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  • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
  • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
  • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08G73/14—Polyamide-imides
• • 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
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  • 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • C—CHEMISTRY; METALLURGY
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  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

• the present invention relates to a solution composition (polyimide precursor composition) containing a polyimide precursor from which a polyimide having excellent transparency, mechanical properties, and heat resistance is obtained, and a method for producing the polyimide.
• the present invention also relates to a polyimide, a polyimide film, and a substrate that are excellent in transparency, mechanical properties, and heat resistance.
• Aromatic polyimide is essentially yellowish brown due to intramolecular conjugation and the formation of charge transfer complexes. For this reason, as a means to suppress coloration, for example, introduction of fluorine atoms into the molecule, imparting flexibility to the main chain, introduction of bulky groups as side chains, etc. inhibits intramolecular conjugation and charge transfer complex formation. Thus, a method for expressing transparency has been proposed.
• Patent Document 1 discloses a highly transparent aromatic polyimide containing a fluorine atom.
• Patent Documents 2 to 4 disclose semi-alicyclic polyimides having high transparency using an aromatic tetracarboxylic dianhydride as a tetracarboxylic acid component and an alicyclic diamine as a diamine component.
• Patent Documents 5 to 8 disclose various highly translucent semi-alicyclic polyimides using an alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and an aromatic diamine as a diamine component. Has been.
• Patent Documents 9 and 10 disclose polyimides using decahydro-1,4: 5,8-dimethananaphthalene-2,3,6,7-tetracarboxylic acids as tetracarboxylic acid components.
• Non-Patent Document 1 discloses a polyimide using (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethananaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid as a tetracarboxylic acid component.
• Non-Patent Document 2 uses (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethananaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acids as the tetracarboxylic acid component.
• 4arH, 8acH 4arH, 8acH
• 5c, 8c-dimethananaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acids as the tetracarboxylic acid component.
• Disclosed polyimide 4arH, 8acH
• Non-Patent Document 3 discloses, as a tetracarboxylic acid component, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid. Polyimides using acid dianhydrides are disclosed. Further, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic dianhydride used here is 6 It is described that it contains various stereoisomers.
• Patent Document 11 also discloses norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid as a tetracarboxylic acid component.
• Polyimides using dianhydrides are disclosed.
• Semi-alicyclic polyimide using alicyclic tetracarboxylic dianhydride as the tetracarboxylic acid component and aromatic diamine as the diamine component has high transparency, bending resistance, and high heat resistance, but depending on the application Further, there is a demand for polyimide having higher heat resistance.
• Patent Document 12 is obtained from a tetracarboxylic acid component containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a main component and a diamine component containing paraphenylenediamine as a main component.
• a polyamic acid solution composition containing a polyamic acid and a phosphorus compound is cast on a base material, heat-treated, and a polyimide laminate having a thickness of less than 50 ⁇ m and forming a phosphorus-containing polyimide layer on the base material.
• a manufacturing method is disclosed.
• Patent Document 12 The phosphorus compounds used in the examples of Patent Document 12 are triphenyl phosphate, monoethyl phosphate ester, monolauryl phosphate ester, and polyphosphoric acid. Patent Document 12 describes that this manufacturing method can form a highly heat-resistant polyimide layer in which thermal decomposition is suppressed in a temperature range of 500 ° C. to 650 ° C.
• the present invention has been made in view of the situation as described above, and is a polyimide having excellent transparency and mechanical properties, and a polyimide precursor composition from which a polyimide having higher heat resistance can be obtained even with the same composition. It aims at providing the manufacturing method of (the solution composition containing a polyimide precursor) and a polyimide.
• a polyimide precursor composition comprising a phosphorus compound which contains a phosphorus atom and has a boiling point at 1 atm lower than a decomposition temperature and 350 ° C. or less.
• X 1 is a tetravalent group having an alicyclic structure
• Y 1 is a divalent group having an aromatic ring
• R 1 and R 2 are each independently hydrogen, C 1-6 Or an alkylsilyl group having 3 to 9 carbon atoms.
• X 2 is a tetravalent group having an aromatic ring
• Y 2 is a divalent group having an alicyclic structure
• R 3 and R 4 are each independently hydrogen, 1 to 6 carbon atoms; Or an alkylsilyl group having 3 to 9 carbon atoms.
• R 5 and R 6 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• Item 2 The polyimide precursor composition according to Item 1, wherein the phosphorus compound has a boiling point of 200 ° C or less at 1 atm. 3. Item 3. The polyimide precursor composition according to Item 1 or 2, wherein the phosphorus compound is trimethyl phosphate, trimethyl phosphite, dimethyl phosphite, or diethyl phosphite. 4). 4. A method for producing polyimide, wherein the polyimide precursor composition according to any one of items 1 to 3 is heat-treated to imidize the polyimide precursor. 5.
• a polyimide having excellent transparency and mechanical properties and a polyimide precursor composition (solution composition containing a polyimide precursor) from which a polyimide having higher heat resistance can be obtained with the same composition, and polyimide A manufacturing method can be provided.
• the polyimide obtained from the polyimide precursor composition of the present invention is highly transparent, has higher heat resistance, has a low linear thermal expansion coefficient, and can easily form a fine circuit. Yes, it can be suitably used to form substrates for display applications and the like. Moreover, the polyimide of this invention can be used suitably also in order to form the board
• the polyimide precursor composition of the present invention is at least one of a repeating unit represented by the chemical formula (1), a repeating unit represented by the chemical formula (2), or a repeating unit represented by the chemical formula (3). And a phosphorus compound having a boiling point at 1 atm lower than the decomposition temperature and 350 ° C. or lower.
• the polyimide precursor containing the repeating unit represented by the chemical formula (1) and the polyimide precursor containing the repeating unit represented by the chemical formula (2) are semi-alicyclic polyimide precursors, and the chemical formula ( The polyimide precursor containing the repeating unit represented by 3) is an aromatic polyimide precursor containing a fluorine atom.
• the use of an additive such as a phosphorus compound that can cause coloring is not preferred.
• a polyimide having higher heat resistance can be obtained from a polyimide precursor having the same composition while maintaining high transparency. It is obtained when the phosphorus compound added to the polyimide precursor composition is a phosphorus compound whose boiling point at 1 atm such as phosphoric acid is higher than the decomposition temperature, or a phosphorus compound whose boiling point at 1 atm such as triphenyl phosphate exceeds 350 ° C. The transparency of the polyimide decreases.
• the polyimide precursor composition of the present invention includes a repeating unit represented by the chemical formula (1), a repeating unit represented by the chemical formula (2), or a repeating unit represented by the chemical formula (3).
• X 1 in the chemical formula (1) is preferably a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms, and Y 1 is a divalent having an aromatic ring having 6 to 40 carbon atoms. Are preferred.
• Examples of the tetracarboxylic acid component that gives the repeating unit of the chemical formula (1) include 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxybisphthalic acid, cyclohexane-1,2,4,5- Tetracarboxylic acid, [1,1′-bi (cyclohexane)]-3,3 ′, 4,4′-tetracarboxylic acid, [1,1′-bi (cyclohexane)]-2,3,3 ′, 4 '-Tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,2', 3,3'-tetracarboxylic acid, 4,4'-methylenebis (cyclohexane-1,2-dicarboxylic acid), 4 , 4 '-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-oxybis (cyclohex
• Examples of the diamine component that gives the repeating unit of the chemical formula (1) include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-diamino-biphenyl, and 2,2′-bis (trifluoromethyl) benzidine.
• the polyimide precursor containing at least one repeating unit represented by the chemical formula (1) can contain other repeating units other than the repeating unit represented by the chemical formula (1).
