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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/025—Electric or magnetic properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
  • C08K5/3447—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0346—Organic insulating material consisting of one material containing N
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
  • B32B2379/08—Polyimides

Definitions

• the present invention relates to a polyimide precursor composition and a polyimide film with improved thermal decomposition resistance, which are suitably used for electronic device applications such as flexible device substrates.
• polyimide film Due to its excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability, polyimide film has been widely used in fields such as electrical and electronic devices and semiconductors.
• optical materials such as optical fibers and optical waveguides in the field of optical communication, and liquid crystal alignment films and protective films for color filters in the field of display devices is progressing.
• studies on plastic substrates that are lightweight and excellent in flexibility as an alternative to glass substrates and development of displays that can be bent or rolled are being actively pursued.
• Polyimide is generally colored in yellowish brown, which limits its use in transmissive devices such as liquid crystal displays equipped with a backlight. Polyimide films with excellent light transmittance have been developed, and expectations are rising for use as substrates for display applications (see Patent Documents 1 to 3).
• Patent Documents 4 to 8 disclose a polyimide film obtained from a monomer component containing a tetracarboxylic dianhydride having two norbornane ring (bicyclo[2.2.1]heptane ring) structures bonded by a single bond. It is
• TFTs thin film transistors
• a-Si TFTs amorphous silicon TFTs
• LTPS TFTs low temperature polysilicon TFTs
• high temperature polysilicon TFTs oxide TFTs.
• a film formation temperature of 300° C. to 400° C. is required even for an amorphous silicon TFT, which can be formed at a relatively low temperature.
• high-temperature deposition is advantageous for forming a semiconductor layer with high charge mobility.
• the polyimide film has insufficient thermal decomposition resistance, for example, in the TFT formation process, outgassing due to decomposition of the polyimide causes swelling between the polyimide film and the barrier film, or contamination of the manufacturing equipment. Sometimes.
• a material that is stable at high temperatures that is, a film that is excellent in thermal decomposition resistance at the process temperature and generates extremely little gas is preferable. Also from the viewpoint of process margin, a film having a high thermal decomposition (starting) temperature is preferable.
• a polyimide film with a sufficiently small coefficient of linear thermal expansion (CTE) and excellent thermal properties can be used as a substrate for flexible electronic devices. is preferred.
• Patent Documents 4 to 8 state that the objective is to provide a polyimide having excellent light transmittance and heat resistance.
• a polyimide film which satisfies a sufficiently small coefficient of linear thermal expansion and thermal decomposition resistance at the same time while having light transmittance and mechanical properties within a satisfactory range.
• Patent Document 8 2,2′-vinorbornane-5,5′,6,6′-tetracarboxylic dianhydride (hereinafter abbreviated as BNBDA if necessary) and 2,2′-bis(3, 4-dicarboxyphenyl)hexafluoropropanoic dianhydride (hereinafter abbreviated as 6FDA if necessary) and 2,2′-bis(trifluoromethyl)benzidine (hereinafter abbreviated as TFMB if necessary) as a diamine component are reacted. It is described that a polyimide film was produced using the polyimide solution obtained by the above method.
• BNBDA 2,2′-vinorbornane-5,5′,6,6′-tetracarboxylic dianhydride
• 6FDA 2,2′-bis(3, 4-dicarboxyphenyl)hexafluoropropanoic dianhydride
• TFMB 2,2′-bis(trifluoromethyl)benzidine
• the polyimide film described in Patent Document 8 has a large coefficient of linear thermal expansion and lacks heat resistance indicated by thermal decomposition temperature and glass transition temperature. Therefore, there is a strong demand for realization of a polyimide film which is excellent in these properties and which is suitable for use as a flexible electronic device substrate, for example.
• the present invention has been made in view of the conventional problems, and provides a polyimide film having a sufficiently small linear thermal expansion coefficient, excellent mechanical properties, and particularly excellent light transparency and thermal decomposition resistance. It is an object of the present invention to provide a precursor composition that can be produced and a polyimide film obtained from this precursor composition.
• a polyimide precursor whose repeating unit is represented by the following general formula (I), At least one imidazole compound contained in an amount ranging from more than 0.01 mol to 2 mol or less per 1 mol of repeating units of the polyimide precursor, and a polyimide precursor characterized by containing a solvent. Composition.
• X 1 is a tetravalent aliphatic or aromatic group
• Y 1 is a divalent aliphatic or aromatic group
• R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, provided that 70 mol % or more of X 1 is represented by formula (1-1):
• the imidazole compound is at least one selected from the group consisting of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole.
• polyimide film obtained from the polyimide precursor composition according to any one of the above items 1 to 3, wherein a film having a thickness of 10 ⁇ m has a light transmittance of 80% or more at a wavelength of 400 nm. Polyimide precursor composition.
• polyimide precursor composition according to any one of the above items 1 to 4, wherein a polyimide film obtained from this polyimide precursor composition exhibits a 5% weight loss temperature of 490°C or higher.
