Classifications

• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
  • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
  • C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
  • C08G59/5066—Aziridines or their derivatives
• • 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
  • C08G73/18—Polybenzimidazoles
• • 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
  • C08G73/22—Polybenzoxazoles
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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

Definitions

• the present invention relates to a method for producing a substrate and a composition used therefor.
• wholly aromatic polyimide obtained from aromatic tetracarboxylic dianhydride and aromatic diamine is due to the rigidity of the molecule, the fact that the molecule is resonance-stabilized, the strong chemical bond, etc.
• Excellent heat resistance, mechanical properties, electrical properties, oxidation resistance and hydrolysis resistance Widely used as film, coating agent, molded part, insulation material in fields such as electricity, battery, automobile and aerospace industry. in use.
• polyimide obtained by polycondensation of pyromellitic dianhydride and 4,4'-oxydianiline is excellent in heat resistance and electrical insulation, has high dimensional stability, and is used for flexible printed circuit boards.
• the polyimide film is produced by removing a solvent from a polyamic acid solution obtained by reacting pyromellitic dianhydride and 4,4'-oxydianiline and performing a thermal imidization step.
• the polyimide film is generally formed on a relatively rigid substrate such as a stainless steel belt.
• Patent Document 1 polyimide synthesized from pyromellitic dianhydride, 4,4′-oxydianiline and p-phenylenediamine is excellent in thermal dimensional stability (Patent Document 1 and Patent Document 2).
• the film obtained using the above conventional polyimide-forming composition has a problem that when the film is formed on a support, the substrate or the film itself is warped due to shrinkage deformation at the time of film formation. Yes.
• An object of the present invention is to provide a low-cost and simple method for producing a substrate and a composition used for the production method that can more effectively avoid the occurrence of warping and twisting.
• the present invention has been made in view of the above problems, and a coating film is formed by applying a film-forming composition containing a precursor of a specific heterocyclic-containing polymer and an organic solvent on a support and drying it.
• a step of peeling the formed film from the support, the method for producing a substrate includes finding that a substrate with reduced warpage and twisting can be obtained, and further, adhesion to the support and peeling.
• the inventors have found a composition and a production method that are compatible with the properties, and have completed the present invention.
• the present invention provides the following [1] to [8].
• a cyclization step (C) forming a device on the film obtained by the cyclization step; (D) peeling the film on which the element is formed from the support; Including Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of at least one differential scanning calorimetry (DSC selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole and polybenzimidazole).
• DSC Glass transition temperature
• DSC differential scanning calorimetry
• the organic solvent contains at least one solvent selected from N, N′-dimethylimidazolidinone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide.
• a film-forming composition which is a polymer having a Tg) in the range of 230 to 420 ° C.
• the substrate manufacturing method of the present invention it is possible to easily manufacture a substrate with less warping and twisting.
• the film-forming composition of the present invention is a composition comprising a precursor of a polymer such as polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole and the like having a specific glass transition temperature (Tg) and an organic solvent. Therefore, it is possible to more effectively avoid the occurrence of warping and twisting when manufacturing the substrate.
• a polymer such as polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole and the like having a specific glass transition temperature (Tg) and an organic solvent. Therefore, it is possible to more effectively avoid the occurrence of warping and twisting when manufacturing the substrate.
• adheresiveness refers to a property in which, for example, in the step (b) or the step (c), the film formed on the support and the substrate and the support are difficult to peel off.
• peelability means, for example, a property that the substrate can be peeled from the support with few peeling marks in the step (d).
• the method for producing a substrate of the present invention includes (a) applying a film forming composition containing a precursor of a heterocyclic ring-containing polymer and an organic solvent to a support and drying to form a coating film; (B) The coating film is heated at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer.
• a cyclization step (C) forming a device on the film obtained by the cyclization step; (D) peeling the film on which the element is formed from the support; Including Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of at least one differential scanning calorimetry (DSC selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole and polybenzimidazole).
• DSC Glass transition temperature
• DSC temperature increase rate 20 ° C./min
• DSC differential scanning calorimetry
• Tg is a polymer in the range of 230 to 420 ° C.
• Step (a) First, the process of apply
• the film-forming composition used in this step is glass by differential scanning calorimetry (DSC, heating rate 20 ° C./min) selected from polyimide, polybenzoxazole, polybenzothiazole, and polybenzimidazole. It contains a precursor that can be a polymer having a transition temperature (Tg) in the range of 230 to 420 ° C. and an organic solvent. Each of the precursor and the organic solvent may be used alone or in combination of two or more.
• DSC differential scanning calorimetry
• blend additives such as antioxidant, a ultraviolet absorber, and surfactant, in the said film formation composition in the range which does not impair the objective of this invention.
• heterocyclic ring-containing polymer and the precursor of the heterocyclic ring-containing polymer will be described.
• the precursor of the heterocyclic ring-containing polymer preferably has a polystyrene-reduced weight average molecular weight of 25,000 to 500,000, more preferably 50,000 to 400,000 by gel permeation chromatography (GPC). is there.