• the tetracarboxylic acid component and diamine component that give other repeating units are not particularly limited, and any other known aromatic or aliphatic tetracarboxylic acids or known aromatic or aliphatic diamines can be used. .
• Other tetracarboxylic acid components may be used alone or in combination of two or more.
• Other diamine components may be used alone or in combination of two or more.
• the content of other repeating units other than the repeating unit represented by the chemical formula (1) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is 10 mol% or less.
• X 2 in the chemical formula (2) is preferably a tetravalent group having an aromatic ring having 6 to 40 carbon atoms
• Y 2 is a divalent having an alicyclic structure having 4 to 40 carbon atoms.
• tetracarboxylic acid component giving the repeating unit of the chemical formula (2) examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxotetrahydrofuran-3- Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′- Biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) sulfone dianhydride, m-terphenyl-3, 4,3 ′, 4′-tetracarboxylic dianhydride, p-terphenyl-3,4,3 ′, 4′-
• Examples of the diamine component that gives the repeating unit of the chemical formula (2) include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1, 4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4- Diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4-bis (aminomethyl) cyclohexane, 1 , 3-Bis
• the polyimide precursor containing at least one type of repeating unit represented by the chemical formula (2) may contain other repeating units other than the repeating unit represented by the chemical formula (2).
• the tetracarboxylic acid component and diamine component that give other repeating units are not particularly limited, and any other known aromatic or aliphatic tetracarboxylic acids or known aromatic or aliphatic diamines can be used. .
• Other tetracarboxylic acid components may be used alone or in combination of two or more.
• Other diamine components may be used alone or in combination of two or more.
• the content of other repeating units other than the repeating unit represented by the chemical formula (2) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is 10 mol% or less.
• X 3 in the chemical formula (3) is preferably a tetravalent group having an aromatic ring having 6 to 40 carbon atoms
• Y 3 is a divalent group having an aromatic ring having 6 to 40 carbon atoms.
• The may be one in which one of X 3 or Y 3 contains a fluorine atom, or may be both of X 3 and Y 3 contains a fluorine atom.
• Examples of the tetracarboxylic acid component containing a fluorine atom that gives the repeating unit of the chemical formula (3) include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane and its tetracarboxylic acid dicarboxylic acid.
• Derivatives such as anhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, tetracarboxylic acid chlorides and the like can be mentioned.
• tetracarboxylic acid component not containing a fluorine atom examples include 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, Pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4 , 4′-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) sulfone dianhydride, m-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, p-terphenyl-3 , 4,3 ′, 4′-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane,
• Examples of the diamine component containing a fluorine atom that gives the repeating unit of the chemical formula (3) include 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-hydroxyphenyl) Hexafluoropropane is mentioned.
• diamine component not containing a fluorine atom examples include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-diamino-biphenyl, m-tolidine, 4,4′-diaminobenzanilide, 3, 4′-diaminobenzanilide, N, N′-bis (4-aminophenyl) terephthalamide, N, N′-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis ( 4-aminophenyl) terephthalate, biphenyl-4,4′-dicarboxylic acid bis (4-aminophenyl) ester, p-phenylenebis (p-aminobenzoate), bis (4-aminophenyl)-[1,1′- Biphenyl] -4,4′-dicarboxylate, [1,1′-biphenyl]
• the polyimide precursor containing at least one repeating unit represented by the chemical formula (3) can contain other repeating units other than the repeating unit represented by the chemical formula (3).
• the tetracarboxylic acid component and diamine component that give other repeating units are not particularly limited, and any other known aromatic or aliphatic tetracarboxylic acids or known aromatic or aliphatic diamines can be used. .
• Other tetracarboxylic acid components may be used alone or in combination of two or more.
• Other diamine components may be used alone or in combination of two or more.
• the content of other repeating units other than the repeating unit represented by the chemical formula (3) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is 10 mol% or less.
• the polyimide precursor may include at least one repeating unit represented by the chemical formula (1) and at least one repeating unit represented by the chemical formula (2). ) And at least one repeating unit represented by the chemical formula (3), and at least one of the repeating units represented by the chemical formula (2). 1 type and at least 1 type of the repeating unit represented by the said Chemical formula (3) may be included, or at least 1 type of the repeating unit represented by the said Chemical formula (1) and the said Chemical formula (2) ) And at least one repeating unit represented by the chemical formula (3) may be included. Also in that case, the content of other repeating units other than the repeating units represented by the chemical formulas (1), (2) and (3) is preferably 30 mol% or less or 30% with respect to all repeating units. It is preferable that it is less than mol%, more preferably 20 mol% or less, still more preferably 10 mol% or less.
• the polyimide precursor includes, for example, a repeating unit represented by the following chemical formula (1-1-1), more preferably a repeating unit represented by the following chemical formula (1-1-2).
• a polyimide precursor is preferred.
• a 1 is a divalent group having an aromatic ring
• R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. is there.
• a 1 is a divalent group having an aromatic ring
• R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. is there.
• one of the acid groups at the 2-position or 3-position of the decahydro-1,4: 5,8-dimethananaphthalene ring is amino.
• polyimide precursor is represented by chemical formula (1-1-1), more preferably represented by chemical formula (1-1-2), in which A 1 is a group represented by the following chemical formula (1-1-A). It is preferable to include at least one repeating unit.
• V 1 , U 1 , and T 1 are each independently a hydrogen atom, a methyl group, or a trifluoromethyl group.
• Z 1 and W 1 are each independently a direct bond or a group consisting of a group represented by the formula: —NHCO—, —CONH—, —COO—, —OCO— 1 type selected from
• the polyimide precursor is decahydro-1,4: 5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid, and more preferably (4arH, 8acH) Decahydro-1t, 4t: 5c, 8c-dimethananaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acids and the like (tetracarboxylic acids and the like are tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid A tetracarboxylic acid component including a silyl ester, a tetracarboxylic acid ester, a tetracarboxylic acid derivative such as tetracarboxylic acid chloride) and a diamine component having an aromatic ring, more preferably A 1 is represented by the chemical formula (1-1-1- A) which gives a repeating unit of the chemical formula (1
• Examples of the tetracarboxylic acid component that provides the repeating unit of the chemical formula (1-1-1) include 1-decahydro-1,4: 5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid and the like. Species may be used alone, or a plurality of species may be used in combination.
• the tetracarboxylic acid component giving the repeating unit of the chemical formula (1-1-2) includes (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethananaphthalene-2t, 3t, 6c, 7c-tetra
• One kind such as carboxylic acids may be used alone, or a plurality of kinds may be used in combination.
• the diamine component that gives the repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2) gives that in which A 1 is a group represented by the chemical formula (1-1-A) Preferably it contains a diamine.
• the diamine component that gives the repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2) in which A 1 is a group represented by the chemical formula (1-1-A) has an aromatic ring
• the aromatic rings are independently linked by a direct bond, an amide bond, or an ester bond.
• the connection position of the aromatic rings is not particularly limited, but it may form a linear structure by bonding at the 4-position to the amino group or the connection group of the aromatic rings, and the resulting polyimide may have low linear thermal expansion.
• a methyl group or a trifluoromethyl group may be substituted on the aromatic ring.
• the substitution position is not particularly limited.
• a diamine component that gives a repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2) in which A 1 is a group represented by the chemical formula (1-1-A) is particularly limited.
• Benzidine m-tolidine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, N, N′-bis (4-aminophenyl) terephthalamide, N, N′-p-phenylenebis ( p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4′-dicarboxylic Bis (4-amin
• the resulting polyimide has both high heat resistance and high transmittance.
• these diamines may be used alone or in combination of two or more. o-Tolidine is not preferred because of its high risk.
