanediamine (CHDA), cis-1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis ( (Aminomethyl) cyclohexane, 1.3-adamantanediamine, 1,3-bis (4-aminophenyl) adamantane, cycloaliphatic diamines such as 1,3-cyclohexanediamine, 1,6-hexamethylenediamine, 1,10- Aliphatic diamines such as decamethylenediamine, diamines containing a fluorene skeleton such as 9,9-bis (4-aminophenyl) fluorene (BAFL), 9.9-bis [(4-aminophenoxy) phenyl] fluorene, 4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl s
• the polyamic acid of the present invention can be obtained as a polyamic acid solution (or a polyamic acid solution composition) by reacting a tetracarboxylic acid component and a diamine component in a solvent.
• This reaction is carried out at a relatively low temperature of, for example, 100 ° C. or less, preferably 80 ° C. or less in order to suppress the imidization reaction by using approximately equimolar amounts of the tetracarboxylic acid component and diamine component.
• the reaction temperature is usually 25 ° C. to 100 ° C., preferably 40 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C.
• the reaction time is about 0.1 to 24 hours, preferably It is preferably about 2 to 12 hours.
• the reaction can be carried out in an air atmosphere, but usually it is suitably carried out in an inert gas atmosphere, preferably in a nitrogen gas atmosphere.
• the molar ratio of the tetracarboxylic acid component to the diamine component is preferably about 0.90 to 1.10, more preferably about 0.95 to 1.05.
• the solvent used for preparing the polyamic acid is not particularly limited.
• Cyclic ester solvents carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1, 3-Dimethyl-2-imida Rijinon, sulfolane, and dimethyl sulfoxide.
• alcohol solvents such as methanol and ethanol, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl Cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, Toluene, chlorobenzene, N-methylcaprolactam, hexamethylphosphorotriamide, bis
• the polyamic acid solution composition of the present invention contains at least the polyamic acid of the present invention and a solvent.
• the solvent is not particularly limited as long as the polyamic acid is dissolved, and examples thereof include the same solvents as those used for preparing the polyamic acid.
• the solvent may be a mixture of two or more.
• the silica is further added in an amount of 1 to 100 parts by weight, preferably 5 to 90 parts by weight, more preferably 10 to 10 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic acid component and the diamine component. Included in an amount of 90 parts by weight.
• the polyamic acid solution composition preferably further contains silica in an amount of 5 to 70 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component.
• the linear expansion coefficient at a high temperature (for example, a linear expansion coefficient of 300 to 400 ° C.) is reduced while maintaining high transparency of the polyimide obtained from the polyamic acid solution composition. be able to. Moreover, it is possible to control the linear expansion coefficient of the obtained polyimide at a particularly high temperature, depending on the amount of silica added.
• the silica used in the present invention has a particle diameter measured by a dynamic light scattering method of 200 nm or less, more preferably 1 to 60 nm, particularly preferably 1 to 50 nm, from the viewpoint of transparency of the resulting polyimide and dispersibility of silica. More preferably, it is 10 to 30 nm.
• a tetracarboxylic acid component and a diamine component are reacted in a solvent to obtain a polyamic acid solution (or a polyamic acid solution composition), and then silica is added thereto. It can be produced by adding 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component.
• a colloidal solution obtained by dispersing colloidal silica in an organic solvent is added to a polyamic acid solution obtained by reacting a tetracarboxylic acid component and a diamine component in a solvent. And it is preferable to produce a polyamic acid solution composition by mixing.
• the colloidal silica solvent is not particularly limited.
• PMA propylene glycol monomethyl ether acetate
• ethylene glycol mono-n-propyl examples include ether (NPC), ethylene glycol (EG), isopropanol (IPA), methanol, methyl ethyl ketone, methyl isobutyl ketone, xylene, n-butanol, and propylene glycol monomethyl ether.
