WO2011122199A1 - 基板の製造方法およびそれに用いられる組成物 - Google Patents
基板の製造方法およびそれに用いられる組成物 Download PDFInfo
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- WO2011122199A1 WO2011122199A1 PCT/JP2011/054489 JP2011054489W WO2011122199A1 WO 2011122199 A1 WO2011122199 A1 WO 2011122199A1 JP 2011054489 W JP2011054489 W JP 2011054489W WO 2011122199 A1 WO2011122199 A1 WO 2011122199A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/001—Phase modulating patterns, e.g. refractive index patterns
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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 / hydrolysis resistance, etc. In fields such as electricity, batteries, automobiles and aerospace industries, as films, coating agents, molded parts, insulating materials Widely used.
- polyimide polyimide film obtained by polycondensation of pyromellitic dianhydride and 4,4'-oxydianiline is excellent in heat resistance and electrical insulation, has high dimensional stability, and is a flexible printed circuit board. It is used for etc.
- 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 support 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 conventional polyimide formation composition
- the substrate or the film itself warps due to shrinkage deformation at the time of film formation. Problems that arise are pointed out. Therefore, it is difficult to produce a flexible substrate such as a flexible printed circuit board or a flexible display substrate from these polyimides (formation composition) where smoothness, flexibility, flexibility and dimensional stability are required. It was.
- the conventional polyimide film is formed on a support such as a silicon wafer or non-alkali glass, it is difficult to achieve both adhesion and peelability of the resulting film to the support.
- 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 inventor produces a substrate on a support using a polyimide-based film forming composition containing a polyamic acid having a specific structural unit and an organic solvent.
- a polyimide-based film forming composition containing a polyamic acid having a specific structural unit and an organic solvent.
- the present invention provides the following [1] to [10].
- a polyimide film-forming composition containing a polyamic acid having a structural unit represented by the following formula (1) and an organic solvent is applied to a support and dried, and a coating film containing polyamic acid is applied. Forming, and (B) heating the coating film containing the polyamic acid to obtain a polyimide film; (C) forming a device on the polyimide film; (D) peeling the polyimide film on which the element is formed from the support;
- a method for manufacturing a substrate comprising:
- a plurality of R 1 are each independently a monovalent organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 200.
- the polyamic acid is a component containing (A) at least one acyl compound selected from the group consisting of tetracarboxylic dianhydride and a reactive derivative thereof; and (B) a component containing an imino forming compound;
- the component (A) includes (A-1) an acyl compound having a structural unit represented by the above formula (1).
- the component (B) is (B-1) the above formula (1).
- the content of the imino-forming compound having the structural unit represented by the formula (1) in the component (B) is 5 with respect to 100% by mass of the total amount of the component (B).
- the polyamic acid contains the component (A) and the component (B) in a molar ratio of the component (A) and the component (B) (component (B) / component (A)) 0.8 to
- the organic solvent is composed of N, N′-dimethylimidazolidinone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile, and ethylene glycol monoethyl ether.
- the method for producing a substrate according to any one of [1] to [5], wherein at least one solvent selected from the group comprises 50% by weight or more based on the total amount of the organic solvent.
- a composition for forming a polyimide-based film comprising a solvent
- a plurality of R 1 are each independently a monovalent organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 200.
- the substrate manufacturing method of the present invention it is possible to easily manufacture a substrate with less warping and twisting.
- composition for forming a polyimide-based film of the present invention is composed of a composition containing a polyamic acid having the structural unit represented by the above formula (1) and an organic solvent, warping and twisting are generated when a substrate is produced. Can be avoided more effectively.
- the polyimide-based film forming composition of the present invention By using the polyimide-based film forming composition of the present invention, even when film formation is performed on a support such as a silicon wafer or non-alkali glass, warpage that may occur on a substrate or film accompanying shrinkage deformation during film formation Can be reduced. For this reason, the polyimide film-forming composition of the present invention is suitable for use in applications requiring smoothness, flexibility, flexibility and dimensional stability, in particular for the production of flexible substrates such as flexible printed circuit boards and flexible display substrates. Yes. Furthermore, according to the method for producing a substrate of the present invention, even when a silicon wafer, non-alkali glass or the like is used as a support, it is possible to achieve both adhesion to the support and peelability. A polyimide film and a substrate can be easily produced.
- adheresion refers to a property that the polyimide film formed on the support and the substrate and the support are difficult to peel off, for example, in the step (b) or the step (c).
- peelability means, for example, the property that in step (d), there are few peeling traces and the substrate can be peeled from the support.
- a polyimide film-forming composition containing a polyamic acid having a structural unit represented by the following formula (1) and an organic solvent is applied to a support and dried.
- a step of forming a coating film containing an acid (b) a step of heating the coating film containing the polyamic acid to obtain a polyimide film, (c) a step of forming an element on the polyimide film, d) peeling the polyimide film on which the element is formed from the support.
- a plurality of R 1 are each independently an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 200.
- C1-20 means “1 to 20 carbon atoms”. Similar descriptions in the present invention have similar meanings.
- R 1 is a monovalent organic group having 1 to 20 carbon atoms, at least selected from the group consisting of monovalent hydrocarbon groups having 1 to 20 carbon atoms, and oxygen atoms and nitrogen atoms. Examples thereof include monovalent organic groups having 1 to 20 carbon atoms and containing one kind of atom.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t- A butyl group, a pentyl group, a hexyl group, etc. are mentioned.
- the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group.
- the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
- Examples of the organic group having 1 to 20 carbon atoms including an oxygen atom include an organic group consisting of a hydrogen atom, a carbon atom and an oxygen atom.
- the organic group having an ether bond, a carbonyl group and an ester group can be used. There may be mentioned 20 organic groups.
- Examples of the organic group having 1 to 20 carbon atoms having an ether bond include alkoxy groups having 1 to 20 carbon atoms, alkenyloxy groups having 2 to 20 carbon atoms, alkynyloxy groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. Examples thereof include an aryloxy group and an alkoxyalkyl group having 1 to 20 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.
- examples of the organic group having 1 to 20 carbon atoms having a carbonyl group include an acyl group having 2 to 20 carbon atoms. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.
- Examples of the organic group having 1 to 20 carbon atoms having an ester group include acyloxy groups having 2 to 20 carbon atoms. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.
- Examples of the organic group having 1 to 20 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, and a nitrogen atom. Specifically, an imidazole group, a triazole group, a benzimidazole group, a benztriazole group, etc. Is mentioned.
- Examples of the organic group having 1 to 20 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom.
- an oxazole group, an oxadiazole group examples include a benzoxazole group and a benzoxadiazole group.
- At least one of the plurality of R 1 in the formula (1) contains an aryl group from the viewpoint of effectively avoiding the occurrence of warping and twisting of the resulting polyimide film. More specifically, the plurality of R 1 are preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms.
- the alkyl group (i) having 1 to 10 carbon atoms is preferably a methyl group
- the aryl group (ii) having 6 to 12 carbon atoms is preferably a phenyl group.
- N in the formula (1) is an integer of 1 to 200, preferably 3 to 200, more preferably 10 to 200, more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably 35 to 80. Is an integer.
- n in the formula (1) is within the above range, the polyimide obtained from the polyamic acid can easily form a microphase separation structure, so that the occurrence of warping and twisting of the resulting polyimide film can be suppressed. The cloudiness of the film and the decrease in mechanical strength are suppressed.
- Step (a) First, the process of apply
- the polyimide film-forming composition used in this step contains a polyamic acid having a structural unit (1) and an organic solvent.