• polyimide precursor composition according to any one of the above items 1 to 5, wherein the polyimide film obtained from this polyimide precursor composition has a linear thermal expansion coefficient of 20 ppm/K or less.
• the linear thermal expansion coefficient is sufficiently small, and excellent mechanical properties, in addition, polyimide precursor composition capable of producing a polyimide film particularly excellent in light transmittance and thermal decomposition resistance and a polyimide film obtained from this precursor composition.
• a polyimide film and a polyimide film/substrate laminate obtained using the polyimide precursor composition Furthermore, according to another aspect of the present invention, it is possible to provide a method for manufacturing a flexible electronic device using the polyimide precursor composition, and a flexible electronic device.
• a “flexible (electronic) device” means that the device itself is flexible, and the device is usually completed by forming semiconductor layers (transistors, diodes, etc. as elements) on a substrate.
• a “flexible (electronic) device” is distinguished from devices such as COF (Chip On Film) in which a “hard” semiconductor element such as an IC chip is mounted on a conventional FPC (Flexible Printed Circuit Board).
• Suitable flexible (electronic) devices include display devices such as liquid crystal displays, organic EL displays, and electronic papers, and light receiving devices such as solar cells and CMOS.
• the polyimide precursor composition of the present invention will be described below, and then the method for producing a flexible electronic device will be described.
• a polyimide precursor composition for forming a polyimide film contains a polyimide precursor, an imidazole compound and a solvent. Both the polyimide precursor and the imidazole compound are dissolved in a solvent.
• the polyimide precursor has the following general formula (I):
• X 1 is a tetravalent aliphatic or aromatic group
• Y 1 is a divalent aliphatic or aromatic group
• R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
• R 1 and R 2 are independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to
• X 1 has a structure represented by the following formula (1-1), that is, 2,2'-vinorbornane-5,5',6 ,6′-tetracarboxylic dianhydride (hereinafter abbreviated as BNBDA if necessary).
• BNBDA 2,2'-vinorbornane-5,5',6 ,6′-tetracarboxylic dianhydride
• Y 1 has a structure represented by the following formula (B-1), that is, m-tolysine (abbreviated as m-TD if necessary). It is the structure from which
• a polyimide film having a sufficiently small coefficient of linear thermal expansion, excellent optical transparency and mechanical properties, and particularly excellent thermal decomposition resistance can be obtained. can be manufactured.
• the polyimide precursor will be explained by the monomers (tetracarboxylic acid component, diamine component, and other components) that give X 1 and Y 1 in the general formula (I), and then the production method will be explained.
• the tetracarboxylic acid component means a tetracarboxylic acid, a tetracarboxylic dianhydride, and other tetracarboxylic acid silyl esters, tetracarboxylic acid esters, tetracarboxylic acid chlorides, and the like, which are used as raw materials for producing polyimide.
• a tetracarboxylic dianhydride it is convenient to use a tetracarboxylic dianhydride in terms of production, and in the following explanation, an example using a tetracarboxylic dianhydride as a tetracarboxylic acid component will be described.
• the diamine component is a diamine compound having two amino groups (--NH 2 ), which is used as a raw material for producing polyimide.
• a polyimide film means both a film formed on a (carrier) substrate and present in a laminate, and a film after peeling off the substrate.
• the material which comprises the polyimide film ie, the material obtained by heat-processing (imidating) the polyimide precursor composition, may be called "polyimide material.”
• X 1 and tetracarboxylic acid component preferably 70 mol% or more of X 1 is a structure represented by formula (1-1), more preferably 80 mol% or more, even more preferably 90 mol % or more, most preferably 95 mol % or more (100 mol % is also highly preferred) is a structure represented by formula (1-1).
• the tetracarboxylic dianhydride that gives the structure of formula (1-1) as X 1 is 2,2′-vinorbornane-5,5′,6,6′-tetracarboxylic dianhydride (BNBDA).
• X 1 is a tetravalent aliphatic group or aromatic group (abbreviated as “other X 1 ”) other than the structure represented by formula (1-1), without impairing the effects of the present invention. It can be contained in a range of amounts. That is, the tetracarboxylic acid component can contain, in addition to BNBDA, other tetracarboxylic acid derivatives in amounts that do not impair the effects of the present invention.
• the amount of the other tetracarboxylic acid derivative is less than 30 mol%, more preferably less than 20 mol%, still more preferably less than 10 mol% (0 mol% is also preferable) with respect to 100 mol% of the tetracarboxylic acid component. be.
• X 1 is a tetravalent group having an aromatic ring, it is preferably a tetravalent group having an aromatic ring and having 6 to 40 carbon atoms.
• Examples of the tetravalent group having an aromatic ring include the following.
• Z 1 is a direct bond or the following divalent group:
• Z2 in the formula is a divalent organic group
• Z3 and Z4 are each independently an amide bond, an ester bond and a carbonyl bond
• Z5 is an organic group containing an aromatic ring.