• GPC gel permeation chromatography
• the heterocycle-containing polymer preferably includes a component (A) containing a compound having four functional groups such as a carboxyl group, an acid chloride group, an ester group, an amino group, an isocyanate group, a hydroxy group, and a mercapto group;
• the heterocyclic ring-containing polymer obtained by making the component (B) containing the compound which has these two functional groups react can be mentioned.
• the component (A) includes a compound having two acid anhydride groups.
• the polyimide has a glass transition temperature (Tg) of 230 to 420 ° C., preferably 240 to 400, as determined by differential scanning calorimetry (DSC, heating rate 20 ° C./min). ° C, more preferably 250 to 380 ° C.
• Tg glass transition temperature
• Examples of the precursor capable of forming a polyimide having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min) include, for example, tetracarboxylic acid as component (A).
• examples thereof include polyamic acid obtained by reacting acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and the like and diamine, diisocyanate compound, trimethylsilylated diamine and the like as the component (B).
• the polyimide precursor specifically, as the component (A), at least one acyl compound selected from (A1) (A-1) 4,4′-oxydiphthalic dianhydride and reactive derivatives thereof (Hereinafter also referred to as “compound (A-1)”), and (A-2) at least one acyl compound selected from pyromellitic dianhydride and reactive derivatives thereof (hereinafter referred to as “compound (A-2)”).
• the component (A1) comprises at least one acyl compound (A-1) selected from 4,4′-oxydiphthalic dianhydride and reactive derivatives thereof, pyromellitic dianhydride and reactive derivatives thereof.
• a component comprising at least one compound selected from the group consisting of at least one acyl compound (A-2) selected from
• the glass transition temperature is changed to the cyclization temperature by reacting the component (A1) with the component (B1). Since a polymer (polyimide) close to (approximately 250 ° C.) can be easily obtained, it has excellent adhesion and releasability to a support, particularly a support such as a silicon wafer or non-alkali glass, and warpage or twisting occurs. A film and a substrate with a small amount can be manufactured.
• the compounding ratio of the compound (A-1) to the compound (A-2) is preferably 10:90 to 90:10, more preferably 20:80 to 50:50 (however, the sum of both is 100 mol).
• Examples of the reactive derivative of 4,4′-oxydiphthalic dianhydride include 4,4′-oxydiphthalic acid alkyl ester. Specifically, 4,4′-oxydiphthalic acid monomethyl ester, 4 , 4'-oxydiphthalic acid dimethyl ester, 4,4'-oxydiphthalic acid trimethyl ester, 4,4'-oxydiphthalic acid tetramethyl ester, 4,4'-oxydiphthalic acid monoethyl ester, 4,4'-oxydiphthalic acid diethyl ester 4,4′-oxydiphthalic acid triethyl ester, 4,4′-oxydiphthalic acid tetraethyl ester, and the like.
• Examples of the reactive derivative of pyromellitic dianhydride include pyromellitic acid alkyl ester. Specifically, pyromellitic acid monomethyl ester, pyromellitic acid dimethyl ester, pyromellitic acid trimethyl ester, pyromellitic acid Examples include meritic acid tetramethyl ester, pyromellitic acid monoethyl ester, pyromellitic acid diethyl ester, pyromellitic acid triethyl ester, and pyromellitic acid tetraethyl ester.
• 4,4'-oxydiphthalic acid and pyromellitic acid unsubstituted phenyl ester or para-substituted phenyl ester are also included.
• 4,4′-oxydiphthalic dianhydride and pyromellitic dianhydride are preferably used as the component (A1).
• a polyamic acid is synthesized at a lower temperature than when a compound that is not an anhydride is used. be able to.
• these (A1) components can be used individually by 1 type or in mixture of 2 or more types.
• the amount of at least one acylated compound (A-1) selected from 4,4′-oxydiphthalic dianhydride and its reactive derivative is selected from the viewpoint of obtaining a substrate excellent in smoothness without warping.
• the content is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, based on the total amount (total amount of component (A1)).
• the amount of the at least one acylated compound (A-2) selected from pyromellitic dianhydride and its reactive derivative is 50 to 50% based on the total amount of the acyl compound from the viewpoint of heat resistance and peelability. It is preferably 90 mol%, more preferably 55 to 85 mol%.
• acyl compound in addition to the above 4,4′-oxydiphthalic dianhydride, pyromellitic dianhydride, and reactive derivatives thereof, other acyl compounds can be further used.
• Other acyl compounds include aromatic tetracarboxylic dianhydrides (except 4,4′-oxydiphthalic dianhydride, pyromellitic dianhydride, and reactive derivatives thereof), aliphatic tetracarboxylic Examples thereof include at least one selected from the group consisting of acid dianhydrides, alicyclic tetracarboxylic dianhydrides, and reactive derivatives thereof.
• aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is preferably used from the viewpoint of excellent transparency and good solubility in an organic solvent.