• the solvent of colloidal silica is preferably selected according to the solvent of the polyamic acid solution so that desired physical properties can be obtained, and is usually preferably a solvent having high compatibility with the polyamic acid solution. Depending on the choice of solvent, the transparency and / or linear expansion coefficient of the resulting polyimide may change.
• organic solvent to be used may be one type or two or more types.
• the colloidal silica solution to be added is not particularly limited in the content of colloidal silica, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass. Preferably it is.
• the polyamic acid solution composition of the present invention may contain other additive components such as fillers other than silica, if necessary.
• the filler to be added preferably has a particle size of 200 nm or less, more preferably 50 nm or less.
• various inorganic fillers such as titanium oxide and zirconium oxide can be used.
• the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N-methyl-2-pyrrolidone solution at a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more. , Preferably 0.4 dL / g or more.
• the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the mechanical strength and heat resistance of the resulting polyimide are excellent.
• the solid content concentration resulting from the polyamic acid is not particularly limited, but is preferably 5% by mass to 45% by mass with respect to the total amount of the polyimide precursor and the solvent. %, More preferably 7% by mass to 40% by mass, and still more preferably 9% by mass to 30% by mass.
• the solid content concentration is lower than 5% by mass, productivity and handling during use may be deteriorated, and when it is higher than 45% by mass, the fluidity of the solution may be lost.
• the solution viscosity at 30 ° C. of the polyamic acid solution composition of the present invention is not particularly limited, but is preferably 1000 Pa ⁇ sec or less, more preferably 0.1 to 500 Pa ⁇ sec, still more preferably 0.1 to 300 Pa ⁇ sec. sec, particularly preferably 0.1 to 200 Pa ⁇ sec, is suitable for handling. If the solution viscosity exceeds 1000 Pa ⁇ sec, the fluidity may be lost, and uniform application to metal or glass may be difficult, and if it is lower than 0.1 Pa ⁇ sec, the solution may be applied to metal or glass. Sagging or repelling may occur at the time of application, and it may be difficult to obtain a polyimide with high characteristics or a substrate for a polyimide flexible device.
• the polyamic acid solution composition of the present invention is excellent in transparency, and can obtain a polyimide whose linear expansion coefficient, in particular, the linear expansion coefficient at a high temperature is controlled to be relatively low.
• the polyamic acid solution composition of the present invention can suitably obtain polyimide by removing the solvent by heat treatment and imidizing (dehydrating ring closure).
• the heat treatment conditions are not particularly limited, but after drying in a temperature range of 50 ° C. to 150 ° C. and 150 ° C. to 250 ° C., heat treatment is further performed at a temperature of 300 ° C. to 400 ° C., preferably 350 ° C. to 400 ° C. Is preferred.
• This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove the solvent. Further, defoaming may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, problems such as foaming may occur and polyimide having good characteristics may not be obtained.
• the imidation reaction can also be performed by chemically reacting a polyamic acid, which is a polyimide precursor, with a dehydrating reagent in the presence of a catalyst such as pyridine or triethylamine.
• a catalyst such as pyridine or triethylamine.
• the imidization method is not particularly limited, and a known thermal imidization or chemical imidization method can be suitably applied.
• the polyimide obtained from the polyamic acid solution composition of the present invention has high transparency. According to the present invention, for example, when a film having a film thickness of 10 ⁇ m is used, a polyimide having a light transmittance at a wavelength of 400 nm of 70% or more, further 75% or more, and further 80% or more can be obtained.
• the linear expansion coefficient at a high temperature exceeding 200 ° C. is controlled to be relatively low.
• the linear expansion coefficient at 300 to 400 ° C. A polyimide having a concentration of 350 ppm / ° C. or lower, further 250 ppm / ° C. or lower, or 10 to 200 ppm / ° C. can be obtained.
• the light transmittance at a wavelength of 400 nm in a film having a thickness of 10 ⁇ m is 70% or more, and the linear expansion coefficient at 300 to 400 ° C. is 350 ppm / ° C. or less, further 250 ppm / ° C. or less.