• Z 2 specifically includes an aliphatic hydrocarbon group having 2 to 24 carbon atoms and an aromatic hydrocarbon group having 6 to 24 carbon atoms.
• Z 5 specifically includes an aromatic hydrocarbon group having 6 to 24 carbon atoms.
• the following groups are particularly preferred because they can achieve both high heat resistance and high light transmittance in the resulting polyimide film.
• Z 1 is a direct bond or a hexafluoroisopropylidene bond.
• Z1 is a direct bond, since the obtained polyimide film can achieve both high heat resistance, high light transmittance, and a low coefficient of linear thermal expansion.
• Z 1 is the following formula (3A):
• Z 11 and Z 12 are each independently, preferably the same, a single bond or a divalent organic group.
• Z 11 and Z 12 are preferably organic groups containing an aromatic ring, such as formula (3A1):
• Z 13 and Z 14 are each independently a single bond, -COO-, -OCO- or -O-, where when Z 14 is bonded to a fluorenyl group, Z 13 is -COO-, -OCO- or -O- and Z 14 is preferably a single bond structure;
• R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably methyl;
• n is an integer of 0 to 4, preferably 1.
• Examples of the tetracarboxylic acid component that gives the repeating unit of general formula (I) in which X 1 is a tetravalent group having an aromatic ring 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-dicarboxy phenyl)sulfone, m-terphenyl-3,4,3′,4′-tetracarboxylic acid, p-terphenyl-3,
• tetracarboxylic acid components that give repeating units of general formula (I), wherein X 1 is a tetravalent group having an aromatic ring containing a fluorine atom, include 2,2-bis(3,4-dicarboxy phenyl)hexafluoropropane and its derivatives such as tetracarboxylic dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester and tetracarboxylic acid chloride.
• tetracarboxylic acid component may be used alone or in combination of multiple types.
• X 1 is a tetravalent group having an alicyclic structure
• it is preferably a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms, at least one aliphatic 4- to 12-membered ring, More preferably, it has an aliphatic 4-membered ring or an aliphatic 6-membered ring.
• Preferred tetravalent groups having an aliphatic 4-membered ring or an aliphatic 6-membered ring include the following.
• R 31 to R 38 are each independently a direct bond or a divalent organic group.
• R 41 to R 47 and R 71 to R 73 are each independently of the formula: —CH 2 — , —CH ⁇ CH—, —CH 2 CH 2 —, —O—, and —S—
• R 48 is an organic ring containing an aromatic or alicyclic structure base.
• R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 are a direct bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or Oxygen atom (--O--), sulfur atom (--S--), carbonyl bond, ester bond and amide bond.
• Examples of the organic group containing an aromatic ring as R 48 include the following.
• W 1 is a direct bond or a divalent organic group
• n 11 to n 13 each independently represent an integer of 0 to 4
• R 51 , R 52 and R 53 each independently is an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.
• W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).
• R 61 to R 68 in formula (6) each independently represent either a direct bond or a divalent group represented by formula (5) above.
• the tetravalent group having an alicyclic structure the following groups are particularly preferred because the obtained polyimide can have both high heat resistance, high light transmittance, and a low coefficient of linear thermal expansion.
• Examples of the tetracarboxylic acid component that gives the repeating unit of formula (I) in which X 1 is a tetravalent group having an alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidene diphenoxybis phthalic 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,
• Y 1 preferably has a structure represented by formula (B-1) in an amount of preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol % or more, still more preferably 80 mol % or more, still more preferably 90 mol % or more (100 mol % is also preferred) is the structure represented by formula (B-1).
• the diamine compound that gives the structure of formula (B-1) as Y 1 is m-tolidine (abbreviation: m-TD).
• Y 1 a divalent aliphatic group or aromatic group (abbreviated as “other Y 1 ”) other than the structure represented by formula (B-1) may be used without impairing the effects of the present invention. It can be contained in a range of amounts. That is, the diamine component can contain other diamine compounds in addition to m-TD in an amount within a range that does not impair the effects of the present invention.
• the amount of the other diamine compound is 50 mol% or less (preferably less than 50 mol%), more preferably 40 mol% or less (preferably less than 40 mol%), more preferably 30 mol% or less with respect to 100 mol% of the diamine component.
• mol % or less (preferably less than 30 mol %), more preferably 20 mol % or less (preferably less than 20 mol %), still more preferably 10 mol % or less (preferably less than 10 mol %) (0 mol % is also preferable) ).
• the ratio of the structure of formula (B-1) in Y 1 is less than 100 mol%.
• n1 and n2 each independently represent an integer of 0 to 4
• B 1 and B 2 each independently represent an alkyl group having 1 to 6 carbon atoms
• a halogen group or a carbon represents one selected from the group consisting of fluoroalkyl groups of numbers 1 to 6
• each X is independently a direct bond or represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- represents one selected from the group consisting of the group consisting of, excluding the above formula (B-1).
• It preferably contains a structure represented by
• n1 and n2 are preferably 0 or 1
• B 1 and B 2 are preferably a methyl group or a trifluoromethyl group.