- a polyamic acid having a structural unit (1)
- organic solvent By using such a polyamic acid, it is possible to obtain a substrate excellent in the balance between adhesion and peelability and smoothness without warping.
- blend additives such as antioxidant, a ultraviolet absorber, and surfactant, with the said polyimide-type film formation composition in the range which does not impair the objective of this invention.
- the polyamic acid having the structural unit (1) is preferably a component containing at least one acyl compound selected from the group consisting of (A) tetracarboxylic dianhydride and a reactive derivative thereof (in the present invention, “(A ) Component ”) and (B) a component containing an imino-forming compound (also referred to as“ component (B) ”in the present invention).
- an acyl compound having (A-1) structural unit (1) hereinafter also referred to as “compound (A-1)”
- compound (B-1) an imino-forming compound having the structural unit (1)
- both the compound (A-1) and the compound (B-1) can be used.
- a polyamic acid corresponding to the structure of the raw material compound used can be obtained, and a polyamic acid having a structural unit derived from the compound can be obtained in an amount corresponding to the amount of the raw material compound used. it can.
- the component (A) includes at least one acyl compound selected from tetracarboxylic dianhydrides and reactive derivatives thereof.
- at least one compound selected from the group consisting of the compound (A-1) and an acyl compound (A-2) other than the compound (A-1) is included.
- the compound (A-1) include at least one acyl compound selected from a tetracarboxylic dianhydride having the structural unit (1) and a reactive derivative thereof, preferably the following formula (2) ), Compounds represented by formula (2A), formula (2B) and formula (2C), and the like.
- Examples of the reactive derivative include a tetracarboxylic acid having the structural unit (1), an acid ester of the tetracarboxylic acid, and an acid chloride of the tetracarboxylic acid.
- R 1 and n are each independently synonymous with R 1 and n in the formula (1), and a preferred range is also It is the same.
- R 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
- each of R 11 independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
- the monovalent organic group having 1 to 20 carbon atoms In the formula (1), the same groups as the monovalent organic group having 1 to 20 carbon atoms in R 1 can be used.
- Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in R 2 include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an arylene group having 6 to 20 carbon atoms. Can be mentioned.
- the alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
- the cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.
- the arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 12 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
- the compound (A-1) preferably has a number average molecular weight of 200 to 10,000 from the viewpoint of obtaining a polyamic acid and / or a polyimide excellent in heat resistance (high glass transition temperature) and water resistance. More preferably, it is 8,000.
- the component (A) contains the compound (A-1)
- the component (A) contains 10 to 60 masses of the compound (A-1) with respect to 100 mass% of the total amount of all acyl compounds (component (A)).
- % Preferably 20 to 50% by mass, more preferably 25 to 50% by mass, and particularly preferably 30 to 50% by mass.
- the amount of compound (A-1) used is preferably within the above range.
- the preferable blending amount of the compound (A-1) with respect to the total amount of 100% by mass of the total acyl compound (component (A)) is the case where the compound (B-1) is not used when the polyamic acid is synthesized.
- the compound (A-1) and the compound (B-1) are used as raw materials when synthesizing the polyamic acid, the total of the compound (A-1) and the compound (B-1) to be used It is preferable that the amount is the same as the preferable blending amount of the compound (A-1).
- acyl compounds other than compound (A-1) include, for example, aromatic tetracarboxylic dianhydrides, aliphatic tetra Examples thereof include at least one compound selected from the group consisting of carboxylic 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 viewpoints of heat resistance, low linear expansion coefficient (dimensional stability), and low water absorption.
- acyl compound (A-2) a compound having a group represented by the following formula (4) is preferable from the viewpoint of effectively avoiding warpage and twisting of the resulting polyimide film, and the following formula (4) A compound having a group represented by ') is more preferred.
- each R 4 independently represents a hydrogen atom or an alkyl group
- the hydrogen atom of the alkyl group may be substituted with a halogen atom
- each A independently represents an ether group, a thioether group, a ketone group, A group containing at least one group selected from the group consisting of an ester group, a sulfonyl group, an alkylene group, an amide group and a siloxane group, wherein the hydrogen atom of the alkylene group may be substituted with a halogen atom
- D is an ether group
- the hydrogen atom of the alkylene group may be substituted with a halogen atom
- each b independently represents 1 or 2
- c independently represents an integer of 1 to 3
- f represents an integer of
- the alkyl group in R 4 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, ethyl Group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and the like.
- Any hydrogen atom in these alkyl groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- examples of the alkylene group in D include a methylene group or an alkylene group having 2 to 20 carbon atoms, and the hydrogen atom of the methylene group and the alkylene group may be substituted with a halogen atom.
- the alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and is a dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylidene group, fluorene group. And a group in which any hydrogen atom in these alkylene groups is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- A each independently represents an ether group (—O—), a thioether group (—S—), a ketone group (—C ( ⁇ O) —), an ester group (—COO—), a sulfonyl group (—SO 2 —), Selected from the group consisting of an alkylene group (—R 7 —), an amide group (—C ( ⁇ O) —NR 8 —) and a siloxane group (—Si (R 9 ) 2 —O—Si (R 9 ) 2 —) And a hydrogen atom of the alkylene group may be substituted with a halogen atom.
- R 8 and R 9 each independently represent a hydrogen atom, an alkyl group or a halogen atom, and the hydrogen atom of this alkyl group may be substituted with a halogen atom.
- Examples of the alkyl group for R 8 and R 9 include the same groups as the alkyl group for R 4 .
- the halogen atom is preferably a chlorine atom or a fluorine atom.
- Examples of the alkylene group (—R 7 —) in A include the same groups as the alkylene group in D, and among these, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, and a fluorene group are preferable.
- R 4 is preferably a hydrogen atom
- A is preferably an ether group
- D is preferably a sulfonyl group.
- F is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- the total amount of the total acyl compound (component (A)) is 100.
- the component (A) is preferably contained in an amount of 40% by mass or more, more preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and more preferably 50 to 75%. More preferably, it is contained in an amount of 50% to 70% by mass. From the viewpoint of obtaining a substrate (polyimide film) excellent in heat resistance and adhesion to the substrate and peelability, the amount of the acyl compound (A-2) used is preferably within the above range.
- the component (B) is an imino forming compound.
- the “imino forming compound” refers to a compound that reacts with the component (A) to form an imino (group), and specifically includes a diamine compound, a diisocyanate compound, a bis (trialkylsilyl) amino compound, and the like. Can be mentioned.
- the component (B) preferably contains at least one selected from the group consisting of the compound (B-1) and an imino forming compound (B-2) other than the compound (B-1).
- Examples of the imino forming compound having the structural unit (1) include compounds represented by the following formulas (3) and (3A).
- R 1 and n are each independently synonymous with R 1 and n in the formula (1), and the preferred range is also the same.
- R 11 has the same meaning as R 11 in the formula (2A) and (2C).
- R 3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include those represented by the formulas (2), (2A), ( Examples of 2B) and (2C) include the same groups as the divalent hydrocarbon group having 1 to 20 carbon atoms in R 2 .
- the compound (B-1) has a number average molecular weight calculated from the amine value of 500 to 10,000 from the viewpoint of obtaining a polyamic acid and / or polyimide having excellent heat resistance (high glass transition temperature) and water resistance. Preferably, it is 1,000 to 9,000, more preferably 3,000 to 8,000.
- the imino-forming compound (B-1) can be used alone or in combination of two or more.
- the component (B) includes the imino forming compound (B-1) having the structural unit represented by the above formula (1)
- the total amount of all the imino forming compounds (component (B)) is 100% by mass (B )
- Component preferably contains 5-70% by mass of compound (B-1), more preferably 10-60% by mass, more preferably 15-55% by mass. From the viewpoint of obtaining a polyimide film excellent in heat resistance and adhesion to the substrate and peelability, the amount of the imino forming compound (B-1) is preferably included in the above range.