• a polyimide can be obtained. There has never been a polyamic acid solution composition that is excellent in transparency and at the same time can obtain a polyimide whose linear expansion coefficient at a high temperature is controlled to be low.
• the thickness of the polyimide film of the present invention can be appropriately selected depending on the application, and is preferably about 1 ⁇ m to 100 ⁇ m, more preferably about 1 ⁇ m to 50 ⁇ m.
• the polyimide obtained from the polyamic acid solution composition of the present invention has high transparency, it can be suitably used for electrical devices, electronic devices, and optical devices that require transparency, such as liquid crystal displays, It can be suitably used as a display device such as an EL display or electronic paper, a touch panel, a solar cell, a substrate of an LED lighting device, or a protective film. In particular, it can be suitably used as a substrate for flexible devices such as display devices such as liquid crystal displays, organic EL displays and electronic paper, and light receiving devices such as light receiving elements of thin film solar cells.
• the polyamic acid solution composition of the present invention may contain other additive components depending on the use of the resulting polyimide.
• the polyamic acid solution composition of the present invention can be particularly suitably used as a polyimide precursor composition for flexible device substrates.
• a polyamic acid solution composition is applied or sprayed onto the surface of a substrate to form a coating film comprising a polyamic acid solution composition layer, and the polyamic acid solution composition is heated.
• the substrate for polyimide flexible device is obtained by processing.
• the polyamic acid solution composition can be suitably obtained by removing the solvent by heat treatment and imidization (dehydration ring closure) to obtain a polyimide flexible device substrate.
• the heat treatment conditions are not particularly limited, but after drying in a temperature range of 50 ° C. to 150 ° C. and 150 ° C. to 250 ° C., heat treatment is further performed at a temperature of 300 ° C. to 400 ° C., preferably 350 ° C. to 400 ° C. Is preferred.
• This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove the solvent. Further, defoaming may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, defects such as foaming may occur and a good flexible device substrate may not be obtained.
• a polyimide precursor composition (polyamic acid solution composition) is applied onto a carrier substrate as a support, and heat-treated to form a solid polyimide resin film. After the circuit is formed on the polyimide resin film, the polyimide resin film having the circuit formed on the surface is peeled from the carrier substrate.
• the polyamic acid solution composition can be applied by any method that can form a coating film having a uniform thickness on a carrier substrate (support). For example, application by die coating, spin coating, or screen printing is possible.
• a coating film made of the polyamic acid solution composition is formed on the carrier substrate, and the solvent is removed by heat treatment at a relatively low temperature to remove the self-supporting film (the state in which the film does not flow, polymerization and
• the substrate for flexible devices is formed by the method of dehydration and imidization by heat treatment in the state where the self-supporting film is left as it is or after being peeled off from the base material if necessary. Can be suitably obtained.
• solvent removal or “dehydration / imidization” does not mean that only solvent removal or only dehydration / imidation proceeds in the step. A considerable degree of dehydration and imidization also proceeds in the solvent removal step, and removal of the residual solvent proceeds in the dehydration and imidization step.
• the polyamic acid solution composition of the present invention may contain other additive components depending on the use of the polyimide flexible device substrate obtained. Moreover, the polyimide flexible device board
• substrate obtained may laminate
• the thickness of the polyimide resin film is preferably 1 to 20 ⁇ m.
• the thickness is less than 1 ⁇ m, the polyimide resin film cannot maintain sufficient resistance, and when used as a flexible device substrate, it may not withstand stress and may be destroyed.
• the thickness of the polyimide resin film exceeds 20 ⁇ m, it is difficult to reduce the thickness of the flexible device.
• the thickness of the polyimide resin film is more preferably 2 to 10 ⁇ m.
• a circuit necessary for a display device or a light receiving device is formed on the polyimide resin film formed as described above.
• This process varies depending on the type of device.
• an amorphous silicon TFT for example, is formed on a polyimide resin film.