• a diamine component that gives A 1 in the chemical formula (1-1-1) or the chemical formula (1-1-2) (that is, the chemical formula (1-1-1) or the chemical formula (1-1-2)
• the diamine component that gives a repeating unit other diamines other than the diamine component that gives a structure in which A 1 has the structure of the chemical formula (1-1-A) can be used in combination.
• Other aromatic or aliphatic diamines can be used as other diamine components.
• a 1 represents the chemical formula (1-1-A) in 100 mol% of the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2).
• the ratio of the repeating units represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) which are groups represented by the formula is preferably 50 mol% or more, more preferably 70 mol% in total. More preferably, it is 90 mol% or more, and particularly preferably 100 mol%.
• the proportion of the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) in which A 1 is a group represented by the chemical formula (1-1-A) is from 50 mol% If it is small, the linear thermal expansion coefficient of the resulting polyimide may increase.
• the chemical formula (1-A) in 100 mol% of the diamine component giving the repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2), the chemical formula (1
• the proportion of the diamine components that give the structure of (-1-A) is preferably 70 mol% or less, more preferably 80 mol% or less, and still more preferably 90 mol% or less in total.
• diamines such as a diamine having an ether bond (—O—) such as 4,4′-oxydianiline, 4,4′-bis (4-aminophenoxy) biphenyl, and the like are represented by the chemical formula (1- 1-1) or 100 mol% of the diamine component which gives the repeating unit of the chemical formula (1-1-2), for example, 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably It may be preferable to use it at 10 mol% or less.
• the chemical formula (1-1-1) or the A 1 in the chemical formula (1-1-2) is preferably the chemical formula (1-1-A).
• a 1 is a group represented by the chemical formula (1-1-A).
• a diamine component that gives a repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2) is preferable.
• a diamine component that gives A 1 in the chemical formula (1-1-1) or the chemical formula (1-1-2) (that is, the chemical formula (1-1-1) or the chemical formula (1-1-2)
• a diamine component which gives a repeating unit) gives a repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2) in which A 1 is a group represented by the chemical formula (1-1-A).
• the polyimide precursor containing the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) of the present invention is such that A 1 is represented by the chemical formula (1-1). It may be preferable to include at least two types of repeating units of the chemical formula (1-1-1) or the chemical formula (1-1-2) which are groups represented by -A). In other words, in the chemical formula (1-1-1) or the diamine component that gives the repeating unit of the chemical formula (1-1-2), A 1 is a group represented by the chemical formula (1-1-A). It may be preferable to include at least two kinds of diamine components that give a repeating unit of a certain chemical formula (1-1-1) or chemical formula (1-1-2).
• a diamine component that gives A 1 in the chemical formula (1-1-1) or the chemical formula (1-1-2) contains at least two kinds of diamine components that give A 1 having the structure of the chemical formula (1-1-A), so that the resulting polyimide has high transparency and low linear thermal expansion. (I.e., a polyimide having high transparency and a low linear thermal expansion coefficient can be obtained).
• the polyimide precursor containing the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) of the present invention has the chemical formula (1-1-1- 1) or a diamine component giving A 1 in the chemical formula (1-1-2) (that is, a diamine component giving a repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2))
• a 1 includes at least two kinds of diamine components that give the structure of the chemical formula (1-1-A), and one of them is 4,4′-diaminobenzanilide.
• the diamine component that gives A 1 in the chemical formula (1-1-1) or the chemical formula (1-1-2) includes at least two kinds of diamine components that give the structure of the chemical formula (1-1-A), One of them is 4,4′-diaminobenzanilide, so that a polyimide having high heat resistance in addition to high transparency and low linear thermal expansion can be obtained.
• the polyimide precursor containing the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) of the present invention is represented by the chemical formula (1-1-1).
• the diamine component that gives A 1 in the chemical formula (1-1-2) is 2. It is preferable that at least one selected from 2,2′-bis (trifluoromethyl) benzidine and p-phenylenediamine and 4,4′-diaminobenzanilide are included.
• a diamine component that gives A 1 in the chemical formula (1-1-1) or the chemical formula (1-1-2) (that is, the chemical formula (1-1-1) or the chemical formula (1)
• the diamine component which gives the repeating unit of -1-2) preferably contains 4,4′-diaminobenzanilide in an amount of 20 mol% to 80 mol% and includes p-phenylenediamine and 2,2 ′.
• -It is preferable to contain 20 mol% or more and 80 mol% or less of either or both of bis (trifluoromethyl) benzidine, more preferably 30 mol% or more and 70 mol of 4,4'-diaminobenzanilide.
• 4,4′-diaminobenzanilide is contained in an amount of 40 mol% to 60 mol%, and p-phenylenediamine and 2,2′-bis (trifluoromethyl) benzidine. It is more preferable that it is contained in 40 mol% or more and 60 mol% or less in either or both.
• the polyimide precursor of the present invention may contain other repeating units other than the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2).
• aromatic or aliphatic tetracarboxylic acids can be used as the tetracarboxylic acid component that gives other repeating units.
• the diamine component giving another repeating unit is a repeating unit of the chemical formula (1-1-1) or the chemical formula (1-1-2) in which A 1 is a group represented by the chemical formula (1-1-A).
• the diamine illustrated as a diamine component to give may be sufficient.
• aromatic or aliphatic diamines can be used as the diamine component that gives other repeating units.
• the polyimide precursor comprises a total of repeating units represented by the chemical formula (1-1-1) or the chemical formula (1-1-2), preferably in a total of 50 repeating units. It is preferable to contain at least mol%, more preferably at least 70 mol%, even more preferably at least 90 mol%, particularly preferably at least 100 mol%.
• the ratio of the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) is 50 mol% or more, the film forming property is improved, and the linear thermal expansion coefficient of the resulting polyimide Becomes extremely small.
• the repeating unit represented by the chemical formula (1-1-1) or the chemical formula (1-1-2) is preferably 50 mol in 100 mol% of all repeating units. % To 99 mol%, more preferably 60 mol% to 95 mol%, particularly preferably 70 mol% to 95 mol%.
• a polyimide precursor including a repeating unit represented by the following chemical formula (1-2-1) is preferable, and the following chemical formula (1-2-2) and the following chemical formula
• the total content of the repeating units represented by the chemical formula (1-2-2) and the chemical formula (1-2-3) includes at least one repeating unit represented by (1-2-3).
• a polyimide precursor that is 80 mol% or more based on the unit is more preferable.
• a 2 is a divalent group having an aromatic ring, and R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. is there.
• a 2 is a divalent group having an aromatic ring, and R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. is there.
• a 2 is a divalent group having an aromatic ring, and R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. is there.
• the chemical formula (1-2-1), the chemical formula (1-2-2), and the chemical formula (1-2-3) are represented by 5 of two norbornane rings (bicyclo [2.2.1] heptane).
• a group represented by —COOR 1 in which one of the acid groups at the 6-position or the 6-position reacts with an amino group to form an amide bond (—CONH—), and one of them does not form an amide bond, or —COOR 2 represents a group represented by 2 ; That is, in the chemical formula (1-2-1), the chemical formula (1-2-2), and the chemical formula (1-2-3), there are four structural isomers, that is, (i) —COOR 1 at the 5-position.
• polyimide precursor repeating units, more preferably A 2 is represented by the following chemical formula
• a 2 is represented by the following chemical formula (1-2-A) is a group represented by the formula (1-2-1) ( It is preferable that at least one repeating unit represented by chemical formula (1-2-2) and / or chemical formula (1-2-3), which is a group represented by 1-2-A), is included.
• V 2 , U 2 , and T 2 each independently represent a hydrogen atom, a methyl group, or a trifluoromethyl group.