- the preferable blending amount of the compound (B-1) with respect to 100% by mass of the total imino-forming compound (component (B)) is that when the compound (A-1) is not used when the polyamic acid is synthesized. It is.
- imino-forming compounds other than compound (B-1) include aromatic diamines, aliphatic diamines, and alicyclic diamines. And at least one compound selected from the group consisting of:
- aromatic diamine examples include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether (4,4′-ODA), 3, 4'-diaminodiphenyl ether (3,4'-ODA), 3,3'-diaminodiphenyl ether (3,3'-ODA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4 ′ -Diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-d
- aliphatic diamines examples include aliphatic diamines having 2 to 30 carbon atoms, and specific examples thereof include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-heptanediamine, Alkylene diamines such as 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine; oxydi (2-aminoethane) And oxyalkylenediamines such as oxydi (2-aminopropane) and 2- (2-aminoethoxy) ethoxyaminoethane. These aliphatic diamines can be used for imidization reaction alone or in combination of two or more.
- alicyclic diamine what has at least 1 alicyclic group in a molecule
- numerator can be used, and any group of a monocyclic ring, a polycyclic ring, and a condensed ring is sufficient as an alicyclic group. Good.
- an alicyclic diamine having 4 to 30 carbon atoms is preferably used, and 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane, , 4'-diamino-3,3 ', 5,5'-tetramethylcyclohexylmethane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1-amino-3-aminomethyl-3,5,5- Trimethylcyclohexane, 2,2-bis (4,4′-diaminocyclohexyl) propane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 2,3-diaminobicyclo [2.2.1] Heptane, 2,5-diaminobicyclo [2.2.1] heptane
- imino forming compounds can be used alone or in combination of two or more.
- a compound having a group represented by the following formula (5) is preferable from the viewpoint of effectively avoiding the occurrence of warping and twisting of the obtained polyimide-based film.
- a compound having a group represented by 5 ′) is more preferable.
- each R 5 independently represents an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, an amide group or a siloxane group-containing group, a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group.
- Group, a nitro group, a cyano group or a sulfo group, the hydrogen atom of the alkyl group and alkylene group may be substituted with a halogen atom, a1 independently represents an integer of 1 to 3, and a2 each independently 1 or 2; a3 independently represents an integer of 1 to 4; and e represents an integer of 0 to 3.
- a and D are each independently synonymous with A and D in formula (4), and preferred groups are also the same.
- R 5 is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, a nitro group, a cyano group or a sulfo group, and preferably a hydrogen atom or an alkyl group.
- the alkyl group in R 5 has the same meaning as the alkyl group in R 4 in the formula (4).
- the alkylene group in R 5 represents the formula (4). Inside, it is synonymous with the alkylene group in D.
- E is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
- each R 5 is independently the same as R 5 in the formula (5).
- the imino-forming compound (B-2) other than the compound (B-1) is 40 to 90% by mass in the component (B) when the total amount of all imino-forming compounds (component (B)) is 100% by mass. %, Preferably 50 to 80% by mass, more preferably 50 to 75% by mass, and particularly preferably 50 to 70% by mass. From the viewpoint of obtaining a substrate (polyimide film) excellent in heat resistance and adhesion to the substrate and peelability, the amount of the imino-forming compound (B-2) used is preferably within the above range.
- a composition for forming a polyimide film containing a polyamic acid and an organic solvent can be obtained by reacting the component (A) and the component (B) in an organic solvent.
- a specific method of reacting the component (A) and the component (B) at least one (B) imino-forming compound is dissolved in an organic solvent, and then the obtained solution is mixed with at least one (A) And a method of adding an acyl compound and stirring at a temperature of 0 to 100 ° C. for 1 to 60 hours.
- 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, tetrahydrofuran, cyclohexanone, acetonitrile and ethylene glycol monoethyl ether; and phenolic solvents such as cresol, xylenol and halogenated phenol.
- N, N′-dimethylimidazolidinone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile and ethylene glycol monoethyl ether are preferred.
- at least one solvent selected from N, N′-dimethylimidazolidinone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile, and ethylene glycol monoethyl ether is used in an amount of 50% by weight or more, preferably 70 to 100% by weight based on the total amount of the organic solvent used (100% by weight).
- the organic solvent it is possible to use a mixed solvent of an amide solvent and an ether solvent, a ketone solvent, a nitrile solvent, and an ester solvent selected from the group consisting of an ester solvent.
- the coating film (film) is more preferable from the viewpoints of adhesion, peelability, residual stress, and the like. Further, when the mixed solvent is used, a drying rate at the time of film formation is increased, the film quality is not deteriorated, a polyimide-based film is excellent in productivity, and a composition having a high polyamic acid concentration can be obtained.
- the non-amide solvent is preferably a solvent that selectively evaporates during the following vacuum drying and is almost completely removed from the coating film formed on the substrate, and has a boiling point in the range of 40 to 200 ° C.
- a certain solvent is preferable, and a solvent in the range of 100 to 170 ° C. is more preferable.
- the boiling point means the boiling point in the atmosphere at 1 atm.
- the non-amide solvent preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ether solvents and nitrile solvents. Since these solvents have relatively high polarity, there is a tendency that a composition having excellent storage stability can be obtained.
- the ether solvent is preferably an ether having 3 to 10 carbon atoms, and more preferably an ether having 3 to 7 carbon atoms.
- preferable ether solvents include mono- or dialkyl ethers such as ethylene glycol, diethylene glycol, and ethylene glycol monoethyl ether, cyclic ethers such as dioxane and tetrahydrofuran (THF), and aromatic ethers such as anisole. Can be mentioned. Of these, tetrahydrofuran is preferred.
- These ether solvents can be used singly or in combination of two or more.
- the ketone solvent is preferably a ketone having 3 to 10 carbon atoms, and more preferably a ketone having 3 to 6 carbon atoms from the viewpoint of boiling point and cost.
- cyclohexanone is a solvent that can obtain a composition excellent in drying property, productivity, etc., is selectively evaporated during the following vacuum drying, and is almost completely removed from the coating film formed on the substrate. It is preferable from the point of being.
- ketone solvents can be used singly or in combination of two or more.
- the nitrile solvent is preferably a nitrile having 2 to 10 carbon atoms, and more preferably a nitrile having 2 to 7 carbon atoms.
- acetonitrile is preferable from the viewpoint of a low boiling point.
- These nitrile solvents can be used singly or in combination of two or more.
- the ester solvent is preferably an ester having 3 to 10 carbon atoms, and more preferably an ester having 3 to 6 carbon atoms.
- the amide solvent is preferably an amide having 3 to 10 carbon atoms, and more preferably an amide having 3 to 6 carbon atoms.
- an amide solvent having a boiling point of 200 ° C. or higher is preferable.
- Preferred amide solvents include alkylamides such as N, N-dimethylformamide and N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone (NMP).
- N-methyl-2-pyrrolidone and N, N-dimethylacetamide remain after vacuum drying or primary drying by evaporating the non-amide solvent, and at the time of secondary drying performed at 200 ° C. to 500 ° C. It is more preferable because it volatilizes at an evaporation rate that can maintain the smoothness of the surface of the coating film, and N-methyl-2-pyrrolidone is more preferable in consideration of environmental pollution and the like.
- these amide solvents can be used singly or in combination of two or more.
- the mixed solvent is preferably a mixed solvent of N-methyl-2-pyrrolidone and cyclohexanone, or a mixed solvent of N-methyl-2-pyrrolidone and acetonitrile, particularly from the viewpoint of drying property and productivity.