• aromatic tetracarboxylic dianhydrides are preferably used from the viewpoint of low linear expansion coefficient (dimensional stability) and low water absorption.
• the component (B1) is an aromatic imino forming compound represented by the following formula (1).
• X is independently —NH 2 or —N ⁇ C ⁇ O, —NHSi (R 25 ) (R 26 ) (R 27 ), and Y is independently a direct bond ( single bond), - CH 2 -, - O -, - S -, - C (CH 3) 2 - from a single group selected, Z is a direct bond, -CH 2 -, - O - , - S —, —C (CH 3 ) 2 —,> C ⁇ O, —SO 2 —, wherein R 1 to R 16 are each independently hydrogen, carbon atoms having 1 to 12 carbon atoms.
• R 25 to R 27 are each independently an alkyl group having 1 to 15 carbon atoms.
• Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon (alkyl) group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 carbon atoms. To 12 aromatic hydrocarbon (aryl) groups.
• the linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and is a linear or branched carbon group having 1 to 5 carbon atoms.
• a hydrogen group is more preferable.
• linear or branched hydrocarbon group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.
• a methyl group an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.
• n-hexyl group n-heptyl group and the like.
• an alicyclic hydrocarbon group having 3 to 12 carbon atoms an alicyclic hydrocarbon group having 3 to 8 carbon atoms is preferable, and an alicyclic hydrocarbon group having 3 or 4 carbon atoms is more preferable.
• Preferred examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; cyclobutenyl group, cyclopentenyl group and cyclohexenyl group. And the like.
• the bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.
• Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group.
• the bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.
• Examples of the alkyl group having 1 to 15 carbon atoms represented by R 25 to R 27 include a linear or branched alkyl group having 1 to 15 carbon atoms, and a linear or branched alkyl group having 1 to 12 carbon atoms.
• a straight-chain or branched alkyl group having 1 to 8 carbon atoms is more preferable, and a straight-chain or branched alkyl group having 1 to 5 carbon atoms is more preferable.
• Preferred examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , N-hexyl group, n-heptyl group and the like.
• the “imino forming compound” refers to a compound for reacting with the component (A) to form an imino (group).
• aromatic imino-forming compound examples include bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (3-aminophenoxy) phenyl] ketone.
• bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] propane, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferably used.
• the aromatic imino forming compound represented by (2) is preferred.
• a film (film) having more excellent heat resistance and less warpage can be obtained.
• aromatic imino forming compounds bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-amino) Phenoxy) phenyl] propane is more preferably used.
• the polyimide precursor is a compound having a structure containing —CO—NH— and —CO—OH, or a derivative thereof (specifically, for example, —CO—NH— and —CO—OR).
• R is an alkyl group or the like
• H of —CO—NH— and OH of —CO—OH are dehydrated to form a cyclic
• a polyimide having a chemical structure (—CO—N—CO— (hereinafter also referred to as an imide ring structure)) (hereinafter referred to as a structure containing —CO—NH— and —CO—OH or —CO—NH—
• a structure containing —CO—OR is also referred to as an amic acid structure).
• the glass transition temperature (Tg) of the polybenzoxazole by differential scanning calorimetry is 230 to 420 ° C., preferably Is 240 to 400 ° C, more preferably 250 to 380 ° C.
• a precursor capable of forming polybenzoxazole having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate of 20 ° C./min) is, for example, bisamino as the component (A). Obtained by reacting the hydroxy compound (A2) with the component (B2) containing at least one compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid ester and the like as the component (B). Can do.
• a polyhydroxyamide which is one of the polybenzoxazole precursors, can be obtained by reacting a bisaminohydroxy compound with a dicarboxylic acid, and polybenzoxazole can be obtained by dehydrating and cyclizing this by heating or the like. be able to.
• bisaminohydroxy compound (A2) examples include 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2′-bis (3-amino-4-hydroxy- 5-trifluoromethylphenyl) hexafluoropropane, 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2′-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2′- Bis (3-amino-4-hydroxyphenyl) propane, 2,2′-bis (4-amino-3-hydroxyphenyl) propane, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4 '-Diamino-3,3'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-dia
• the component (B2) includes o-phthalic acid, terephthalic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyl Dicarboxylic acid, 4,4'-dicarboxydiphenyl sulfone, 2,2'-bis (4-carboxyphenyl) propane, 2,2'-bis (4-carboxyphenyl) hexafluoropropane, 2,6-naphthalenedicarboxylic acid 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, bis (4-carboxyphenyl) methane, 5,5′-dithiobis (2-nitrobenzoic acid), 1,10-bis (4-carboxyphenoxy) ) Decane, ethylene glycol bis (4-carboxyphenyl) ether, and
• the polybenzoxazole precursor is a compound having a structure containing —CO—NH— and —OH, or a derivative thereof (specifically, for example, —CO—NH— and —OR (however, , R is an alkyl group or the like), and is dehydrated by heating or the like to form a cyclic chemical structure (—O—C ⁇ N— (hereinafter also referred to as an oxazole ring structure). )) (Hereinafter, a structure containing —CO—NH— and —OH or —CO—NH— and —OR (wherein R is an alkyl group or the like). The structure is also called a hydroxyamide structure.)