• the TFT includes a gate metal layer, a silicon nitride gate dielectric layer, and an ITI pixel electrode.
• a structure necessary for a liquid crystal display can be formed by a known method. Since the polyimide resin film obtained in the present invention is excellent in various properties such as heat resistance and toughness, the method for forming a circuit or the like is not particularly limited.
• the polyimide resin film having the circuit and the like formed on the surface as described above is peeled off from the carrier substrate.
• the peeling method For example, it can peel by irradiating a laser etc. from the carrier substrate side. Since the polyimide resin film obtained by the present invention has high flexibility and toughness, it can be physically peeled off from the carrier substrate (support).
• Examples of the flexible device in the present invention include a display device such as a liquid crystal display, an organic EL display, and electronic paper, a light receiving device such as a solar cell, and a CMOS.
• the present invention is particularly suitable for application to a device that is desired to be thin and flexible.
• the solid content concentration of the polyamic acid solution is a value obtained by drying the polyamic acid solution at 350 ° C. for 30 minutes and obtaining the weight W 1 before drying and the weight W 2 after drying by the following formula.
• Linear expansion coefficient (CTE) A polyimide film having a thickness of 10 ⁇ m is cut into a strip shape having a width of 4 mm to obtain a test piece, and a TMA / SS6100 (manufactured by SII Technology Co., Ltd.) is used. The temperature was raised to ° C. From the obtained TMA curve, linear expansion coefficients from 50 ° C. to 200 ° C. and from 300 ° C. to 400 ° C. were obtained.
• Example 1 Colloidal solution prepared by dispersing colloidal silica in N, N-dimethylacetamide in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST; silica particle solid content concentration: 20 wt%; silica 6 g) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 2 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.
• Example 2 To the polyamic acid solution obtained in Reference Example 1, 15 g of a colloidal solution in which colloidal silica is dispersed in N, N-dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST) is added and stirred, and the polyamic acid is stirred. A solution composition was obtained. The addition amount of silica is 5 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.
• Example 3 To the polyamic acid solution obtained in Reference Example 1, 60 g of a colloidal solution in which colloidal silica is dispersed in N, N-dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST) is added and stirred, and the polyamic acid is stirred. A solution composition was obtained. The addition amount of silica is 20 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.
• Example 4 To the polyamic acid solution obtained in Reference Example 1, 120 g of a colloidal solution in which colloidal silica is dispersed in N, N-dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST) is added and stirred, and the polyamic acid is stirred. A solution composition was obtained. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.
• Example 5 Colloidal solution in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA-ST; silica particle solid content concentration: 30 wt%; silica 40 g (particle diameter: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 20 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 6 To the polyamic acid solution obtained in Reference Example 1, 80 g of a colloidal solution (PMA-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate is added and stirred, and the polyamic acid solution is stirred. A composition was obtained. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• PMA-ST colloidal solution
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 7 To the polyamic acid solution obtained in Reference Example 1, 120 g of a colloidal solution (PMA-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate was added and stirred, and the polyamic acid solution was stirred. A composition was obtained. The addition amount of silica is 60 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 8 Colloidal solution obtained by dispersing colloidal silica in ethylene glycol mono-n-propyl ether in the polyamic acid solution obtained in Reference Example 1 (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd .; solid content concentration of silica particles: 30 wt%; silica particle size: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 9 To the polyamic acid solution obtained in Reference Example 1, 120 g of a colloidal solution (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica is dispersed in ethylene glycol mono-n-propyl ether is added and stirred. Thus, a polyamic acid solution composition was obtained.
• the addition amount of silica is 60 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 10 Colloidal solution in which colloidal silica is dispersed in ethylene glycol in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., EG-ST; silica particle solid content concentration: 20 wt%; silica particle diameter: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 11 To the polyamic acid solution obtained in Reference Example 1, 180 g of a colloidal solution in which colloidal silica is dispersed in ethylene glycol (EG-ST, manufactured by Nissan Chemical Industries, Ltd.) was added and stirred to obtain a polyamic acid solution composition. Obtained.