- a mixed solvent of -methyl-2-pyrrolidone and cyclohexanone is preferred.
- a mixed solvent of N, N-dimethylacetamide and tetrahydrofuran is preferable.
- the mixed solvent preferably contains 5 to 95 parts by mass, more preferably 25 to 95 parts by mass of the amide-based solvent with respect to 100 parts by mass of the mixed solvent. More preferably, it contains 65 parts by mass. Further, the mixed solvent particularly preferably contains 40 to 60 parts by mass of the amide solvent with respect to 100 parts by mass of the mixed solvent. When the mixed solvent contains the amide solvent in this amount, the mixed solvent is dried. In addition to a composition with high speed and excellent productivity, a film with excellent film quality characteristics such as white turbidity and tensile strength, storage stability, etc., and excellent adhesion to the substrate and peelability, and a film that does not easily warp are obtained. be able to.
- the amount of the amide solvent is less than 5 parts by mass, the polyamic acid may not dissolve and a composition may not be obtained.
- the amount of the amide solvent exceeds 95 parts by mass, a film is formed. In some cases, the drying speed becomes slow and the productivity is inferior.
- the total amount of the component (B) and the component (A) in the reaction solution is preferably 5 to 30% by mass with respect to the total amount of the reaction solution.
- the polyamic acid is a molar ratio of the component (A) to the component (B) (component (B) / component (A)), using the component (A) and the component (B) as a use ratio (charge ratio). Is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.95 to 1.0. When the molar ratio of the (A) acyl compound and the (B) imino-formation product is less than 0.8 equivalent or more than 1.2 equivalent, the molecular weight becomes low and it becomes difficult to form a polyimide film. There is.
- the composition containing the polyamic acid obtained by the above reaction and the organic solvent can be used as it is as the film forming composition, but the film forming composition can be used as the polyamic acid obtained by the above reaction. It can also be obtained by isolating the acid as a solid and re-dissolving it in an organic solvent.
- an organic solvent to re-dissolve the same thing as the said organic solvent is mentioned, The said mixed solvent is preferable.
- a solution containing polyamic acid and an organic solvent is poured into a poor solvent for polyamic acid such as methanol or isopropanol to precipitate polyamic acid, etc., and filtered, washed, dried, etc. And the like as a solid component.
- a poor solvent for polyamic acid such as methanol or isopropanol
- the polyamic acid is an acid having a structure containing —CO—NH— and —CO—OH or a derivative thereof (for example, —CO—NH— and —CO—OR (where R is An alkyl group and the like)).
- H of —CO—NH— and OH of —CO—OH are dehydrated by heating or the like (H of —CO—NH— and OR of —CO—OR are eliminated)
- a polyimide having a cyclic chemical structure (—CO—N—CO— (hereinafter also referred to as an imide ring structure)) (hereinafter, a structure containing —CO—NH— and —CO—OH, or —CO—
- a structure containing NH— and —CO—OR (where R is an alkyl group or the like) is also referred to as an amic acid structure).
- the polyamic acid has a silicone compound concentration calculated by the following formula of preferably 3 to 50%, more preferably 5 to 40%, and even more preferably 8 to 30%.
- Silicone compound concentration [unit:%] (weight of silicone compound) / ⁇ (weight of (A) total acyl compound) + ((B) weight of total imino forming compound) ⁇ ⁇ 100
- the “weight of the silicone compound” refers to the weight of all the compounds having the structural unit represented by the above formula (1).
- the weight average molecular weight (Mw) of the polyamic acid is preferably 10,000 to 1,000,000, more preferably 10,000 to 200,000, and further preferably 20,000 to 150,000.
- the number average molecular weight (Mn) is preferably from 5,000 to 10,000,000, more preferably from 5,000 to 500,000, particularly preferably from 20,000 to 200,000.
- the strength of the coating film may be lowered.
- the linear expansion coefficient of the obtained polyimide film may increase more than necessary.
- the weight average molecular weight or the number average molecular weight of the polyamic acid exceeds the upper limit, the viscosity of the polyimide-based film-forming composition increases, so the composition when the composition is applied to a support to form a film Since the amount of polyamic acid that can be incorporated into the product is reduced, film thickness accuracy such as flatness of the resulting coating film may be deteriorated.
- the molecular weight distribution (Mw / Mn) of the polyamic acid is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 2 to 4.
- the weight average molecular weight, number average molecular weight, and molecular weight distribution are values measured in the same manner as in the examples.
- the viscosity of the polyimide film-forming composition is usually 500 to 500,000 mPa ⁇ s, preferably 1,000 to 50,000 mPa ⁇ s, although it depends on the molecular weight and concentration of the polyamic acid. If it is less than 500 mPa ⁇ s, the retentivity of the composition during film formation is poor and it may flow down from the support. On the other hand, when it exceeds 500,000 mPa ⁇ s, the viscosity is too high, and it is difficult to adjust the film thickness, and it may be difficult to form a polyimide film.
- the viscosity of the composition is a value measured at 25 ° C. in the atmosphere using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., viscometer MODEL RE100).
- the concentration of the polyamic acid in the polyimide film-forming composition is preferably adjusted so that the viscosity of the composition is in the above range, and is usually 3 to 60% by mass, preferably depending on the molecular weight of the polyamic acid. Is 5 to 40% by mass, more preferably 10 to 40% by mass, and particularly preferably 10 to 30% by mass. If it is less than 3% by mass, problems such as difficulty in increasing the film thickness and poor productivity, easy formation of pinholes, and poor film thickness accuracy such as flatness may occur. On the other hand, if it exceeds 60% by mass, the viscosity of the composition may be too high to form a film, and a polyimide film lacking in surface smoothness may be obtained.
- the viscosity of the composition for forming a polyimide film and the concentration of polyamic acid in the composition are in the above ranges, the composition is coated on a support using a slit coating method that is excellent in productivity and the like.
- a polyimide film excellent in film thickness accuracy and the like can be formed with high productivity in a short time.
- the polyimide film-forming composition may contain a partially imidized polyamic acid.
- This partially imidized polyamic acid is synthesized by a method using a dehydrating agent (chemical partial imidation) or a method of heat treatment at about 160 to 220 ° C. in solution (thermal partial imidization), and at a lower temperature. Since partial cyclization can be performed by heating at, a chemical partially imidized product such as chemical imidization is preferable.
- the dehydrating agent examples include acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, acid chlorides corresponding to these compounds, and carbodiimide compounds such as dicyclohexylcarbodiimide.
- acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride
- acid chlorides corresponding to these compounds examples include acid chlorides corresponding to these compounds, and carbodiimide compounds such as dicyclohexylcarbodiimide.
- thermal partial imidation it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, it is preferable to azeotropically remove water using benzene, toluene, xylene or the like.
- 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).
- the partial imidization is at least a part of 100 mol% of functional groups that contribute to the cyclization reaction such as —CO—NH— or —CO—OH in the polyamic acid.
- the ratio of the imide ring structure (hereinafter also referred to as ring closure rate) is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably Is carried out so as to be 20 to 50 mol%.
- the alkali-free glass is a glass that does not contain an alkaline component such as potassium or sodium.
- a film can be formed using a support such as a silicon wafer or non-alkali glass (plate). Since such a support has high dimensional stability under heating conditions, there is little dimensional change even when heat is applied in the step (a) or the step (b). For this reason, the polyimide-based film provided on the support also has less dimensional change, and the element can be easily formed at a desired position.