• Z 2 and W 2 are each independently a direct bond, or a group consisting of groups represented by the formula: —NHCO—, —CONH—, —COO—, —OCO— 1 type selected from
• the polyimide precursor is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′- Tetracarboxylic acids and the like, more preferably trans-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetra Carboxylic acids and / or cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acids (Tetracarboxylic acids are tetracarboxylic acids, tetracarboxylic dianhydrides, tetracarboxylic acid silyl esters,
• a tetracarboxylic acid component containing represents a carboxylic acid derivative), a diamine component having an aromatic ring, the formula is a group more preferably A 2 is represented by the formula (1-2-A) (1-2- 1)
• Examples of the tetracarboxylic acid component that provides the repeating unit of the chemical formula (1-2-1) include norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, One kind of 6,6 ′′ -tetracarboxylic acid or the like may be used alone, or a plurality of kinds may be used in combination.
• Examples of the tetracarboxylic acid component that provides the repeating unit of the chemical formula (1-2-2) include trans-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-
• One kind of 5,5 ′′, 6,6 ′′ -tetracarboxylic acid or the like may be used alone, or a plurality of kinds may be used in combination.
• Examples of the tetracarboxylic acid component that gives the repeating unit of the chemical formula (1-2-3) include cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-
• One kind of 5,5 ′′, 6,6 ′′ -tetracarboxylic acid or the like may be used alone, or a plurality of kinds may be used in combination.
• a tetracarboxylic acid component (trans-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ) that gives the repeating unit of the chemical formula (1-2-2) is used.
• a tetracarboxylic acid component trans-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇
• One or more of '-spiro-2' '-norbornane-5,5' ', 6,6' '-tetracarboxylic acids, etc. may be used, and the above chemical formula (1-2-3) may be repeated.
• Tetracarboxylic acid component giving units (cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetra Only one or more of carboxylic acids may be used, and a tetracarboxylic acid component (trans-endo-en) that provides the repeating unit of the chemical formula (1-2-2) may be used.
• Tetracarboxylic acid component cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′ giving a repeating unit of (1-2-3)
• Tetracarboxylic acid component cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′ giving a repeating unit of (1-2-3)
• ', 6,6' '-tetracarboxylic acids, etc. may be used.
• the polyimide precursor has a total content of repeating units represented by the chemical formulas (1-2-2) and (1-2-3) of 80 mol% or more based on all repeating units. That is, that is, at least one repeating unit represented by the chemical formula (1-2-2) and the chemical formula (1-2-3) is included, and the repeating unit is preferably added to all repeating units in total. Is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, particularly preferably 99 mol% or more. It contains at least one repeating unit represented by the chemical formula (1-2-2) and the chemical formula (1-2-3), and the repeating unit is preferably 80 mol% or more in total in all repeating units. By including, the linear thermal expansion coefficient of the polyimide obtained becomes small.
• the diamine component giving the repeating unit of the chemical formula (1-2-1), the chemical formula (1-2-2), or the chemical formula (1-2-3) is represented by A 2 having the chemical formula (1-2-A It is preferred to include a diamine that gives what is a group represented by:
• the connection position of the aromatic rings is not particularly limited, but it may form a linear structure by bonding at the 4-position to the amino group or the connection group of the aromatic rings, and the resulting polyimide may have low linear thermal expansion. .
• a methyl group or a trifluoromethyl group may be substituted on the aromatic ring.
• the substitution position is not particularly limited.
• a 2 is the structure of chemical formula (1-2-A)
• the resulting polyimide has both high heat resistance and high transmittance.
• these diamines may be used alone or in combination of two or more. In some embodiments, one in which the diamine component is only one of 4,4′-diaminobenzanilide can be excluded. In one embodiment, the diamine component is 4,4′-diaminobenzanilide and A 2 is a structure other than the chemical formula (1-2-A).
• a diamine component that gives a repeating unit of the chemical formula (1-2-3) (other than the diamine component that gives a structure in which A 2 has the structure of the chemical formula (1-2-A)) ) Can be excluded.
• o-tolidine is not preferred because of its high risk.
• a 2 represents the chemical formula (1-2-2-
• diamines other than the diamine component giving the structure of A) can be used in combination.
• Other aromatic or aliphatic diamines can be used as other diamine components.
• Examples of other diamine components include 4,4′-oxydianiline, 3,4′-oxydianiline, 3,3′-oxydianiline, bis (4-aminophenyl) sulfide, p-methylenebis (phenylenediamine) ), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 3,3-bis ((aminophenoxy) phenyl) propane, 2 , 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-aminophenoxy) dipheny ) Sulfone,
• the polyimide precursor of the present invention has at least one repeating unit represented by the chemical formula (1-2-1) in which A 2 is represented by the chemical formula (1-2-A), more preferably A 2 Is represented by the chemical formula (1-2-A), and at least one repeating unit of the chemical formula (1-2-2) and / or A 2 is represented by the chemical formula (1-2-A). It is preferable that at least one repeating unit of the chemical formula (1-2-3) is included.
• the diamine component that gives the repeating unit of the chemical formula (1-2-1), more preferably the repeating unit of the chemical formula (1-2-2) and the chemical formula (1-2-3) is A 2. It preferably contains a diamine component that gives a structure of the chemical formula (1-2-A).
• the diamine component giving A 2 in the chemical formula (1-2-2) and the chemical formula (1-2-3) is more preferably the repeating unit of the chemical formula (1-2-1).
• the heat resistance of the resulting polyimide is improved by being a diamine component giving a structure of -A).
• the polyimide precursor of the present invention contains 100 mol% of the diamine component that gives A 2 in the chemical formula (1-2-1) or the chemical formula (1-2-2) and the chemical formula (1-2-3).
• the total ratio of the diamine components giving the structure of the chemical formula (1-2-A) is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol%. It is preferably at least mol%, particularly preferably at least 100 mol%.
• the proportion of the diamine component giving the structure of the chemical formula (1-2-A) is less than 50 mol%, the resulting polyimide may have a large linear thermal expansion coefficient.
• the chemical formula (1-2-1) or A in the chemical formula (1-2-2) and the chemical formula (1-2-3) is used.
• the ratio of the diamine component giving the structure of the chemical formula (1-2-A) to the total of 100 mol% of the diamine component giving 2 is preferably 80 mol% or less, more preferably 90 mol% or less or 90 mol%. It may be preferable to be less than.
• other aromatic or aliphatic diamines such as 4,4′-oxydianiline are represented by the chemical formula (1-2-1), the chemical formula (1-2-2), and the chemical formula (1-2).
• -3) In 100 mol% of the diamine component giving the repeating unit, it is preferably less than 20 mol%, more preferably 10 mol% or less, more preferably less than 10 mol%.
• the polyimide precursor containing a repeating unit represented by the chemical formula (1-2-1) of the present invention is one in which A 2 is represented by the chemical formula (1-2-A). It may be preferable to include at least two repeating units of the chemical formula (1-2-1).
• the polyimide precursor containing the repeating unit represented by the chemical formula (1-2-2) and / or the repeating unit represented by the chemical formula (1-2-3) according to the present invention includes: It may be preferable to include at least two repeating units of the chemical formula (1-2-2) or the chemical formula (1-2-2) in which 2 is represented by the chemical formula (1-2-A).
• a diamine component that gives a repeating unit of the chemical formula (1-2-1) or a diamine component that gives a repeating unit of the chemical formula (1-2-2) and the chemical formula (1-2-3) It may be preferable to include at least two diamine components that give A 2 having the structure of the chemical formula (1-2-A).
• the diamine component that gives A 2 in the chemical formula (1-2-1) or A 2 in the chemical formula (1-2-2) and the chemical formula (1-2-3) is the chemical formula (1-2).
• the polyimide precursor of the present invention may contain at least two repeating units of the chemical formula (1-2-2) in which A 2 has the structure of the chemical formula (1-2-A).