• the glass transition temperature (Tg) of the polybenzothiazole by differential scanning calorimetry is 230 to 420 ° C., preferably Is 240 to 400 ° C, more preferably 250 to 380 ° C.
• a precursor capable of forming polybenzothiazole having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is, for example, bismercapto as the component (A). Obtained by reacting the amino compound (A3) with the component (B3) containing at least one compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester and the like as the component (B). be able to.
• polymercaptoamide which is one of polybenzothiazole precursors
• polybenzothiazole precursors can be obtained by reacting a bismercaptoamino compound with a dicarboxylic acid
• polybenzothiazole is obtained by dehydrating cyclization by heating or the like. be able to.
• bismercaptoamino compound (A3) examples include 2,2′-bis (3-amino-4-mercaptophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-mercapto5).
• [(B3) component] As said (B3) component, the compound similar to the compound quoted by said (B2) can be mentioned. In addition, these (B3) components can be used individually by 1 type or in mixture of 2 or more types.
• the polybenzothiazole precursor is a compound having a structure containing —CO—NH— and —SH or a derivative thereof (specifically, for example, —CO—NH— and —SR (provided that , R is an alkyl group or the like), and is dehydrated by heating or the like to form a cyclic chemical structure (—S—C ⁇ N— (hereinafter also referred to as a thiazole ring structure). )) (Hereinafter, a structure containing —CO—NH— and —SH or —CO—NH— and —SR (where R is an alkyl group or the like). The structure is also referred to as a mercaptoamide structure.)
• the glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min) of the polybenzimidazole is 230 to 420 ° C., preferably 240 to 400 ° C, more preferably 250 to 380 ° C.
• a precursor capable of becoming a polybenzimidazole having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is, for example, tetraamine (A4) as the component (A).
• the component (B) can be obtained by reacting the component (B4) containing at least one compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid ester and the like.
• polyaminoamide which is one of the polybenzimidazole precursors, can be obtained by reacting an aromatic tetraamine compound with dicarboxylic acid, and polybenzimidazole can be obtained by dehydrating cyclization by heating or the like. Can do.
• tetraamine (A4) examples include 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraaminonaphthalene, 2,3,6,7-tetraaminonaphthalene, 3, 3 ', 4,4'-tetraaminodiphenylmethane, 3,3', 4,4'-tetraaminodiphenylethane, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3 Mention may be made of aromatic tetraamines such as ', 4,4'-tetraaminodiphenylthioether and 3,3', 4,4'-tetraaminodiphenylsulfone. In addition, these (A4) components can be used individually by 1 type or in mixture of 2 or more types.
• Examples of (B4) include the same compounds as those mentioned in (B2) above. In addition, these (B4) components can be used individually by 1 type or in mixture of 2 or more types.
• the polybenzimidazole precursor is a compound having a structure containing —CO—NH— and —NH 2 or a derivative thereof (specifically, for example, —CO—NH— and —NR 2).
• R has a structure containing an alkyl group, etc.
• R is dehydrated by heating or the like to form a cyclic chemical structure (—NH—C ⁇ N— (hereinafter also referred to as an imidazole ring structure).
• a structure containing —CO—NH— and —NH 2 , or —CO—NH— and —NR 2 (where R is an alkyl group or the like)).
• a structure including.) Is also referred to as an aminoamide structure.
• composition for film formation The film-forming composition containing the precursor of the heterocyclic ring-containing polymer and the organic solvent has components (A) (components (A1) to (A4)) and components (B) ((B1) to (B4)), respectively. It can be obtained by reacting the component) in an organic solvent. As a specific method for reacting the component (A) and the component (B), at least one component (B) is dissolved in an organic solvent, and then the resulting solution is mixed with at least one component (A). And the like) and the mixture is stirred for 1 to 60 hours at a temperature of 0 to 100 ° C.
• organic solvent examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, N, N′-dimethylimidazolidinone, and tetramethyl.
• Aprotic polar solvents such as urea; phenolic solvents such as cresol, xylenol, and halogenated phenol; Of these, N, N′-dimethylimidazolidinone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide are preferable.
• At least one organic solvent selected from N, N′-dimethylimidazolidinone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide is used as the total amount of organic solvent (100 wt%). It is preferably contained in an amount of 50% by weight or more, preferably 70 to 100% by weight.
• solvents can be used alone or in combination of two or more.
• the total amount of the component (A) and the component (B) in the reaction solution is preferably 5 to 30% by mass of the total amount of the reaction solution.
• the (A) component and the (B) component are reacted so that the molar ratio of the (A) component to the (B) component ((A) component / (B) component) is 0.8 to 1.2. It is more preferable that the reaction is carried out so as to be 0.95 to 1.0.