• the structure of formula (G-1) is contained in Y 1 in a proportion of preferably more than 0 mol % and 50 mol % or less, more preferably more than 5 mol % and 50 mol % or less.
• mechanical properties such as breaking strength and optical properties can be improved.
• the structure of formula (G-1) is represented by formula (B-2):
• “Other Y 1 ” other than formula (G-1) (regardless of whether it contains the structure of formula (G-1) or not; the same shall apply hereinafter), “other Y 1 ” has an aromatic ring
• a divalent group having an aromatic ring having 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms is preferred.
• divalent groups having an aromatic ring examples include the following. However, those included in formula (G-1) are excluded.
• W 1 is a direct bond or a divalent organic group
• n 11 to n 13 each independently represent an integer of 0 to 4
• R 51 , R 52 and R 53 each independently is an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.
• W 1 examples include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).
• R 61 to R 68 in formula (6) each independently represent either a direct bond or a divalent group represented by formula (5) above.
• W 1 is a direct bond or a formula: -NHCO-, -CONH-, -COO-, -OCO-
• W 1 is one selected from the group consisting of groups represented by the formulas: -NHCO-, -CONH-, -COO-, and -OCO-, wherein R 61 to R 68 are direct bonds.
• Any one of the divalent groups represented by formula (6) is also particularly preferred.
• “other Y 1 ” is selected unlike formula (D-1) or formula (D-2).
• W 1 is represented by the following formula (3B):
• Z 11 and Z 12 are each independently, preferably the same, a single bond or a divalent organic group.
• Z 11 and Z 12 are preferably organic groups containing aromatic rings, such as formula (3B1):
• Z 13 and Z 14 are each independently a single bond, -COO-, -OCO- or -O-, where when Z 14 is bonded to a fluorenyl group, Z 13 is -COO-, -OCO- or -O- and Z 14 is preferably a single bond;
• R 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably phenyl;
• n is an integer of 0 to 4, preferably 1.
• Another preferred group is a compound in which W1 is a phenylene group in the above formula (4), that is, a terphenyldiamine compound, and particularly preferred is a compound in which all are para bonds.
• R 61 and R 62 are 2,2-propylidene groups in the structure of formula (4) above where W 1 is the first phenyl ring of formula (6).
• W 1 is represented by the following formula (3B2):
• Examples of diamine components that give repeating units of general formula (I) wherein Y 1 is a divalent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-diamino- biphenyl, 2,2′-bis(trifluoromethyl)benzidine, 3,3′-bis(trifluoromethyl)benzidine, m-tolidine, 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)-[
• Examples of the diamine component that gives the repeating unit of general formula (I), wherein Y 1 is a divalent group having an aromatic ring containing a fluorine atom 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.
• preferred diamine compounds include 9,9-bis(4-aminophenyl)fluorene, 4,4′-(((9H-fluorene-9,9-diyl)bis([1,1′-biphenyl]-5 ,2-diyl))bis(oxy))diamine, [1,1′:4′,1′′-terphenyl]-4,4′′-diamine, 4,4′-([1,1′-binaphthalene] -2,2'-diylbis(oxy))diamines.
• a diamine component may be used individually and can also be used in combination of multiple types.
• Y 1 is a divalent group having an alicyclic structure, it is preferably a divalent group having an alicyclic structure having 4 to 40 carbon atoms, at least one aliphatic 4- to 12-membered ring, More preferably, it has an aliphatic 6-membered ring.
• divalent groups having an alicyclic structure examples include the following.
• V 1 and V 2 are each independently a direct bond or a divalent organic group
• n 21 to n 26 each independently represent an integer of 0 to 4
• R 81 to R 86 each independently represents an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group or a trifluoromethyl group
• V 1 and V 2 include a direct bond and a divalent group represented by formula (5) above.
• the divalent group having an alicyclic structure the following are particularly preferable because they can achieve both high heat resistance and a low coefficient of linear thermal expansion of the resulting polyimide.
• divalent groups having an alicyclic structure the following are preferred.
• Examples of the diamine component that gives the repeating unit of general formula (I) wherein Y 1 is a divalent group having an alicyclic structure include 1,4-diaminocyclohexane and 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-diamino Cyclobutane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptan
• any of aliphatic tetracarboxylic acids (especially dianhydrides) other than alicyclic and/or aliphatic diamines is used.
• the content is preferably less than 30 mol%, more preferably less than 20 mol%, and still more preferably less than 10 mol% ( including 0%).
• “Other Y 1 ” has a structure represented by formula (4), and specific compounds include p-phenylenediamine, 3,3′-bis(trifluoromethyl)benzidine, m-tolidine, 4,4′. -By including a diamine compound such as bis(4-aminophenoxy)biphenyl, the light transmittance of the resulting polyimide film may be improved.
• the structure represented by the formula (3B) as the “other Y 1 ”, and specific compounds such as 9,9-bis(4-aminophenyl)fluorene and other diamine compounds are included to increase Tg. In some cases, the film thickness can be improved and the retardation in the film thickness direction can be reduced.