• the may be one a 2 contains at least two repeating units of the structure in which the chemical formula (1-2-3) of the formula (1-2-a), also, a 2 is the chemical formula ( At least one repeating unit of the chemical formula (1-2-2) having the structure of 1-2-A) and the chemical formula (1-2) of A 2 having the structure of the chemical formula (1-2-A) It may contain at least one type of repeating unit -3).
• the polyimide precursor of the present invention comprises: (I) A 2 is m 2 and / or n 2 is 1 to 3, and Z 2 and / or W 2 are each independently —NHCO—, —CONH—, —COO—, or —OCO—
• the chemical formula (1-2-1) having the structure of the chemical formula (1-2-A), preferably the chemical formula (1-2-2) and the chemical formula (1-2-3) Including at least one repeating unit (I),
• a 2 is a structure of the above chemical formula (1-2-A) in which m 2 and n 2 are 0, or m 2 and / or n 2 is 1 to 3, Z 2 and
• the repeating unit (I) for example, the chemical formula (1-2-1) wherein A 2 is represented by any one of the following chemical formulas (D-1) to (D-3):
• the repeating unit of formula (1-2-1) is more preferred, wherein A 2 is represented by any one of the following chemical formulas (D-1) to (D-2).
• the diamine component which is a benzanilide and A 2 is represented by the following chemical formula (D-3) and gives the repeating unit of the chemical formula (1-2-1) is bis (4-aminophenyl) terephthalate, These diamines may be used alone or in combination of two or more.
• the repeating unit (II) includes, for example, the chemical formula (1-2-1) in which A 2 is represented by any one of the following chemical formulas (D-4) to (D-6)
• the repeating unit of formula (1-2-1), wherein A 2 is represented by any of the following chemical formulas (D-4) to (D-5), is more preferred.
• the diamine component giving the repeating unit of A 2 is represented by the following Formula Formula is represented by (D-4)
• (1-2-1) is a p- phenylenediamine
• a 2 is represented by the following formula (D)
• the diamine component that gives the repeating unit represented by the chemical formula (1-2-1) represented by the formula (-5) is 2,2′-bis (trifluoromethyl) benzidine
• a 2 is represented by the following chemical formula (D— 6)
• the diamine component that gives the repeating unit represented by the chemical formula (1-2-1) represented by 6) is m-tolidine, and these diamines may be used alone or in combination of two or more. Can also be used.
• the ratio of one or more of the repeating units (I) is 30 mol% or more and 70 mol% in total in all repeating units represented by the chemical formula (1-2-1).
• the ratio of one or more repeating units (II) is 30 mol% or more and 70 mol% or less in the total repeating units represented by the chemical formula (1-2-1) in total.
• the ratio of one or more of the repeating units (I) is 40 mol% or more and 60 mol% or less in the total repeating units represented by the chemical formula (1-2-1).
• the ratio of one or more kinds is 40 mol% or more and 60 mol% or less in the total repeating units represented by the chemical formula (1-2-1).
• the ratio of the repeating unit (I) is more preferably less than 60 mol% in the total repeating units represented by the chemical formula (1-2-1), % Or less is more preferable, and 40 mol% or less is particularly preferable.
• the repeating unit represented by the chemical formula (1-2-1) other than the repeating unit (I) and the repeating unit (II) for example, A 2 has a plurality of fragrances. Having a ring and aromatic rings connected by an ether bond (—O—)), in all repeating units represented by the chemical formula (1-2-1), preferably less than 20 mol%, More preferably, it may be preferred to contain 10 mol% or less, particularly preferably less than 10 mol%.
• the ratio of one or more repeating units (I) is 20 mol% or more and 80 mol% or less in total in all repeating units represented by the chemical formula (1-2-1).
• the ratio of one or more of the repeating units (II) is preferably 20 mol% or more and 80 mol% or less in the total repeating units represented by the chemical formula (1-2-1).
• the polyimide precursor containing the repeating unit of the chemical formula (1-2-1) or the chemical formula (1-2-2) and / or the chemical formula (1-2-3) of the present invention is In the chemical formula (1-2-1), or a diamine component that gives A 2 in the chemical formula (1-2-2) and the chemical formula (1-2-3) (of the chemical formula (1-2-1)
• a diamine component which gives a repeating unit or a repeating unit of the chemical formula (1-2-2) and the chemical formula (1-2-3) is at least two of the diamine components which give the structure of the chemical formula (1-2-A)
• one of them is 4,4′-diaminobenzanilide.
• the chemical formula (1-2-1), or the diamine component giving A 2 in the chemical formula (1-2-2) and the chemical formula (1-2-3) is a structure of the chemical formula (1-2-A). It contains at least two kinds of diamine components that give odor, and one of them is 4,4'-diaminobenzanilide, so that a polyimide having high heat resistance in addition to high transparency and low linear thermal expansion can be obtained. It is done.
• the polyimide precursor containing the repeating unit of the chemical formula (1-2-1) or the chemical formula (1-2-2) and / or the chemical formula (1-2-3) of the present invention is In the chemical formula (1-2-1), or a diamine component that gives A 2 in the chemical formula (1-2-2) and the chemical formula (1-2-3) (of the chemical formula (1-2-1) A repeating unit, or a diamine component that gives a repeating unit of the chemical formula (1-2-2) and the chemical formula (1-2-3)) from 2,2′-bis (trifluoromethyl) benzidine and p-phenylenediamine. It is particularly preferred that it contains at least one selected and 4,4′-diaminobenzanilide.
• the chemical formula (1-2-1), or the diamine component that gives A 2 in the chemical formula (1-2-2) and the chemical formula (1-2-3) is preferably 4,4′-diaminobenzanilide.
• 4,4′-diaminobenzanilide is 30 More than 70 mol% and more than 70 mol%, and more than 30 mol% and less than 70 mol% in either or both of p-phenylenediamine and 2,2′-bis (trifluoromethyl) benzidine
• a polyimide having both high transparency, low linear thermal expansion and heat resistance can be obtained.
• the diamine component that gives A 2 in the chemical formula (1-2-1) or the chemical formula (1-2-2) and the chemical formula (1-2-3) is 60 mol of 4,4′-diaminobenzanilide. More preferably, it is contained in less than 50%, more preferably contained in 50 mol% or less, and particularly preferably contained in 40 mol% or less.
• the polyimide precursor of the present invention has a repeating unit other than the repeating unit represented by the chemical formula (1-2-1) or the chemical formula (1-2-2) and the chemical formula (1-2-3). Units can be included.
• aromatic or aliphatic tetracarboxylic acids can be used as the tetracarboxylic acid component that gives other repeating units.
• bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, ( 4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene
• Derivatives such as -2t, 3t, 6c, 7c-tetracarboxylic acid, and these acid dianhydrides are more preferred because the polyimide is easy to produce and the resulting polyimide has excellent heat resistance.
• These acid dianhydrides may be used alone or in combination of two or more.
• the diamine component that provides other repeating units may be a diamine component that provides the structure of the chemical formula (1-2-A).
• a 2 is a repeating unit of the chemical formula (1-2-1) having the structure of the chemical formula (1-2-A), or A 2 is the chemical formula (
• the diamine exemplified as the diamine component giving the repeating unit of the chemical formula (1-2-2) and the chemical formula (1-2-3) having the structure of 1-2-A) can be used. These diamines may be used alone or in combination of two or more.
• aromatic or aliphatic diamines can be used as the diamine component that gives other repeating units.