• the molar ratio of the component (A) to the component (B) is less than 0.8 equivalent or more than 1.2 equivalent, the molecular weight may be low and it may be difficult to form a film (film).
• the composition containing the obtained heterocyclic-containing precursor and the organic solvent can be used as it is as the film-forming composition, but the film-forming composition is obtained from the obtained heterocyclic-containing precursor. It can also be obtained by isolating the body as a solid and then re-dissolving it in an organic solvent. In addition, as an organic solvent which redissolves, the compound similar to the said organic solvent is mentioned.
• a method for isolating a precursor of a heterocyclic ring-containing polymer a solution containing a precursor of a heterocyclic ring-containing polymer and an organic solvent is used as a poor solution for a precursor of a heterocyclic ring-containing polymer such as methanol or isopropanol. Examples thereof include a method in which a polymer precursor is precipitated by being poured into a solvent, and each polymer precursor is separated as a solid component by filtration, washing, drying, or the like.
• the viscosity of the film-forming composition (E-type viscometer, measured at 25 ° C.) is preferably 5,000 to 50,000 cP, and more preferably 7,500 to 30,000 cP. When the viscosity of the film-forming composition is in the above range, a composition having excellent coating properties can be obtained.
• the precursor used before the step (b) can be partially cyclized such as imidization.
• step (b) By performing partial cyclization before step (b), a substrate with better heat resistance can be obtained.
• Examples of this method include a method using a dehydrating agent (chemical partial cyclization such as chemical imidation) and the like. Since partial cyclization can be performed by heating at a lower temperature, chemical imidization and other chemicals are possible. Partial cyclization is preferred.
• a dehydrating agent chemical partial cyclization such as chemical imidation
• acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride
• acid chlorides corresponding to these compounds dicyclohexylcarbodiimide, etc.
• carbodiimide compounds carbodiimide compounds.
• a base catalyst such as pyridine, isoquinoline, trimethylamine, triethylamine, N, N-dimethylaminopyridine, imidazole can be used as necessary.
• the dehydrating agent or the base catalyst is preferably used in an amount of 0.1 to 8 moles per mole of component (A).
• partial cyclization such as partial imidization
• a precursor structure such as an amic acid structure, a hydroxyamide structure, a mercaptoamide structure, and an aminoamide structure in the precursor of the heterocyclic ring-containing polymer.
• At least a part, preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol% of the above compound is partially cyclized such as partial imidization.
• examples of the support to which the film forming composition is applied include a silicon wafer and non-alkali glass.
• the alkali-free glass is a glass that does not contain an alkaline component such as potassium or sodium.
• step (a) or step (b) Since such a support has high dimensional stability under heating conditions, there is little dimensional change even when heat is applied in step (a) or step (b). For this reason, the film (film) provided on the support also has less dimensional change, and the element can be easily formed at a desired position.
• a roll coating method As a method of applying the film-forming composition onto the support, a roll coating method, a gravure coating method, a spin coating method, a method using a doctor blade, or the like can be used.
• the step of drying the coated material can be performed by heating the coated material.
• the organic solvent in the coating film can be evaporated and removed.
• the heating condition is not particularly limited as long as the organic solvent evaporates.
• the heating condition is 60 to 250 ° C. for 1 to 5 hours. Heating may be performed in two stages. For example, after heating at 100 ° C. for 30 minutes, heating at 150 ° C. for 1 hour. Further, if necessary, drying may be performed under a nitrogen atmosphere or under reduced pressure.
• the thickness of the coating film is not particularly limited, but is, for example, 1 to 250 ⁇ m, preferably 2 to 150 ⁇ m, more preferably 5 to 125 ⁇ m.
• the coating film obtained in step (a) is at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer, preferably the glass transition temperature.
• the heterocyclic ring-containing polymer is cyclized by heating at a temperature 60 ° C. lower than the temperature to the glass transition temperature of the heterocyclic ring-containing polymer, preferably 160 to 420 ° C.
• the heating in the step (b) is desirably a temperature higher than the temperature at which the drying (evaporating the organic solvent) in the step (a) is performed by heating.
• the cyclization step (b) is carried out near the glass transition temperature (Tg) ( ⁇ 10 ° C.) of the heterocyclic ring-containing polymer, the resulting film or substrate has good adhesion to the support and peelability. This is preferable.
• the heating temperature in the step (b) is the glass transition temperature of the polymer obtained from those precursors. Decide on the basis of the lowest temperature.
• the precursor of the heterocyclic ring-containing polymer is a polyimide precursor, a polyimide film
• the precursor of the heterocyclic ring-containing polymer is a polybenzoxazole precursor, a polybenzoxazole film
• a polybenzothiazole film is obtained when the precursor of the heterocyclic ring-containing polymer is a polybenzothiazole precursor
• a polybenzimidazole film is obtained when the precursor of the heterocyclic ring-containing polymer is a polybenzimidazole precursor.