• a polyimide precursor can be produced from the above tetracarboxylic acid component and diamine component.
• the polyimide precursor used in the present invention (polyimide precursor containing at least one repeating unit represented by the formula (I) ) is 1) Polyamic acid (R 1 and R 2 are hydrogen), 2) polyamic acid ester (at least part of R 1 and R 2 is an alkyl group), 3) 4) polyamic acid silyl ester (at least a portion of R 1 and R 2 are alkylsilyl groups), can be classified into Polyimide precursors can be easily produced by the following production methods for each of these classifications.
• the method for producing the polyimide precursor used in the present invention is not limited to the following production method.
• a polyimide precursor is prepared by mixing a tetracarboxylic acid dianhydride as a tetracarboxylic acid component and a diamine component in a solvent in approximately equimolar amounts, preferably the molar ratio of the diamine component to the tetracarboxylic acid component number/moles of tetracarboxylic acid component] is preferably from 0.90 to 1.10, more preferably from 0.95 to 1.05. It can be suitably obtained as a polyimide precursor solution by reacting while.
• diamine is dissolved in an organic solvent or water, and tetracarboxylic dianhydride is gradually added to this solution while stirring, and the temperature is adjusted to 0 to 120°C, preferably 5 A polyimide precursor is obtained by stirring in the range of ⁇ 80°C for 1 to 72 hours.
• the reaction is carried out at 80° C. or higher, the molecular weight fluctuates depending on the temperature history during polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.
• the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor tends to increase.
• a tetracarboxylic acid dianhydride is reacted with any alcohol to obtain a diester dicarboxylic acid, which is then reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride.
• the diester dicarboxylic acid chloride and diamine are stirred at ⁇ 20 to 120° C., preferably ⁇ 5 to 80° C. for 1 to 72 hours to obtain a polyimide precursor. When the reaction is carried out at 80° C.
• a polyimide precursor can also be easily obtained by subjecting a diester dicarboxylic acid and a diamine to dehydration condensation using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.
• the polyimide precursor obtained by this method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.
• Polyamic acid silyl ester (direct method)
• the polyamic acid solution obtained by method 1) and the silylating agent are mixed and stirred at 0 to 120° C., preferably 5 to 80° C. for 1 to 72 hours to obtain a polyimide precursor.
• the reaction is carried out at 80° C. or higher, the molecular weight fluctuates depending on the temperature history during polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be stably produced.
• the chlorine atom-free silylating agent includes 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-based catalyst such as pyridine, piperidine, and triethylamine can be used to promote the reaction.
• This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
• Solvents used in preparing the polyimide precursor include water and, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3 -Aprotic solvents such as dimethyl-2-imidazolidinone and dimethyl sulfoxide are preferred, and any type of solvent can be used without any problem as long as the raw material monomer components and the polyimide precursor to be formed dissolve.
• the structure is not limited.
• Solvents include water, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone , ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone and other cyclic ester solvents, ethylene carbonate, propylene carbonate and other carbonate solvents, triethylene glycol and other glycol solvents, m-cresol, p-cresol, 3 Phenolic solvents such as -chlorophenol and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and the like are preferably employed.
• amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide
• a solvent can also be used in combination of multiple types.
• the monomer and solvent are charged at a concentration such that the solid content concentration (polyimide conversion mass concentration) of the polyimide precursor is, for example, 5 to 45% by mass, and the reaction is carried out.
• the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in N-methyl-2-pyrrolidone 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 obtained polyimide is excellent in mechanical strength and heat resistance.
• the polyimide precursor composition contains at least one imidazole compound.
• the imidazole compound is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-phenylimidazole, imidazole and benzimidazole. is mentioned. From the viewpoint of storage stability of the polyimide precursor composition, 2-phenylimidazole and benzimidazole are preferred.
• the imidazole compound may be used in combination of multiple compounds.
• the content of the imidazole compound in the polyimide precursor composition can be appropriately selected in consideration of the balance between the effect of addition and the stability of the polyimide precursor composition.
• the amount of the imidazole compound is preferably from more than 0.01 mol to 2 mol or less with respect to 1 mol of repeating units of the polyimide precursor. Addition of an imidazole compound is effective in improving light transmittance, coefficient of linear thermal expansion and/or mechanical properties. may become.
• the content of the imidazole compound is more preferably 0.02 mol or more, still more preferably 0.025 mol or more, still more preferably 0.05 mol or more, and more preferably 0.05 mol or more per 1 mol of the repeating unit. It is preferably 1.5 mol or less, still more preferably 1.2 mol or less, even more preferably 1.0 mol or less, still more preferably 0.8 mol or less, and most preferably 0.6 mol or less.
• the polyimide precursor composition used in the present invention comprises at least one polyimide precursor, at least one imidazole compound as described above, and a solvent.
• the above-described solvent used in preparing the polyimide precursor can be used.