- a support such as a silicon wafer or non-alkali glass (plate). Since such a support has high dimensional stability under heating conditions, there is little dimensional change even when heat is applied in the step (a) or the step (b). For this reason, the polyimide-based 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 forming a coating film by applying a polyimide film-forming composition on a support, a roll coating method, a gravure coating method, a spin coating method, a dipping method, a doctor blade, a die, a coater, a spray, a brush, The method etc. which apply
- the thickness of the obtained coating film after drying is not particularly limited, but is, for example, 1 to 500 ⁇ m, preferably 1 to 450 ⁇ m, more preferably 1 to 250 ⁇ m, and more preferably. Is 2 to 150 ⁇ m, more preferably 10 to 125 ⁇ m.
- the process of drying the said coating film can be specifically performed by heating a coating film.
- 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. Note that heating may be performed in two or more stages. For example, after heating at 70 ° C. for 30 minutes, heating at 120 ° C. for 30 minutes.
- the heating atmosphere is not particularly limited, but is preferably in the air or in an inert gas atmosphere, and particularly preferably in an inert gas atmosphere.
- the inert gas include nitrogen, argon, helium and the like from the viewpoint of colorability, and nitrogen is preferable.
- the organic solvent in the coating film may be evaporated and removed by vacuum drying before or in place of the heating.
- vacuum drying since the solvent can be easily removed from the coating film without blowing hot air or the like to the coating film formed on the support, a polyimide film excellent in flatness can be obtained, Since it is fixed from the surface of the coating film containing polyamic acid, a polyimide film having excellent flatness and uniform film quality can be formed with good reproducibility.
- the pressure in the apparatus is decreased until the pressure (decompression degree) in the apparatus containing the coating film is 760 mmHg or less, preferably 100 mmHg or less, more preferably 50 mmHg or less, and particularly preferably 1 mmHg or less. Is desirable. If it exceeds 760 mmHg, the evaporation rate when the solvent is further removed from the coating film after vacuum drying is remarkably slowed, and the productivity may be deteriorated.
- the vacuum drying is desirably performed for 0 to 60 minutes, preferably 0 to 30 minutes, more preferably 0 to 20 minutes, when the pressure drops to a predetermined value.
- the coating film obtained in the step (a) is heated to obtain a polyimide film.
- the obtained coating film is subjected to dehydration cyclization (thermal imidization) by, for example, heat treatment at 160 ° C. to 350 ° C.
- the temperature of the thermal imidization is higher than the temperature when drying (evaporating the organic solvent) in the step (a) is performed by heating, and is 200 to 350 ° C. from the viewpoint of peelability of the obtained substrate.
- it is 230 to 270 ° C, more preferably 240 to 250 ° C.
- the thermal imidization temperature is particularly preferably not higher than the glass transition temperature of the polyimide film from the viewpoint of peelability.
- the ratio of the imide ring structure is preferably 75 mol% or more, more preferably 85 mol% or more, particularly preferably 90 mol% or more, in a total of 100 mol% of the amic acid structure and the imide ring structure. To be done. When the ratio of the imide ring structure is less than 75 mol%, the water absorption rate of the polyimide-based film may increase or the durability may decrease.
- the polyimide film is composed of polyimide or the like, and the glass transition temperature measured by differential scanning calorimetry (DSC, temperature rising rate 20 ° C./min) of the polyimide is preferably 350 ° C. or higher, more preferably 450 ° C. That's it.
- DSC differential scanning calorimetry
- the imide group concentration of the polyimide obtained from polyamic acid is preferably 2.5 to 7.5 mmol / g, assuming that the imidization rate is 100 mol%, and preferably 3.0 to 6. It is more preferably 0 mmol / g, further preferably 3.5 to 5.5 mmol / g.
- the thickness of the polyimide film (film) is preferably 1 to 250 ⁇ m, more preferably 2 to 150 ⁇ m, and particularly preferably 10 to 125 ⁇ m.
- the glass transition temperature (Tg) of the polyimide film is preferably 350 ° C. or higher, and more preferably 450 ° C. or higher. By having such a glass transition temperature, it has excellent heat resistance.
- substrate is manufactured by forming an element on the polyimide-type 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.
- a light emitting element such as an organic EL element or a TFT element
- it can be used as a flexible display substrate.
- a module such as a metal wiring or a semiconductor integrated circuit is formed, it can be used as a flexible wiring substrate.
- a gate electrode is provided by forming a film of metal, metal oxide, or the like on the polyimide film obtained in the step (b) by sputtering or the like and then etching.
- the temperature at which a film of metal or metal oxide is formed by sputtering or the like may be appropriately selected according to the polyimide film forming composition to be used, the support and the element to be formed, but is 210 ° C. to 400 ° C.
- the temperature is 220 to 370 ° C, more preferably 230 to 350 ° C.
- a gate insulating film such as a silicon nitride film is formed on the polyimide film provided with the gate electrode by a plasma CVD method or the like. Further, 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 depending on the polyimide-based film forming composition to be used, the support and the element to be formed. It is preferably 400 ° C., more preferably 220 to 370 ° C., and 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 bottom gate type thin film transistor element has been described.
- the TFT element is not limited to this structure, and may be a top gate type or the like.
- the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are formed of a conductive material.
- the conductive material 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 polyimide film.
- a metal oxide because a transparent electrode can be formed.
- an organic EL element for example, an insulating layer, a first electrode, an organic semiconductor layer, a second electrode, and a protective layer are formed on the polyimide film in order from the film surface side. Is mentioned.
- a copper layer is provided on the polyimide film by a lamination 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 hot pressing a metal foil such as a copper foil on the film.
- a seed layer made of a Ni-based metal bonded to the polyimide-based film is formed by a vapor deposition method or a sputtering method.
- a copper layer having a predetermined film thickness can be provided by a wet plating method or the like.
- the polyimide film (film) has excellent heat resistance and excellent adhesion to the support, a substrate having a wide range of temperature that can be applied when forming an element on the film (film) and excellent performance is obtained. Can do.
- Step (d) Next, the substrate obtained in the step (c) is peeled from the support. Since the substrate obtained from the polyimide-based film forming composition is excellent in releasability, the entire surface of the 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, and a method of peeling by dipping in a solvent such as water or alcohol.
- 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 1 to 16 or Comparative Examples 1 and 2, the glass transition temperature of polyimide was set to 20 ° C./min using a Rigaku 8230 DSC measuring apparatus. It was measured.
- Weight average molecular weight The weight average molecular weight of the polyamic acid obtained in the following Examples 1 to 16 or Comparative Examples 1 and 2 was measured using an HLC-8020 GPC apparatus manufactured by TOSOH. As the solvent, N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used, and the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.
- NMP N-methyl-2-pyrrolidone
- Example 1 A 2,2′-dimethyl-4,4′-diaminobiphenyl (hereinafter referred to as “m-TB”) as a component (B-2) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. 6) 77.0 g (28.6 mmol) and amino acid-modified methylphenyl silicone at both ends as a component (B-1) (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) 2.57 g (0. 6 mmol) was added.
- m-TB 2,2′-dimethyl-4,4′-diaminobiphenyl
- the obtained polyamic acid solution was applied on a non-alkali glass support with a spin coater (rotated at 300 rpm for 5 seconds and then rotated at 1100 rpm for 10 seconds), then at 70 ° C. for 30 minutes, and then at 120 ° C.
- a coating film was obtained by drying for 30 minutes.
- the coating film obtained as the imidization step was further dried at 250 ° C. for 2 hours, and then peeled off from the alkali-free glass support to obtain a polyimide film (film) having a film thickness of 30 ⁇ m (0.03 mm).