• the synthesis method of norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ ′-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acids and the like is not particularly limited. Can be synthesized by the method described in Patent Document 11. As described in Non-Patent Document 3, some stereoisomers may be included depending on the synthesis method. Purification of norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2 ′′ -norbornane-5,5 ′′, 6,6 ′′ -tetracarboxylic acid, etc. By doing so, the stereoisomers can be separated individually or several mixtures can be fractionated.
• the isomers may be isolated and used for polymerization or the like, or the isomers may be used as a mixture in polymerization or the like.
• R 1 and R 2 in the chemical formula (1), R 3 and R 4 in the chemical formula (2), and R 5 and R 6 in the chemical formula (3) are each independently hydrogen, carbon. Either an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. R 1 and R 2 , R 3 and R 4 , R 5 and R 6 can change the type of functional group and the introduction rate of the functional group by the production method described later.
• R 1 and R 2 , R 3 and R 4 , R 5 and R 6 are hydrogen, polyimide tends to be easily produced.
• R 1 and R 2 , R 3 and R 4 , R 5 and R 6 are alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, the storage stability of the polyimide precursor tends to be excellent.
• R 1 and R 2 , R 3 and R 4 , R 5 and R 6 are more preferably a methyl group or an ethyl group.
• R 1 and R 2 , R 3 and R 4 , R 5 and R 6 are alkylsilyl groups having 3 to 9 carbon atoms, the solubility of the polyimide precursor tends to be excellent.
• R 1 and R 2 , R 3 and R 4 , R 5 and R 6 are more preferably a trimethylsilyl group or a t-butyldimethylsilyl group.
• R 1 and R 2 , R 3 and R 4 , R 5 and R 6 are each 25% or more, preferably 50 % Or more, more preferably 75% or more can be an alkyl group or an alkylsilyl group.
• the polyimide precursor of the present invention R 1 and R 2, R 3 and R 4, the chemical structure R 5 and R 6 are taken, 1) a polyamic acid (R 1 and R 2, R 3 and R 4, R 5 And R 6 are hydrogen), 2) polyamic acid ester (R 1 and R 2 , R 3 and R 4 , at least part of R 5 and R 6 are alkyl groups), 3) 4) polyamic acid silyl ester (R 1 And at least part of R 2 , R 3 and R 4 , R 5 and R 6 can be classified as an alkylsilyl group.
• the polyimide precursor of this invention can be easily manufactured with the following manufacturing methods for every classification. However, the manufacturing method of the polyimide precursor of this invention is not limited to the following manufacturing methods.
• the polyimide precursor of the present invention comprises a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent in an equimolar amount, preferably a molar ratio of the diamine component to the tetracarboxylic acid component
• the number of moles of the component / the number of moles of the tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, imidization at a relatively low temperature of 120 ° C. or less. It can obtain suitably as a polyimide precursor solution composition by reacting, suppressing.
• diamine is dissolved in an organic solvent, and tetracarboxylic dianhydride is gradually added to this solution while stirring, and 0 to 120 ° C., preferably 5 to 80 ° C.
• a polyimide precursor is obtained by stirring for 1 to 72 hours in the range of ° C.
• the order of addition of diamine and tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor is likely to increase.
• the molar ratio of the tetracarboxylic acid component and the diamine component is an excess of the diamine component, an amount of a carboxylic acid derivative substantially corresponding to the excess number of moles of the diamine component is added as necessary, The molar ratio of the components can be approximated to the equivalent.
• a carboxylic acid derivative herein, a tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution, that is, substantially does not participate in molecular chain extension, or a tricarboxylic acid that functions as a terminal terminator and its anhydride, Dicarboxylic acid and its anhydride are preferred.
• a polyimide precursor can be easily obtained by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus condensing agent or a carbodiimide condensing agent.
• the polyimide precursor obtained by this method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.
• silylating agent that does not contain chlorine as the silylating agent used here, because it is not necessary to purify the silylated diamine.
• the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane.
• N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.
• an amine catalyst such as pyridine, piperidine or triethylamine can be used to accelerate the reaction.
• This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
• a polyimide precursor is obtained by mixing the polyamic acid solution obtained by the method 1) and a silylating agent and stirring at 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours.
• the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.
• silylating agent used here it is preferable to use a silylating agent not containing chlorine because it is not necessary to purify the silylated polyamic acid or the obtained polyimide.
• examples of the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane.
• N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.
• Any of the above production methods can be suitably carried out in an organic solvent, and as a result, a solution or solution composition containing a polyimide precursor can be easily obtained.
• Solvents used in preparing the polyimide precursor are, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide
• An aprotic solvent such as N, N-dimethylacetamide is preferred, but any type of solvent can be used without any problem as long as the raw material monomer component and the polyimide precursor to be produced are dissolved.
• the structure is not limited.
• amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ - Cyclic ester solvents such as methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenols such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol A system solvent, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed.
• the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more, more preferably 0. .3 dL / g or more, particularly 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 polyimide precursor composition of the present invention contains a polyimide precursor and a phosphorus compound, and can be prepared by adding a phosphorus compound to a polyimide precursor solution or a solution composition obtained by the above production method. Moreover, a solvent may be removed or added as needed, and desired components other than a phosphorus compound may be added. In addition, a tetracarboxylic acid component (tetracarboxylic dianhydride, etc.), a diamine component and a phosphorus compound are added to a solvent, and the tetracarboxylic acid component and the diamine component are reacted in the presence of the phosphorus compound to obtain the polyimide of the present invention. A precursor composition (a solution composition containing a polyimide precursor and a phosphorus compound) can also be obtained.
• the phosphorus compound used in the present invention contains a phosphorus atom and has a boiling point at 1 atm lower than the decomposition temperature and 350 ° C. or less, preferably less than 300 ° C., more preferably less than 250 ° C., further preferably 210 ° C. or less, particularly A compound having a temperature of 200 ° C. or lower is preferable.
• a phosphorus compound whose boiling point at 1 atm is lower than the decomposition temperature and 350 ° C. or less, preferably less than 300 ° C., more preferably less than 250 ° C., further preferably 210 ° C. or less, particularly preferably 200 ° C. or less.
• a polyimide with higher heat resistance can be obtained while maintaining high transparency.
• the phosphorus compound used in the present invention is not particularly limited as long as the boiling point at 1 atm is lower than the decomposition temperature and 350 ° C. or less, but preferably has a PO bond, and trimethyl phosphate (boiling point at 1 atm: 197 ° C.), trimethyl phosphite (boiling point at 1 atm: 111.5 ° C.), dimethyl phosphite (boiling point at 1 atm: 171 ° C.), diethyl phosphite (boiling point at 1 atm: 188 ° C.), etc. .
• a phosphorus compound may be used individually by 1 type, and can also be used in combination of multiple types.
• content of the phosphorus compound of a polyimide precursor composition is although it does not specifically limit, It is preferable that it is 0.01 mol or more with respect to 1 mol of repeating units of a polyimide precursor, and is 0.03 mol or more. More preferably, it is more preferably 0.05 mol or more, and particularly preferably 0.1 mol or more.
• the upper limit of the content of the phosphorus compound in the polyimide precursor composition is not particularly limited, but is usually preferably 8 mol or less, more preferably 6 mol or less, and even more preferably 5 mol or less with respect to 1 mol of the repeating unit of the polyimide precursor. Preferably, it is less than 5 moles. If the content of the phosphorus compound is too large, the heat resistance or transparency of the resulting polyimide may decrease.
• 1 mol of the repeating unit of the polyimide precursor corresponds to 1 mol of the tetracarboxylic acid component.
• the polyimide precursor composition of the present invention usually contains a solvent.
• the solvent used for the polyimide precursor composition of the present invention is not a problem as long as the polyimide precursor is dissolved, and the structure is not particularly limited.