• the solvent used in preparing the polyimide precursor can be used as it is, that is, as the polyimide precursor solution, but if necessary, it may be used after being diluted or concentrated.
• the imidazole compound is present dissolved in the polyimide precursor composition.
• concentration of the polyimide precursor is not particularly limited, it is usually 5 to 45% by mass in terms of polyimide mass concentration (solid content concentration).
• the polyimide conversion mass is the mass when all repeating units are completely imidized.
• the viscosity (rotational viscosity ) of the polyimide precursor composition of the present invention is not particularly limited. ⁇ sec is preferable, and 0.1 to 100 Pa ⁇ sec is more preferable. In addition, thixotropy can be imparted as necessary. When the viscosity is within the above range, handling is easy during coating or film formation, repelling is suppressed, and leveling is excellent, so that a good film can be obtained.
• the polyimide precursor composition of the present invention contains, if necessary, a chemical imidizing agent (an acid anhydride such as acetic anhydride, an amine compound such as pyridine or isoquinoline), an antioxidant, an ultraviolet absorber, a filler (such as silica). inorganic particles, etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (fluidity aids), and the like.
• a chemical imidizing agent an acid anhydride such as acetic anhydride, an amine compound such as pyridine or isoquinoline
• an antioxidant such as an ultraviolet absorber
• a filler such as silica.
• dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (fluidity aids), and the like.
• the polyimide precursor composition can be prepared by adding and mixing an imidazole compound or a solution of an imidazole compound to the polyimide precursor solution obtained by the method described above.
• a tetracarboxylic acid component and a diamine component may be reacted in the presence of an imidazole compound.
• Polyimides and polyimide films can be produced using the polyimide precursor composition of the present invention.
• the production method is not particularly limited, and any known imidization method can be suitably applied.
• Forms of the obtained polyimide include films, laminates of polyimide films and other substrates, coating films, powders, beads, moldings, foams, and the like.
• the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 5 ⁇ m or more, for example 250 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 100 ⁇ m or less. is 50 ⁇ m or less.
• the polyimide film of the present invention has excellent optical transparency, mechanical properties, thermal properties and heat resistance.
• heat resistance is related to phase change (indicated by glass transition temperature, melting temperature, etc.) and thermal decomposition (indicated by weight reduction). Since the two are different phenomena, they are not directly related.
• the polyimide and polyimide film of the present invention are excellent in both glass transition temperature (Tg) and thermal decomposition resistance, and particularly superior to conventional polyimides in thermal decomposition resistance.
• the thermal decomposition resistance evaluation of polyimide films can be set based on the properties required in the manufacturing process of flexible electronic devices. For example, it can be evaluated by the 5% weight loss temperature of the polyimide film.
• the 5% weight loss temperature is preferably 490°C or higher, more preferably 495°C or higher, and even more preferably 497°C or higher.
• the 5% weight loss temperature is in the "preferred range” it is considered as a material with clearly improved thermal decomposition resistance. If it is within the "further more preferable range”, it is recognized as a material with remarkably improved thermal decomposition resistance. Even if the 5% weight loss temperature is improved by only a few degrees Celsius, the process margin is improved, which is advantageous for stable production of flexible electronic devices.
• the thermal decomposition resistance of the polyimide film can also be evaluated by the weight loss rate when held at a certain high temperature for a certain period of time. For example, it can be evaluated by holding at an appropriate temperature selected from the range of 400° C. to 420° C. for an appropriate time selected from 2 to 6 hours under an inert atmosphere and determining the weight loss rate.
• the polyimide film of the present invention has an extremely low coefficient of linear thermal expansion.
• the coefficient of linear thermal expansion (CTE) of the polyimide film from 150° C. to 250° C. is preferably 20 ppm/K or less, more preferably less than 20 ppm, when measured on a 10 ⁇ m thick film, Even more preferably 15 ppm/K or less, still more preferably 13 ppm/K or less, even more preferably 11 ppm/K or less, most preferably 10 ppm/K or less.
• the glass transition temperature (Tg) of the polyimide film is preferably 390° C. or higher, more preferably 400° C. or higher, still more preferably 410° C. or higher, and It is more preferably 415° C. or higher, still more preferably 420° C. or higher.
• the 400 nm light transmittance of the polyimide film is preferably 80% or more, more preferably 83% or more, and even more preferably 84% or more when measured with a 10 ⁇ m thick film.
• the yellowness index (YI) of the polyimide film is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, and still more preferably 2.2 or less, most preferably 2.0 or less.
• the elongation at break of the polyimide film is preferably 4% or more, more preferably 7% or more when measured with a film having a thickness of 10 ⁇ m.
• the breaking strength of the polyimide film is preferably 150 MPa or more, more preferably 170 MPa or more, still more preferably 180 MPa or more, still more preferably 200 MPa or more, and still more preferably 210 MPa or more.
• the breaking strength for example, a value obtained from a film having a thickness of about 5 to 100 ⁇ m can be used.