• the addition amount of silica is 60 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 12 Colloidal solution obtained by dispersing colloidal silica in isopropanol in the polyamic acid solution obtained in Reference Example 1 (IPA-ST, manufactured by Nissan Chemical Industries, Ltd .; silica particle solid content concentration: 30 wt%; silica particle size: 10 80 g) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).
• This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.
• Example 13 Colloidal solution prepared by dispersing colloidal silica in propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA-ST; solid content concentration of silica particles: 30 wt%; silica particles) 80 g of 10 to 15 nm in diameter were added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.
• Example 14 Colloidal solution prepared by dispersing colloidal silica in propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA-ST; solid content concentration of silica particles: 30 wt%; silica particles) 160 g (diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 80 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.
• Example 15 Colloidal solution prepared by dispersing colloidal silica in methyl ethyl ketone in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-40; solid content concentration of silica particles: 40 wt%; silica particle diameter 10 80 g of ⁇ 15 nm (no surface modification) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.
• Example 16 Colloidal solution prepared by dispersing colloidal silica in methyl ethyl ketone in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., MEK-AC-2101; solid content concentration of silica particles: 30 wt%; silica particle diameter of 10 80 g of ⁇ 15 nm (with surface modification) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.
• Example 17 Colloidal solution obtained by dispersing colloidal silica in ethylene glycol mono-n-propyl ether in the polyamic acid solution obtained in Reference Example 2 (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd .; solid content concentration of silica particles: 30 wt%; silica particle diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.
• Example 18 Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 2 (Nissan Chemical Industry Co., Ltd., IPA-ST-30; silica particle solid content concentration: 30 wt%; silica particle diameter 10 ⁇ 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.
• Example 19 Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., IPA-ST-S; silica particle solid content concentration: 25 wt%; silica particle diameter 8 96 g) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.
• Example 20 Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 2 (IPA-ST-S, manufactured by Nissan Chemical Industries, Ltd .; silica particle solid content concentration: 15 wt%; silica particle diameter 9 (About 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.
• Example 21 Colloidal solution in which colloidal silica is dispersed in ethylene glycol in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., EG-ST; silica particle solid content concentration: 20 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.
• Example 22 Colloidal solution obtained by dispersing colloidal silica in 214 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid content concentration: 30 wt%; silica particle diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.
• Example 23 Colloidal solution obtained by dispersing colloidal silica in 214 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid content concentration: 30 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 80 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.
• Example 24 A colloidal solution obtained by dispersing colloidal silica in 500 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid content concentration: 30 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.
• Example 25 A colloidal solution obtained by dispersing colloidal silica in 500 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid content concentration: 30 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 80 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.
• Example 26 Colloidal solution obtained by dispersing colloidal silica in 214 g of the polyamic acid solution obtained in Reference Example 1 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid content concentration: 30 wt%; silica particle diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.
• Example 27 Colloidal solution prepared by dispersing colloidal silica in 56 g of the polyamic acid solution obtained in Reference Example 1 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid concentration: 30 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition.
• the addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).
• This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C.
• a heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 ⁇ m on the glass plate.
• the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.
• a polyamic acid solution composition capable of obtaining a polyimide having excellent transparency and a linear expansion coefficient, particularly a linear expansion coefficient at a high temperature, which is controlled to be relatively low.
• the polyimide obtained by heat-treating the polyamic acid solution composition of the present invention has high transparency and has a relatively low linear expansion coefficient, particularly a linear expansion coefficient at high temperatures, so that it can be used in electrical, electronic and optical devices.
• a display device such as a liquid crystal display, EL display, or electronic paper, a touch panel, a solar cell, a substrate of an LED lighting device, or a protective film.
• a substrate for flexible devices such as display devices such as liquid crystal displays, organic EL displays and electronic paper, and light receiving devices such as light receiving elements of thin film solar cells.

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