• the obtained coating film is subjected to dehydration cyclization (imidization) by heat treatment at, for example, 160 ° C. to 420 ° C. (Thermal imidization).
• the temperature of the thermal imidization is preferably 160 to 350 ° C., preferably 200 to 350 ° C., preferably 230 to 270 ° C., and 240 to 250 ° C. from the viewpoint of peelability. Is more preferable.
• the thermal imidization temperature is particularly preferably not higher than the glass transition temperature of the precursor used from the viewpoint of peelability.
• the ratio of the imide ring structure (hereinafter also referred to as the cyclization rate) is preferably 75 mol% or more, more preferably 85 mol% or more, in a total of 100 mol% of the amic acid structure and the imide ring structure. Particularly preferably, it is carried out so as to be 90 mol% or more.
• the ratio of the imide ring structure is less than 75 mol%, the water absorption rate of the obtained polyimide film or substrate may be increased, or the durability may be lowered.
• the imide group concentration of the polyimide is preferably 2.5 to 3.7 mmol / g, and preferably 3.0 to 3.7 mmol / g, assuming that the imidization rate is 100 mol%. More preferred is 3.0 to 3.5 mmol / g.
• the precursor of the heterocyclic ring-containing polymer is a polybenzoxazole precursor
• the obtained coating film is subjected to dehydration cyclization by heat treatment at, for example, 160 ° C. to 420 ° C.
• the cyclization temperature is preferably 160 ° C. to 350 ° C., preferably 200 ° C. to 340 ° C., and more preferably 230 ° C. to 330 ° C. from the viewpoint of peelability.
• the cyclization temperature is particularly preferably not higher than the glass transition temperature of the polybenzoxazole precursor used from the viewpoint of peelability.
• the ratio of the oxazole ring structure (hereinafter also referred to as ring closure rate) is preferably 75 mol% or more, more preferably 85, out of the total 100 mol% of the hydroxyamide structure and the oxazole ring structure. It is carried out so as to be at least mol%, particularly preferably at least 90 mol%.
• the proportion of the oxazole ring structure is less than 75 mol%, the water absorption rate of the obtained polybenzoxazole-based film or substrate may be increased or the durability may be decreased.
• the obtained coating film is subjected to dehydration cyclization by heat treatment at 160 ° C. to 420 ° C., for example.
• the cyclization temperature is preferably 160 ° C. to 350 ° C., preferably 200 ° C. to 340 ° C., and more preferably 230 ° C. to 330 ° C. from the viewpoint of peelability.
• the cyclization temperature is particularly preferably not higher than the glass transition temperature of the polybenzothiazole precursor from the viewpoint of peelability.
• the cyclization of the polybenzothiazole precursor is carried out in such a manner that the ratio of the thiazole ring structure (hereinafter also referred to as the ring closure ratio) is 100 mol% in the total 100 mol% of the mercaptoamide structure and the thiazole ring structure. Preferably, it is carried out so as to be 75 mol% or more, more preferably 85 mol% or more, particularly preferably 90 mol% or more.
• the ratio of the thiazole ring structure is less than 75 mol%, the water absorption rate of the obtained polybenzothiazole-based film or substrate may be increased or the durability may be decreased.
• the obtained coating film is subjected to dehydration cyclization by heat treatment at, for example, 160 ° C. to 420 ° C.
• the cyclization temperature is preferably 160 ° C. to 350 ° C., preferably 200 ° C. to 340 ° C., and more preferably 230 ° C. to 330 ° C. from the viewpoint of peelability.
• the cyclization temperature is particularly preferably not higher than the glass transition temperature of the polybenzimidazole precursor from the viewpoint of peelability.
• the ratio of the imidazole ring structure (hereinafter also referred to as the ring closure rate) in the total 100 mol% of the aminoamide structure and the imidazole ring structure is preferably 75 mol. % Or more, more preferably 85 mol% or more, particularly preferably 90 mol% or more.
• the proportion of the imidazole ring structure is less than 75 mol%, the water absorption rate of the obtained polybenzimidazole film or substrate may be increased, or the durability may be lowered.
• the thickness of a film such as a polyimide film is preferably 1 to 250 ⁇ m, more preferably 2 to 150 ⁇ m, and particularly preferably 10 to 125 ⁇ m.
• substrate is manufactured by forming an element on the film
• the element to be formed include light-emitting elements such as organic electroluminescence (EL) elements and thin film transistor (TFT) elements, modules such as metal wirings and semiconductor integrated circuits.
• EL organic electroluminescence
• TFT thin film transistor
• a light emitting element such as an organic EL element or a TFT element
• it can be used as a flexible display substrate or the like.
• a module such as a circuit
• it can be used as a flexible wiring board.
• a gate electrode is provided by forming a film of metal or metal oxide on the film by sputtering or the like and then etching.