• the above preferable properties of the polyimide film are satisfied at the same time.
• a polyimide film can be produced by a known method.
• a typical method is a method in which a polyimide precursor composition is cast-coated on a base material, and then heat-imidated on the base material to obtain a polyimide film. This method is described below in connection with the production of polyimide film/substrate laminates.
• the self-supporting film is peeled off from the substrate, for example, the film is held by a tenter, and both sides of the film are
• a polyimide film can also be obtained by thermal imidization in a degassable state.
• a polyimide film/substrate laminate can be produced using the polyimide precursor composition of the present invention.
• the polyimide film/substrate laminate includes the steps of: (a) applying a polyimide precursor composition onto a substrate; (b) heat-treating the polyimide precursor on the substrate; It can be produced by a process for producing a laminate (polyimide film/substrate laminate) in which films are laminated.
• the method for producing a flexible electronic device of the present invention uses the polyimide film/substrate laminate produced in steps (a) and (b) above, and further steps (c) on the polyimide film of the laminate. (2) forming at least one layer selected from a conductor layer and a semiconductor layer; and (d) separating the base material and the polyimide film.
• step (a) a polyimide precursor composition is cast on a substrate, imidized and desolvated by heat treatment to form a polyimide film, and a laminate of the substrate and the polyimide film (polyimide A film/substrate laminate) is obtained.
• a heat-resistant material is used as the base material.
• a plate-like or A sheet-like base material, or a film or sheet-like base material such as a heat-resistant plastic material (such as polyimide) is used as the base material.
• a flat and smooth plate shape is preferable, and glass substrates such as soda lime glass, borosilicate glass, alkali-free glass, and sapphire glass are generally used; semiconductor substrates such as silicon, GaAs, InP, and GaN (including compound semiconductors); Metal substrates such as iron, stainless steel, copper, and aluminum are used.
• a glass substrate is particularly preferable as the base material. Glass substrates that are flat, smooth, and have a large area have been developed and are readily available.
• the thickness of the plate-like substrate such as a glass substrate is not limited, but from the viewpoint of ease of handling, it is, for example, 20 ⁇ m to 4 mm, preferably 100 ⁇ m to 2 mm.
• the size of the plate-like substrate is not particularly limited, but one side (long side in the case of a rectangle) is, for example, about 100 mm to 4000 mm, preferably about 200 mm to 3000 mm, more preferably about 300 mm to 2500 mm. is.
• These substrates such as glass substrates may have an inorganic thin film (for example, a silicon oxide film) or a resin thin film formed on the surface.
• an inorganic thin film for example, a silicon oxide film
• a resin thin film formed on the surface.
• the method of casting the polyimide precursor composition onto the substrate is not particularly limited, and examples thereof include slit coating, die coating, blade coating, spray coating, inkjet coating, nozzle coating, spin coating, and screen printing. method, bar coater method, electrodeposition method, and other conventionally known methods.
• step (b) the polyimide precursor composition is heat-treated on the substrate to convert it into a polyimide film to obtain a polyimide film/substrate laminate.
• the heat treatment conditions are not particularly limited. For example, after drying in a temperature range of 50°C to 150°C, the maximum heating temperature is, for example, 150°C to 600°C, preferably 200°C to 550°C, more preferably 250°C. It is preferred to process at ⁇ 500°C.
• the thickness of the polyimide film is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 5 ⁇ m or more. If the thickness is less than 1 ⁇ m, the polyimide film cannot maintain sufficient mechanical strength, and when used as a flexible electronic device substrate, for example, it may not withstand stress and break. Also, the thickness of the polyimide film is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 20 ⁇ m or less. When the thickness of the polyimide film increases, it may become difficult to reduce the thickness of the flexible device. The thickness of the polyimide film is preferably 2 to 50 ⁇ m in order to make it thinner while maintaining sufficient resistance as a flexible device.
• the polyimide film/substrate laminate has small warpage. Details of the measurement are described in Japanese Patent No. 6798633.
• the residual stress is preferably less than 27 MPa when the properties of the polyimide film are evaluated in terms of residual stress between the polyimide film and the silicon substrate in the polyimide film/silicon substrate (wafer) laminate.
• the polyimide film is assumed to be placed at 23° C. in a dry state.
• the polyimide film in the polyimide film/substrate laminate may have a second layer such as a resin film or an inorganic film on its surface. That is, after forming a polyimide film on a substrate, a second layer may be laminated to form a flexible electronic device substrate. It preferably has at least an inorganic film, and particularly preferably one that functions as a barrier layer against water vapor, oxygen (air), or the like.
• water vapor barrier layers include silicon nitride (SiN x ), silicon oxide (SiO x ), silicon oxynitride (SiO x N y ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), and zirconium oxide.
• methods for forming these thin films include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition such as plasma CVD and catalytic chemical vapor deposition (Cat-CVD). method (chemical vapor deposition method) and the like are known.
• This second layer can also be multi-layered.
• the second layer has a plurality of layers, it is possible to combine a resin film and an inorganic film. Examples include forming a three-layer structure.