• solvents amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone , Cyclic ester solvents such as ⁇ -methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol Phenol solvents such as acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl
• the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, more preferably 15%, based on the total amount of the solvent, the tetracarboxylic acid component and the diamine component.
• a ratio of not less than mass% is preferred.
• the total amount of the tetracarboxylic acid component and the diamine component is 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. Is preferred.
• This concentration is a concentration approximately approximate to the solid content concentration resulting from the polyimide precursor, but if this concentration is too low, it becomes difficult to control the film thickness of the polyimide film obtained, for example, when producing a polyimide film. Sometimes.
• the viscosity (rotational viscosity) of the polyimide precursor composition is not particularly limited, but the rotational viscosity measured using an E-type rotational viscometer at a temperature of 25 ° C. and a shear rate of 20 sec ⁇ 1 is 0.01 to 1000 Pa ⁇ sec is preferable, and 0.1 to 100 Pa ⁇ sec is more preferable. Moreover, thixotropy can also be provided as needed.
• the viscosity is in the above range, it is easy to handle when coating or forming a film, and the repelling is suppressed and the leveling property is excellent, so that a good film can be obtained.
• the polyimide precursor composition of the present invention includes chemical imidizing agents (acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), antioxidants, fillers (inorganic particles such as silica, etc.) as necessary. ), Dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), release agents and the like.
• chemical imidizing agents as acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline
• antioxidants such as amine compounds such as pyridine and isoquinoline
• fillers inorganic particles such as silica, etc.
• the polyimide of the present invention can be obtained by imidizing the polyimide precursor composition of the present invention as described above (that is, dehydrating and ring-closing reaction of the polyimide precursor).
• the imidization method is not particularly limited, and a known thermal imidation or chemical imidization method can be suitably applied.
• the form of the polyimide obtained can mention suitably a film, the laminated body of a polyimide film and another base material, a coating film, powder, a bead, a molded object, a foam.
• the polyimide precursor composition can be heat-treated to imidize the polyimide precursor.
• the maximum heating temperature of the heat treatment for imidization is not particularly limited, but is usually 200 ° C or higher, preferably higher than 350 ° C, more preferably higher than 380 ° C, and particularly higher than 400 ° C. preferable.
• the maximum heating temperature of the heat treatment for imidization is set to a temperature exceeding 350 ° C., more preferably a temperature exceeding 380 ° C., particularly preferably a temperature exceeding 400 ° C.
• the mechanical properties of the resulting polyimide are improved.
• the upper limit of the maximum heating temperature of heat processing is not specifically limited, Usually, 500 degrees C or less is preferable.
• the polyimide precursor composition of the present invention is cast and applied onto a substrate, and the polyimide precursor composition on the substrate is heat-treated at a maximum heating temperature of 200 ° C. or higher, more preferably 350 ° C. or higher.
• a polyimide can be suitably manufactured by imidating a polyimide precursor.
• the heating profile is not particularly limited and can be selected as appropriate. However, from the viewpoint of productivity, it is preferable that the heat treatment time is short.
• the polyimide precursor composition of the present invention is cast and applied on a substrate, and preferably dried in a temperature range of 180 ° C. or less to form a polyimide precursor composition film on the substrate.
• the heat treatment is performed at a maximum heating temperature of 200 ° C. or more, more preferably at a temperature exceeding 350 ° C.
• a polyimide can be suitably manufactured also by imidizing a polyimide precursor.
• the polyimide obtained from the polyimide precursor composition of the present invention is not particularly limited, but the linear thermal expansion coefficient from 150 ° C. to 250 ° C. when converted into a film is preferably 65 ppm / K or less, More preferably, it is 50 ppm / K or less, More preferably, it is 35 ppm / K or less, More preferably, it is 30 ppm / K or less, Most preferably, it is 20 ppm / K or less.
• the linear thermal expansion coefficient is large, the difference in the linear thermal expansion coefficient with a conductor such as metal is large, which may cause problems such as an increase in warpage when a circuit board is formed.
• the polyimide obtained from the polyimide precursor composition of the present invention is not particularly limited, but preferably has a total light transmittance (average light transmittance of a wavelength of 380 nm to 780 nm) in a film having a thickness of 10 ⁇ m. May be 87% or more, more preferably 88% or more. When used for a display application or the like, if the total light transmittance is low, it is necessary to strengthen the light source, which may cause a problem that energy is applied.
• the polyimide film when a polyimide film such as a display application is used for an application where light is transmitted, it is desirable that the polyimide film has high transparency.
• the polyimide obtained from the polyimide precursor composition of the present invention (polyimide of the present invention) is not particularly limited, but the light transmittance at a wavelength of 400 nm in a film having a thickness of 10 ⁇ m is preferably 75% or more, more preferably 78. % Or more, more preferably 80% or more, particularly preferably more than 80%.
• the film made of the polyimide obtained from the polyimide precursor composition of the present invention depends on the use, but the thickness of the film is preferably 0.1 ⁇ m to 250 ⁇ m, more preferably 1 ⁇ m to The thickness is 150 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, particularly preferably 1 ⁇ m to 30 ⁇ m.
• the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance may be lowered.
• the polyimide obtained from the polyimide precursor composition of the present invention is not particularly limited, but the 1% weight loss temperature, which is an index of heat resistance of the polyimide film, is preferably 440 ° C. or more, more preferably It can be 450 ° C. or higher, more preferably 480 ° C. or higher, and particularly preferably 485 ° C. or higher.
• the 1% weight loss temperature which is an index of heat resistance of the polyimide film
• the polyimide obtained from the polyimide precursor composition of the present invention that is, the polyimide of the present invention has excellent properties such as high transparency, bending resistance and high heat resistance, and also has a very low linear thermal expansion coefficient.
• a transparent substrate for a display, a transparent substrate for a touch panel, or a substrate for a solar cell it can be suitably used.
• the polyimide precursor composition (varnish) of the present invention is cast on a substrate such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat resistant plastic film (polyimide film, etc.), etc.
• a substrate such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat resistant plastic film (polyimide film, etc.), etc.
• a vacuum in an inert gas such as nitrogen, or in the air, drying is performed in a temperature range of 20 to 180 ° C., preferably 20 to 150 ° C. using hot air or infrared rays.
• a polyimide film / substrate laminate or a polyimide film can be produced by heating imidization in air using hot air or infrared rays, for example, at 200 to 500 ° C., preferably at a temperature exceeding the maximum heating temperature of 350 ° C. it can.
• the thickness of the polyimide film here is preferably 1 to 250 ⁇ m, more preferably 1 to 150 ⁇ m, because of the transportability in the subsequent steps.
• the imidization reaction of the polyimide precursor instead of the heat imidation by the heat treatment as described above, contains a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It is also possible to carry out by chemical treatment such as immersion in a solution. In addition, these dehydrating cyclization reagents are previously charged and stirred in a polyimide precursor composition (varnish), and cast and dried on a base material to obtain a partially imidized polyimide precursor. A polyimide film / base material laminate or a polyimide film can be obtained by further heat treatment as described above.
• a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It is also possible to carry out by chemical treatment such as immersion in a solution.
• these dehydrating cyclization reagents are previously charged
• a flexible conductive substrate can be obtained by forming a conductive layer on one side or both sides of the polyimide film / base laminate or the polyimide film obtained in this way.
• a flexible conductive substrate can be obtained, for example, by the following method. That is, as a first method, the polyimide film / substrate laminate is not peeled off from the substrate, and the surface of the polyimide film is sputtered, vapor-deposited, printed, etc. by a conductive substance (metal or metal oxide). A conductive layer of conductive layer / polyimide film / base material is produced. Then, if necessary, a transparent and flexible conductive substrate comprising the conductive layer / polyimide film laminate can be obtained by peeling the conductive layer / polyimide film laminate from the substrate.