• the temperature for forming a film of metal or metal oxide by sputtering or the like may be appropriately selected according to the precursor to be used and the element to be formed, but is preferably 210 ° C. to 400 ° C., preferably 220 to It is more preferable that the temperature is 370 ° C., and 230 to 350 ° C. is preferable.
• a gate insulating film such as a silicon nitride film is formed on the film provided with the gate electrode by a plasma CVD method or the like.
• an active layer made of an organic semiconductor or the like is formed on the gate insulating film by a plasma CVD method or the like.
• the temperature at which a film such as a gate insulating film or an organic semiconductor is formed by plasma CVD or the like may be appropriately selected according to the precursor to be used and the element to be formed, but is preferably 210 ° C. to 400 ° C., More preferably, the temperature is 220 to 370 ° C, and more preferably 230 to 350 ° C.
• a source electrode and a drain electrode are provided by forming a film of metal, metal oxide, or the like on the active layer by sputtering or the like and then etching.
• a thin film transistor element can be manufactured by forming a silicon nitride film or the like by a plasma CVD method or the like as a protective film as necessary.
• the thin film transistor element of the present invention is not limited to this structure, and may be a top gate type.
• the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are formed of a conductive material, and examples thereof include metals and metal oxides.
• metals include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, aluminum, zinc, magnesium, and alloys thereof, and examples of metal oxides , ITO, IZO, ZnO and In 2 O 3 .
• a conductive polymer may be used as the conductive material in consideration of adhesiveness with the film.
• a metal oxide because a transparent electrode can be formed.
• a method of forming the organic EL element for example, a method of forming an insulating layer, a first electrode, an organic semiconductor layer, a second electrode, and a protective layer on the film in order from the film surface side. It is done.
• a copper layer is provided on the film by a laminating method, a metalizing method, or the like, and the metal wiring can be provided by processing the copper layer by a known method.
• a copper layer can be provided by, for example, hot pressing a metal foil such as a copper foil on the film using a roll press machine or the like.
• a seed layer made of a Ni-based metal bonded to the film is formed by vapor deposition or sputtering. Then, a copper layer having a predetermined thickness can be provided by a wet plating method.
• the film (film) is excellent in heat resistance and excellent in adhesion to the support, a temperature range that can be applied when forming an element on the film (film) is wide, and a substrate having excellent performance can be obtained. .
• Step (d) Next, the substrate obtained in the step (c) is peeled from the support. Since the substrate obtained in the step (c) is excellent in releasability, the entire substrate can be easily peeled from the support.
• a masking tape is previously applied to the edge of the substrate, the steps (a) to (c) are performed, and then the substrate is peeled off by peeling off the masking tape.
• Examples thereof include a method of making an incision at the end to make a starting point and peeling off, a method of peeling by immersing in a solvent such as water and alcohol, and the like.
• the temperature at the time of peeling is usually 0 to 100 ° C., preferably 10 to 70 ° C., more preferably 20 to 50 ° C.
• Glass transition temperature (Tg) Using the films obtained in the following examples or comparative examples, the glass transition temperature of each heterocyclic ring-containing polymer was measured using a Rigaku 8230 type DSC measuring apparatus at a heating rate of 20 ° C./min.
• Viscosity The polyamic acid solution (composition) obtained in the following Examples or Comparative Examples was measured at 25 ° C. using a RE-100 type viscosity measuring device manufactured by Toki Sangyo Co., Ltd.
• Thick film coatability [ ⁇ ] was given when there was no coating failure during coating with a spin coater, and [x] was given when the surface was rough or could not be applied over the entire surface.
• Imido group concentration (theoretical value assuming that the imidization rate is 100 mol%) Assuming that the imidization rate is 100 mol%, the molecular weight of the repeating unit in the obtained polymer is ((A) component molecular weight) + ((B) component molecular weight) ⁇ 2 ⁇ (water molecular weight) Is required. Since each of these repeating units contains two imide groups, the imide group concentration (theoretical value assuming that the imidization rate is 100 mol%) of the polymer obtained in the following Examples or Comparative Examples is Was determined by the following formula.
• Example 1 A 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter also referred to as “BAPP”) as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. .) 9.48 g (23.1 mmol) was added. Next, the atmosphere in the flask was replaced with nitrogen, and 58 ml of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) was added and stirred until uniform.
• DMAc N, N-dimethylacetamide
• pyromellitic dianhydride hereinafter also referred to as “PMDA”
• ODPA 4,4′-oxydiphthalic dianhydride
• the viscosity of the obtained composition was measured.
• the polyamic acid was isolated from this composition using a part of obtained composition.
• the weight average molecular weight of the isolated polyamic acid was evaluated.
• the weight average molecular weight was measured about the polyamic acid before imidation. The results are shown in Table 1.