• step (c) using the polyimide/substrate laminate obtained in step (b), on a polyimide film (including a second layer such as an inorganic film laminated on the surface of the polyimide film), At least one layer selected from a conductor layer and a semiconductor layer is formed. These layers may be formed directly on the polyimide film (including the lamination of the second layer) or may be formed indirectly on the lamination of the other layers required for the device. good.
• an appropriate conductor layer and (inorganic, organic) semiconductor layer are selected according to the elements and circuits required by the target electronic device.
• step (d) may be performed immediately after step (c), or after forming at least one layer selected from a conductor layer and a semiconductor layer in step (c), the device structure is further formed. After forming, the step (d) may be performed.
• a TFT liquid crystal display device for example, metal wiring, amorphous silicon or polysilicon TFTs, and transparent pixel electrodes are formed on a polyimide film on which an inorganic film is formed on the entire surface if necessary.
• a TFT includes, for example, a gate metal layer, a semiconductor layer such as an amorphous silicon film, a gate insulating layer, wiring connected to a pixel electrode, and the like.
• a structure necessary for a liquid crystal display can also be formed by a known method.
• a transparent electrode and a color filter may be formed on the polyimide film.
• an organic EL display for example, a transparent electrode, a light-emitting layer, a hole-transporting layer, an electron-transporting layer, etc. are formed on a polyimide film on which an inorganic film is formed on the entire surface if necessary, and a TFT is formed as necessary. can do.
• the polyimide film preferred in the present invention is excellent in various properties such as heat resistance and toughness, there are no particular restrictions on the method of forming the circuits, elements, and other structures necessary for the device.
• the peeling method may be a mechanical peeling method of physically peeling by applying an external force, or a so-called laser peeling method of peeling by irradiating a laser beam from the substrate surface.
• the device is completed by forming or incorporating the structure or parts necessary for the device into a (semi-) product whose substrate is the polyimide film after the base material has been peeled off.
• the polyimide film is peeled off, and a conductor layer is formed on the polyimide film as in the above step (c). and a semiconductor layer and a necessary structure to form a (semi-) product using a polyimide film as a substrate.
• DABAN 4,4'-diaminobenzanilide
• PPD p-phenylenediamine
• TFMB 2,2'-bis(trifluoromethyl)benzidine
• m-TD m-tolidine
• BNBDA 2,2'-vinorbornane-5,5',6,6'-tetracarboxylic dianhydride
• CpODA norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-norbornane- 5,5′′,6,6′′-tetracarboxylic dianhydride
• PMDA-H Cyclohexanetetracarboxylic dianhydride
• Table 1-1 shows the tetracarboxylic acid component and the diamine component
• Table 1-2 shows the structural formula of the imidazole compound.
• Example 1 [Preparation of polyimide precursor composition] 2.12 g (0.010 mol) of m-TD was placed in a reaction vessel purged with nitrogen gas, and N-methyl-2-pyrrolidone was added. % was added and stirred at 50° C. for 1 hour. 3.30 g (0.010 mol) of BNBDA was slowly added to this solution. After stirring at 70° C. for 4 hours, a uniform and viscous polyimide precursor solution was obtained.
• 2-Phenylimidazole as an imidazole compound was dissolved in four times the mass of N-methyl-2-pyrrolidone to obtain a uniform solution with a solid concentration of 20% by mass of 2-phenylimidazole.
• the imidazole compound solution and the polyimide precursor solution synthesized above are mixed so that the amount of the imidazole compound is 0.5 mol with respect to 1 mol of the repeating unit of the polyimide precursor, and the mixture is stirred at room temperature for 3 hours, A homogeneous and viscous polyimide precursor composition was obtained.
• a 6-inch Corning Eagle-XG (registered trademark) (500 ⁇ m thick) was used as a glass substrate.
• a polyimide precursor composition is applied onto a glass substrate by a spin coater, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), thermal imidization is performed by heating from room temperature to 420° C. on the glass substrate as it is, to form a polyimide film.
• a substrate laminate was obtained. The laminate was immersed in water at 40° C. (eg, temperature range of 20° C. to 100° C.) to separate the polyimide film from the glass substrate, and after drying, the properties of the polyimide film were evaluated.
• the film thickness of the polyimide film is about 10 ⁇ m. Table 2 shows the evaluation results.
• Example 2 A polyimide precursor composition was obtained in the same manner as in Example 1, except that the tetracarboxylic acid component, diamine component and imidazole compound were changed to the compounds and amounts (molar ratio) shown in Table 2. Thereafter, a polyimide film was produced in the same manner as in Example 1, and the physical properties of the film were evaluated.
• the present invention can be suitably applied to the manufacture of flexible electronic devices, for example, display devices such as liquid crystal displays, organic EL displays, and electronic paper, and light receiving devices such as solar cells and CMOS.
• display devices such as liquid crystal displays, organic EL displays, and electronic paper
• light receiving devices such as solar cells and CMOS.

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