- membrane the adhesiveness with respect to a support body, peelability, and the curvature of the polyimide-type film
- Example 2 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 6.07 g (28.6 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was used as the component (B-2). As a component (B-1), 2.57 g (0.6 mmol) of amino acid-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 3 To a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube, 6.68 g (31.4 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B-2) As a component (B-1), 1.40 g (0.3 mmol) of amino acid-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 4 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube, 1.42 g (13.1 mmol) of paraphenylenediamine (hereinafter also referred to as “PDA”) as component (B-2) and 2 , 2′-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter also referred to as “BAPP”) 5.39 g (13.1 mmol) and amino acid-modified methylphenyl silicone at both ends as component (B-1) ( 2.36 g (0.5 mmol) manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) was added.
- PDA paraphenylenediamine
- BAPP 2′-bis [4- (4-aminophenoxy) phenyl] propane
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 5 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, 6.46 g (32.1) of 4,4′-diaminodiphenyl ether (hereinafter also referred to as “ODA”) as the component (B-2). 3 mmol) and 1.43 g (0.3 mmol) of amino terminal-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) were added as component (B-1).
- ODA 4,4′-diaminodiphenyl ether
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 6 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube, 6.04 g (28.4 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was used as the component (B-2). As a component (B-1), 2.36 g (1.8 mmol) of amino acid-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number average molecular weight 1,300) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 7 6.41 g (30.2 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B-1) was added to a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube.
- component (B-1) 1.85 g (0.6 mmol) of amino terminally modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161B, number average molecular weight 3,000) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 8 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube, 6.29 g (29.6 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was used as component (B-2). As a component (B-1), 1.98 g (1.2 mmol) of amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-161A, number average molecular weight 1,600) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 9 To a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube, 6.65 g (31.3 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B-2) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 10 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 6.59 g (31.0 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B-2) As a component (B-1), 1.38 g (0.3 mmol) of amino terminal-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 11 6.4 g (31) of 4,4′-diaminodicyclohexylmethane (hereinafter also referred to as “MBCHA”) as a component (B-2) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. .6 mmol) and 1.40 g (0.3 mmol) of both-terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) were added as component (B-1).
- MBCHA 4,4′-diaminodicyclohexylmethane
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 12 2.87 g (25.1 mmol) of 1,4-diaminocyclohexane (hereinafter also referred to as “CHDA”) as a component (B-2) in a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. ) And 3.42 g (0.8 mmol) of amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) were added as components (B-1).
- CHDA 1,4-diaminocyclohexane
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 13 As a component (B-2), 1.99 g (26.2 mmol) of 1,4-diaminocyclohexane and a component (B-1) were added to a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube. 2.56 g (2.0 mmol) of both-terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number average molecular weight 1,300) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- B-2 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl (hereinafter referred to as “B-2) component was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube.
- TFMB a 7.85 g (24.5 mmol)
- (B-1) component both-end amino-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number average molecular weight 1,300) 2.03 g (1 .6 mmol) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 15 In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 6.34 g (29.9 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl was used as component (B-2). As a component (B-1), 2.68 g (0.6 mmol) of amino terminally modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) was added.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 16 Into a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube was added 2.78 g (22.3 mmol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as component (B-2). And (B-1) component both ends amino-modified methyl phenyl silicone (Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) 5.16 g (1.2 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N, N-dimethylacetamide was added and stirred until uniform.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Example 17 The polyamic acid solution (composition) prepared in Example 1 was cast and applied on a non-alkali glass support with a spin coater so that the thickness of the resulting coating film was 25 ⁇ m, and 30 minutes at 70 ° C. Then, it was dried at 120 ° C. for 30 minutes to obtain a coating film. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours.
- a transparent conductive film (element) was formed on the surface of the obtained coating film under an argon atmosphere at 230 ° C. for 5 minutes.
- ITO was used as a target material.
- the specific resistance value of the obtained substrate was 2 ⁇ 10 ⁇ 4 ( ⁇ ⁇ cm).
- membrane was obtained by peeling the polyimide-type film
- substrate was peelable from the support body, and the curvature was not observed.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- a polyimide-based 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 film (film) having a film thickness of 0.03 mm.
- Table 1 shows the physical properties of the obtained polyimide, polyamic acid, and polyimide film.
- Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) are as follows. Column: TSK guard column ALPHA column: TSKgel ALPHA-M, developing solvent: NMP).
- Coating solvent weight Coating varnish weight-Coating polymer weight
- Coating non-amide solvent weight Coating solvent weight x amount of non-amide solvent charge (ratio of non-amide solvent in mixed solvent) (%)
- Solvent weight after vacuum drying coating weight after vacuum drying-weight of polymer applied
- Solvent weight evaporated by vacuum drying solvent weight applied-solvent weight after vacuum drying
- Non-amide solvent weight after vacuum drying non-amide coating applied Weight of solvent ⁇ solvent weight evaporated by vacuum drying
- Composition ratio (%) of non-amide solvent (weight of non-amide solvent after vacuum drying / solvent weight after vacuum drying ⁇ 100)
- Composition ratio (%) of amide solvent 100 ⁇ composition ratio of non-amide solvent (The solvent evaporated by vacuum drying was defined as the solvent having the lowest boiling point in the mixed solvent (non-amide solvent).)
- Tackiness after primary drying The coating after primary drying obtained in the following Examples 18 to 27 and Comparative Example 3 is strongly rubbed with a metal spatula, and there is no tackiness when the coating does not move. The coating film moved was evaluated as having tackiness.
- the residual stress of the coating film is preferably 10 MPa or less, and more preferably 5 MPa or less.
- Imidization rate The imidation rate of polyimide in the polyimide-based film after secondary drying obtained in Examples 18 to 27 and Comparative Example 3 below was calculated using FT-IR (Thermo NICOLET 6700, manufactured by Thermo Fisher Scientific). And quantified by the following method.
- Example 18 In a three-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirring blade at 25 ° C. under a nitrogen stream, 45.23099 g (0.21306 mol) of m-tolidine (m-TB), both ends amino-modified side chain phenyl methyl type silicone X-22-1660B-3 [9.4694 g (0.0021521 mol)], 307 g of dehydrated N-methyl-2-pyrrolidone (NMP) and dehydrated cyclohexanone (CHN) so that the polyamic acid concentration in the varnish is 14%. 307 g was added and stirred for 10 minutes until m-TB and X-22-1660B-3 were completely dissolved.
- NMP N-methyl-2-pyrrolidone
- CHN dehydrated cyclohexanone
- a glass support (horizontal: 300 mm x vertical: 350 mm x thickness: 0.7 mm) is fixed to a control coater stand installed so as to be perpendicular to gravity, and the gap interval is set so that the film thickness becomes 30 ⁇ m after secondary drying.
- Example 18 was carried out in the same manner as in Example 18 except that the amounts of m-TB, X-22-1660B-3 and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- a tough polyimide film having excellent heat resistance, transparency, and smoothness and having no warp could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 18 was carried out in the same manner as in Example 18 except that the amounts of m-TB, X-22-1660B-3 and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- a tough polyimide film having excellent heat resistance, transparency, and smoothness and having no warp could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 21 In Example 18, m-TB32.478g and 4,4′-diaminodiphenyl ether (ODA) 7.8760 g were used instead of m-TB45.23099g, and the amounts of X-22-1660B-3 and PMDA used were shown in Table 2. Example 18 was performed in the same manner as in Example 18 except that the changes were made. The results are shown in Table 2.
- the elongation of the film was improved, and a polyimide-based film having no warpage was obtained with excellent heat resistance, transparency and smoothness.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 22 In Example 18, the same procedure as in Example 18 was performed except that N, N-dimethylacetamide (DMAc) was used instead of NMP as the amide solvent. The results are shown in Table 2.