• the obtained polyamic acid solution was applied on an alkali-free glass support using a spin coater at an arbitrary rotation number and time (5 seconds at 300 rpm, then 10 seconds at 1000 rpm), and 30 minutes at 70 ° C. Subsequently, the coating film was obtained by drying at 120 degreeC for 30 minutes. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours, and then peeled off from the alkali-free glass support to obtain a film (film) having a thickness of 0.1 mm. . As a result of measuring IR (ATR method, FT-IR, 6700, manufactured by NICOLET) spectrum of the obtained film (film), it was confirmed that the amic acid structure disappeared and imidized.
• IR ATR method, FT-IR, 6700, manufactured by NICOLET
• Table 1 shows the evaluation results of the obtained film.
• Example 2 As component (B), 9.29 g (22.5 mmol) of BAPP was used instead of 9.48 g of BAPP, and 2.93 g (13.4 mmol) of PMDA instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A), and 2.78 g of ODPA A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that (9.0 mmol) was used. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 3 As component (B), 9.33 g (22.7 mmol) of BAPP was used instead of 9.48 g of BAPP, and 2.91 g (13.4 mmol) of PMDA and 2.76 g of ODPA instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A) ( 8.9 mmol) was used in the same manner as in Example 1 to obtain a polyamic acid solution (composition). Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 4 As component (B), 8.81 g (23.9 mmol) of 4,4′-bis (4-aminophenoxy) biphenyl (hereinafter also referred to as “BAPB”) was used in place of 9.48 g of BAPP, and PMDA3 was used as component (A).
• a polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that PMDA 2.56 g (11.7 mmol) and ODPA 3.64 g (11.7 mmol) were used instead of .74 g and ODPA 1.77 g. .
• a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. .
• the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm.
• Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 5 As component (B), 9.40 g (22.9 mmol) of BAPP was used instead of 9.48 g of BAPP, and 2.73 g (13.2 mmol) of PMDA and 1.07 g of ODPA instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A) ( 8.8 mmol) was used in the same manner as in Example 1 to obtain a polyamic acid solution (composition). Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 6 As component (B), BAPB 8.94 g (24.3 mmol) was used instead of BAPP 9.48 g, and as component (A), PMDA 3.11 g (14.3 mmol) and ODPA 2.95 g instead of PMDA 3.74 g and ODPA 1.77 g ( A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that 9.5 mmol) was used. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 7 BPP 9.16 g (22.3 mmol) was used instead of BAPP 9.48 g as component (B), PMDA 2.41 g (11.0 mmol) and ODPA 3.43 g instead of PMDA 3.74 g and ODPA 1.77 g as component (A) ( 11.0 mmol) was used in the same manner as in Example 1 to obtain a polyamic acid solution (composition).
• a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. .
• Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 8 BPP 9.658 g (23.5 mmol) was used instead of BAPP 9.48 g as component (B), PMDA 4.27 g (19.6 mmol) and ODPA 1.07 g (PM) instead of PMDA 3.74 g and ODPA 1.77 g as component (A)
• a polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that 3.5 mmol) was used.
• a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. .
• Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 9 6.41 g (29.1 mmol) of 4,4′-diamino-3,3′-dihydroxybiphenyl was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube. Next, the atmosphere in the flask was replaced with nitrogen, and then 58 ml of DMAc was added and stirred until uniform. To the resulting solution, 8.58 g (29.7 mmol) of diphenyl ether 4,4′-dicarbonyl chloride and 5.86 g of triethylamine were added at room temperature (about 25 ° C.), and stirring was continued at that temperature for 24 hours.
• the obtained pale yellow solid was dissolved in DMAc to obtain a 20% solution (composition).
• a coating film was formed on a non-alkali glass support in the same manner as in Example 1 except that the composition was used for coating at an arbitrary rotation speed and time so as to obtain a film having a thickness of 0.1 mm. .
• a cyclization step a film (film) having a thickness of 0.1 mm was obtained by the same operation as in Example 1 except that the obtained coating film was heated at 300 ° C. for 2 hours.
• Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 3 As component (B), 7.29 g (36.4 mmol) of 4,4′-diaminodiphenyl ether (hereinafter also referred to as “ODA”) was used instead of 9.48 g of BAPP, and 3.74 g of PMDA and 1.77 g of ODPA were used as component (A).
• a polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that 7.71 g (35.3 mmol) of PMDA was used instead of.
• a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm.
• Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).
• Example 10 The polyamic acid solution (composition) prepared in Example 1 was cast and applied by a spin coater so that the thickness of the coating film obtained on the alkali-free glass support was 25 ⁇ m, and 30 minutes at 70 ° C. Subsequently, it dried at 120 degreeC for 30 minutes, and obtained the coating film. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours. Next, the rolled copper foil (film thickness: 18 ⁇ m) having the same width as the obtained coating film is laminated so that the roughened surface is in contact with the obtained coating film, and using a roll press machine at a pressure of 5 MPa, 250 ° C., 20 ° C.
• a copper foil was provided as an element by thermocompression bonding for a minute. Thereafter, the polyimide film provided with the copper foil was peeled from the alkali-free glass support to obtain a flexible substrate. The flexible substrate could be peeled from the entire surface of the support, and no warping was observed.

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