• a transparent and flexible conductive substrate comprising the conductive layer / polyimide film laminate can be obtained by peeling the conductive layer / polyimide film laminate from the substrate.
• the polyimide film is peeled off from the substrate of the polyimide film / substrate laminate to obtain a polyimide film, and a conductive substance (metal or metal oxide, conductive organic substance, A conductive layer of conductive carbon, etc.) is formed in the same manner as in the first method, and is a transparent and flexible conductive layer comprising a conductive layer / polyimide film laminate and a conductive layer / polyimide film laminate / conductive layer.
• a substrate can be obtained.
• a gas barrier layer such as water vapor or oxygen, light adjustment by sputtering, vapor deposition or gel-sol method, etc.
• An inorganic layer such as a layer may be formed.
• the conductive layer is preferably formed with a circuit by a method such as a photolithography method, various printing methods, or an ink jet method.
• the substrate of the present invention thus obtained has a circuit of a conductive layer on the surface of a polyimide film composed of the polyimide of the present invention, with a gas barrier layer or an inorganic layer as necessary.
• This substrate is flexible, has excellent transparency, bendability, and heat resistance, and further has a very low linear thermal expansion coefficient and excellent solvent resistance, so that a fine circuit can be easily formed. Therefore, this board
• a transistor inorganic transistor, organic transistor
• a transistor is further formed on this substrate by vapor deposition, various printing methods, an ink jet method or the like to manufacture a flexible thin film transistor, and a liquid crystal element, an EL element, a photoelectric transistor for a display device are manufactured. It is suitably used as an element.
• Linear thermal expansion coefficient (CTE) A polyimide film having a thickness of about 10 ⁇ m is cut into a strip having a width of 4 mm to form a test piece, and TMA / SS6100 (manufactured by SII Nano Technology Co., Ltd.) is used. The length between chucks is 15 mm, the load is 2 g, and the heating rate is 20 ° C. / The temperature was raised to 500 ° C. in minutes. The linear thermal expansion coefficient from 150 ° C. to 250 ° C. was determined from the obtained TMA curve.
• a polyimide film having a film thickness of about 10 ⁇ m was used as a test piece, and the temperature was raised from 25 ° C. to 600 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen stream using a calorimeter measuring device (Q5000IR) manufactured by TA Instruments. From the obtained weight curve, a 1% weight loss temperature was determined.
• Table 1-1 shows tetracarboxylic acid components used in Examples and Comparative Examples
• Table 1-2 shows Examples and Comparative Examples
• Table 1-3 shows Examples and Comparative Examples of Phosphorus Compounds. Describe the structural formula.
• Example 1 0.07 g (0.50 mmol) of trimethyl phosphate and 0.07 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 33.76 g of varnish A obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish A) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.05 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 2 Trimethyl phosphate (0.14 g, 1.00 mmol) and N-methyl-2-pyrrolidone (0.14 g) were added to the reaction vessel to obtain a uniform solution. 33.76 g of varnish A obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish A) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.1 equivalent per mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 3 Trimethyl phosphate 0.28 g (2.00 mmol) and N-methyl-2-pyrrolidone 0.28 g were added to the reaction vessel to obtain a homogeneous solution. 33.76 g of varnish A obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish A) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.2 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 4 A uniform solution was obtained by adding 0.56 g (4.00 mmol) of trimethyl phosphate and 0.56 g of N-methyl-2-pyrrolidone to the reaction vessel. 33.76 g of varnish A obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish A) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.4 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 5 0.25 g (2.00 mmol) of trimethyl phosphite and 0.25 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 33.76 g of varnish A obtained in Synthesis Example 1 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish A) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphite is 0.2 equivalent per mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 6 Trimethyl phosphate (0.14 g, 1.00 mmol) and N-methyl-2-pyrrolidone (0.14 g) were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.1 equivalent per mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 7 Trimethyl phosphate 0.28 g (2.00 mmol) and N-methyl-2-pyrrolidone 0.28 g were added to the reaction vessel to obtain a homogeneous solution.
• 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.2 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 410 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 8 0.14 g (1.0 mmol) of diethyl phosphite and 0.14 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 0.1 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 9 0.28 g (2.0 mmol) of diethyl phosphite and 0.28 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 0.2 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 10 0.55 g (4.0 mmol) of diethyl phosphite and 0.55 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 0.4 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 11 0.97 g (7.0 mmol) of diethyl phosphite and 0.60 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 0.7 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 12 1.38 g (10.0 mmol) of diethyl phosphite and 0.60 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 1.0 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 13 1.80 g (13.0 mmol) of diethyl phosphite and 0.60 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 1.3 equivalents with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 14 2.76 g (20.0 mmol) of diethyl phosphite and 0.60 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of diethyl phosphite is 2.0 equivalents with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 15 0.44 g (4.0 mmol) of dimethyl phosphite and 0.44 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution.
• 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of dimethyl phosphite is 0.4 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 16 2.48 g (20.0 mmol) of trimethyl phosphite and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution. 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphite is 2.0 equivalents per mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 17 4.96 g (40.0 mmol) of trimethyl phosphite and 0.50 g of N-methyl-2-pyrrolidone were added to the reaction vessel to obtain a uniform solution.
• 35.39 g of varnish B obtained in Synthesis Example 2 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish B) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphite is 4.0 equivalents with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 420 ° C. on the glass substrate to thermally imidize it.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 18 Trimethyl phosphate (0.14 g, 1.0 mmol) and N-methyl-2-pyrrolidone (0.14 g) were added to the reaction vessel to obtain a uniform solution. 24.94 g of varnish C obtained in Synthesis Example 3 (10 mmol with respect to the molecular weight of the polyimide precursor repeating unit in varnish C) was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.1 equivalent per mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 400 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• Example 19 A uniform solution was obtained by adding 0.28 g (2.0 mmol) of trimethyl phosphate and 0.28 g of N-methyl-2-pyrrolidone to the reaction vessel. To the solution, 35.95 g of varnish D obtained in Synthesis Example 4 (10 mmol with respect to the molecular weight of the repeating unit of the polyimide precursor in varnish D) was added and stirred at room temperature for 3 hours to obtain a uniform and viscous polyimide. A precursor solution was obtained. When calculated from the charged amount, the number of moles of trimethyl phosphate is 0.2 equivalent with respect to 1 mole of the repeating unit of the polyimide precursor.
• a polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 370 ° C. as it is, and thermally imidized to be colorless.
• a transparent polyimide film / glass laminate was obtained.
• the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
• a polyimide containing a phosphorus compound (phosphoric acid, tributyl phosphate) whose boiling point at 1 atmosphere is higher than the decomposition temperature, or a phosphorus compound (triphenyl phosphate, triphenyl phosphite) whose boiling point at 1 atmosphere exceeds 350 ° C.
• a polyimide containing a phosphorus compound phosphoric acid, tributyl phosphate
• a phosphorus compound triphenyl phosphate, triphenyl phosphite
• the polyimide obtained from the polyimide precursor composition of the present invention has excellent light transmittance, mechanical properties, high heat resistance, and has a low linear thermal expansion coefficient
• the polyimide film of the present invention can be suitably used as a transparent substrate that is colorless and transparent and capable of forming a fine circuit, such as for display applications.
• a polyimide having excellent transparency and mechanical properties and a polyimide precursor composition (solution composition containing a polyimide precursor) from which a polyimide having higher heat resistance can be obtained with the same composition, and polyimide A manufacturing method can be provided.
• the polyimide obtained from this polyimide precursor composition has high transparency, higher heat resistance, low coefficient of thermal expansion, and easy formation of fine circuits. Can be suitably used for forming a substrate for a solar cell or a solar cell.

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