- DMAc N, N-dimethylacetamide
- a tough polyimide film having excellent heat resistance, transparency, smoothness, no warpage, and low linear expansion coefficient could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 23 In Example 18, the same procedure as in Example 18 was performed, except that 430 g of acetonitrile was used instead of CHN 307 g as the non-amide solvent, and the amount of NMP used was changed as shown in Table 2. The results are shown in Table 2.
- a tough polyimide film having excellent heat resistance, transparency, smoothness, no warpage, and low linear expansion coefficient could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- a tough polyimide film having excellent heat resistance, transparency, smoothness, no warpage, and low linear expansion coefficient could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 25 In Example 18, it carried out like Example 18 except having changed the usage-amount of NMP and CHN as shown in Table 2. The results are shown in Table 2.
- a tough polyimide film with excellent heat resistance and smoothness and without warping could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 26 In Example 18, it carried out like Example 18 except having used ethylene glycol monomethyl ether instead of CHN. The results are shown in Table 2.
- a tough polyimide film having excellent heat resistance, transparency, and smoothness and having no warp could be obtained.
- the obtained coating film has a high drying rate and excellent adhesion to the glass support during the primary drying and the secondary drying.
- the polyimide film obtained after the secondary drying is obtained from the glass support. Excellent peelability.
- Example 27 In Example 18, it carried out like Example 18 except having used NMP614 instead of NMP307g and CHN307g. The results are shown in Table 2.
- a polyimide film having excellent heat resistance and smoothness and having no warp could be obtained. Moreover, the obtained coating film is excellent in adhesiveness with the glass support during primary drying and secondary drying, and the polyimide film obtained after secondary drying is excellent in peelability from the glass support. It was.
- Example 27 was carried out in the same manner as in Example 27 except that X-22-1660B-3 was not used and the amounts of m-TB and PMDA used were changed as shown in Table 2. The results are shown in Table 2.
- the varnish obtained in Comparative Example 3 had a slow drying rate. Moreover, the residual stress increased after secondary drying, and a large warp was generated in the polyimide film peeled from the glass support.
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Abstract
Description
(b) 前記ポリアミック酸を含む塗膜を加熱し、ポリイミド系膜を得る工程と、
(c) 前記ポリイミド系膜上に素子を形成する工程と、
(d) 前記素子が形成されたポリイミド系膜を支持体から剥離する工程と、
を含むことを特徴とする基板の製造方法。
(i)前記(A)成分が、(A-1)上記式(1)で表わされる構造単位を有するアシル化合物を含む
(ii)前記(B)成分が、(B-1)上記式(1)で表わされる構造単位を有するイミノ形成化合物を含む
まず、支持体に、構造単位(1)を有するポリアミック酸と有機溶媒とを含むポリイミド系膜形成用組成物を塗布及び乾燥し、ポリアミック酸を含む塗膜を形成する工程について説明する。
(A)成分は、テトラカルボン酸二無水物およびこれらの反応性誘導体より選ばれる少なくとも1種のアシル化合物を含む。好ましくは、上記化合物(A-1)、および化合物(A-1)以外のアシル化合物(A-2)からなる群より選ばれる少なくとも一種の化合物を含む。
上記化合物(A-1)以外のその他のアシル化合物(A-2)としては、例えば、芳香族テトラカルボン酸二無水物、脂肪族テトラカルボン酸二無水物、脂環族テトラカルボン酸二無水物、及びこれらの反応性誘導体からなる群より選ばれる少なくとも1種の化合物が挙げられる。具体例としては、ブタンテトラカルボン酸二無水物、1,2,3,4-シクロブタンテトラカルボン酸二無水物、1,2,3,4-シクロペンタンテトラカルボン酸二無水物、2,3,5-トリカルボキシシクロペンチル酢酸二無水物、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物、3,5,6-トリカルボキシノルボルナン-2-酢酸二無水物、2,3,4,5-テトラヒドロフランテトラカルボン酸二無水物、1,3,3a,4,5,9b-ヘキサヒドロ-5-(テトラヒドロ-2,5-ジオキソ-3-フラニル)-ナフト[1,2-c]-フラン-1,3-ジオン、5-(2,5-ジオキソテトラヒドロフラル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸二無水物、ビシクロ[2,2,2]-オクト-7-エン-2,3,5,6-テトラカルボン酸二無水物などの脂肪族テトラカルボン酸二無水物あるいは脂環族テトラカルボン酸二無水物、及びこれらの反応性誘導体;
4,4’-オキシジフタル酸二無水物、ピロメリット酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ビフェニルスルホンテトラカルボン酸二無水物、1,4,5,8-ナフタレンテトラカルボン酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、3,3’,4,4’-ジメチルジフェニルシランテトラカルボン酸二無水物、3,3’,4,4’-テトラフェニルシランテトラカルボン酸二無水物、2,3,4,5-フランテトラカルボン酸二無水物、4,4’-ビス(3,4-ジカルボキシフェノキシ)ジフェニルスルフィド二無水物、4,4’-ビス(3,4-ジカルボキシフェノキシ)ジフェニルスルホン二無水物、4,4’-ビス(3,4-ジカルボキシフェノキシ)ジフェニルプロパン二無水物、3,3’,4,4’-パーフルオロイソプロピリデンジフタル酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、ビス(フタル酸)フェニルホスフィンオキサイド二無水物、p-フェニレン-ビス(トリフェニルフタル酸)二無水物、m-フェニレン-ビス(トリフェニルフタル酸)二無水物、ビス(トリフェニルフタル酸)-4,4’-ジフェニルエーテル二無水物、ビス(トリフェニルフタル酸)-4,4’-ジフェニルメタン二無水物などの芳香族テトラカルボン酸二無水物、及びこれらの反応性誘導体を挙げることができる。
(B)成分は、イミノ形成化合物である。ここで、「イミノ形成化合物」とは、(A)成分と反応してイミノ(基)を形成する化合物をいい、具体的には、ジアミン化合物、ジイソシアネート化合物、ビス(トリアルキルシリル)アミノ化合物等を挙げることができる。
(B)成分は、好ましくは、上記化合物(B-1)および化合物(B-1)以外のイミノ形成化合物(B-2)からなる群より選ばれる少なくとも一種を含む。
上記化合物(B-1)以外のその他のイミノ形成化合物(B-2)としては、芳香族ジアミン、脂肪族ジアミン、脂環族ジアミンからなる群より選ばれる少なくとも1種の化合物等が挙げられる。
これらの溶媒は1種単独で、あるいは2種以上混合して使用することができる。
なお、これらエーテル系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。
なお、これらケトン系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。
なお、これらニトリル系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。
なお、これらエステル系溶媒は、1種単独であるいは2種以上を組み合わせて用いることができる。
なお、「シリコーン化合物の重量」とは、上記式(1)で表わされる構造単位を有する化合物全ての重量をいう。
次いで、工程(a)で得られた塗膜を加熱し、ポリイミド系膜を得る。工程(b)では、得られた塗膜を、例えば160℃~350℃で熱処理することにより脱水環化する(熱イミド化)。熱イミド化の温度としては、前記工程(a)における乾燥(有機溶媒を蒸発させる)を加熱により行う際の温度よりも高い温度であり、得られる基板の剥離性の観点から200~350℃であることが好ましく、230~270℃であることがより好ましく、240~250℃であることがさらに好ましい。さらに、熱イミド化の温度としては、剥離性の観点から、ポリイミド系膜のガラス転移温度以下であることが特に好ましい。
続いて、前記工程(b)により得られたポリイミド系膜上に、素子を形成することで基板を製造する。形成する素子としては、有機エレクトロルミネッセンス(EL)素子、薄膜トランジスタ(TFT)素子等の発光素子、金属配線、半導体集積回路等のモジュールなど挙げられる。
前記工程(b)で得られたポリイミド系膜上にスパッタ法等で金属や金属酸化物などの膜を形成した後にエッチングするなどして、ゲート電極を設ける。スパッタ法等で金属や金属酸化物などの膜を形成する際の温度は、用いるポリイミド系膜形成用組成物、支持体や形成する素子に応じて適宜選択すればよいが、210℃~400℃であることが好ましく、220~370℃であることがより好ましく、230~350℃であることが好ましい。
ゲート電極を設けたポリイミド系膜上にプラズマCVD法等で窒化珪素膜等のゲート絶縁膜を形成する。さらに、ゲート絶縁膜上にプラズマCVD法などにより有機半導体などからなる活性層を形成する。プラズマCVD法等でゲート絶縁膜や有機半導体などの膜を形成する際の温度は、用いるポリイミド系膜形成用組成物、支持体や形成する素子に応じて適宜選択すればよいが、210℃~400℃であることが好ましく、220~370℃であることがより好ましく、230~350℃であることが好ましい。次に活性層の上にスパッタ法などで金属や金属酸化物などの膜を形成した後にエッチングするなどして、ソース電極およびドレイン電極を設ける。最後に必要に応じてプラズマCVD法等で窒化珪素膜等を形成し、保護膜とすることにより、薄膜トランジスタ素子を製造することができる。
次に、前記工程(c)で得られた基板を前記支持体から剥離する。前記ポリイミド系膜形成用組成物から得られた基板は剥離性に優れるため、容易に基板を支持体から全面剥離することができる。
下記実施例1~16、または、比較例1および2で得られたフィルムを用いてポリイミドのガラス転移温度を、Rigaku社製8230型DSC測定装置を用いて、昇温速度を20℃/minとして測定した。
下記実施例1~16、または、比較例1および2で得られたポリアミック酸のシリコーン化合物濃度は、下記式により求めた。
シリコーン化合物濃度[単位:%]=(シリコーン化合物の重量)/{((A)全アシル化合物の重量)+((B)全イミノ形成化合物の重量)}×100
シリコーン化合物の重量=化合物(A-1)の重量+化合物(B-1)の重量
イミド化率が100モル%であると仮定すると、下記実施例1~16、または、比較例1および2で得られたポリイミド中の繰り返し単位の分子量は、(アシル化合物の分子量)+(ジアミンの分子量)-2×(水の分子量)で求められる。この繰り返し単位1つあたり、2つのイミド基を含むため、下記実施例1~16、または、比較例1および2で得られた重合体のイミド基濃度(イミド化率が100モル%であると仮定した場合の理論値)は、下記式により求めた。
[イミド基濃度](単位:mmol/g)=2/{(アシル化合物の分子量)+(ジアミンの分子量)-2×(水の分子量)}×1000
下記実施例1~16、または、比較例1および2におけるイミド化工程(250℃乾燥)終了後に、室温まで冷却したポリイミド系膜付支持体を300℃まで30分かけて昇温し、その後、30分で室温まで冷却する工程を1サイクルとして、このサイクルを10回繰り返した後、支持体からの剥離がないもの[◎]、このサイクルを5回繰り返した後、支持体からの剥離がないもの[○]、剥離が観察されたものを[×]とした。
下記実施例1~16、または、比較例1および2におけるイミド化工程(250℃乾燥)終了後に、支持体からポリイミド系膜を全面剥離可能なものを[◎]、全面剥離可能で一部剥離痕が残るものを[○]、一部剥離不可を[△]、全面剥離不可を[×]とした。
下記実施例1~16、または、比較例1および2で得られた、支持体から剥離したポリイミド系膜を40×40mmに切り出し、反り(水平な基板上に得られたポリイミド系膜を置いて、該膜の四角における膜と基板との離間距離を測定し、それらの平均値)が1.0mm未満の場合を[◎]、反りが1.0mm以上2.0mm未満の場合を[○]、反りが2.0mm以上3.0mm未満の場合を[△]、反りが3.0mm以上の場合を[×]とした。
下記実施例1~16、または、比較例1および2で得られたポリアミック酸の重量平均分子量は、TOSOH製HLC-8020型GPC装置を使用して測定した。溶媒には、臭化リチウム及び燐酸を添加したN-メチル-2-ピロリドン(NMP)を用い、測定温度40℃にて、ポリスチレン換算の分子量を求めた。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル(以下「m-TB」ともいう。)6.07g(28.6mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)2.57g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド(以下「DMAc」ともいう。)58mlおよびテトラヒドロフラン(以下、「THF」ともいう。)20mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物(以下「PMDA」ともいう。)6.36g(29.2mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。得られた組成物の一部を用いて、該組成物からポリアミック酸を単離した。単離したポリアミック酸の重量平均分子量、シリコーン化合物濃度、イミド基濃度(イミド化率が100モル%であると仮定した場合の理論値)を評価した。
また、上記ポリイミド系膜について、支持体に対する密着性、剥離性、ポリイミド系膜のソリを評価した。
結果を表1に示す。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.07g(28.6mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)2.57g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.36g(29.2mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.68g(31.4mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)1.40g(0.3mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlとテトラヒドロフラン20mlとを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.93g(31.8mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分としてパラフェニレンジアミン(以下「PDA」ともいう。)1.42g(13.1mmol)および2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(以下「BAPP」ともいう。)5.39g(13.1mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)2.36g(0.5mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlとテトラヒドロフラン20mlとを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物5.84g(26.8mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として4,4’-ジアミノジフェニルエーテル(以下「ODA」ともいう。)6.46g(32.3mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)1.43g(0.3mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlとテトラヒドロフラン20mlとを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物7.11g(32.6mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.04g(28.4mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-9409,数平均分子量1,300)2.36g(1.8mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.60g(30.3mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-1)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.41g(30.2mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-161B,数平均分子量3,000)1.85g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.73g(30.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.29g(29.6mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-161A,数平均分子量1,600)1.98g(1.2mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.73g(30.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.65g(31.3mmol)を添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.15g(28.2mmol)と(A-1)成分として両末端酸無水物変性メチルシリコーン(GELEST製,DMS-Z21,数平均分子量700)2.19g(3.1mmol)とを室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.59g(31.0mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)1.38g(0.3mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分として1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(以下「PMDAH」ともいう。)7.03g(31.4mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として4,4’-ジアミノジシクロヘキシルメタン(以下「MBCHA」ともいう。)6.64g(31.6mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)1.40g(0.3mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物6.96g(31.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として1,4-ジアミノシクロヘキサン(以下「CHDA」ともいう。)2.87g(25.1mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)3.42g(0.8mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてジフェニル-3,3’,4,4’-テトラカルボン酸二無水物(以下「s-BPDA」ともいう。)8.71g(25.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として1,4-ジアミノシクロヘキサン2.99g(26.2mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-9409,数平均分子量1,300)2.56g(2.0mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてジフェニル-3,3’,4,4’-テトラカルボン酸二無水物9.46g(28.1mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビフェニル(以下「TFMB」ともいう。)7.85g(24.5mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-9409,数平均分子量1,300)2.03g(1.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分として1,2,3,4-シクロブタンテトラカルボン酸二無水物(以下「CBDA」ともいう。)5.12g(26.1mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル6.34g(29.9mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)2.68g(0.6mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分として1,2,3,4-シクロブタンテトラカルボン酸二無水物5.98g(30.5mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル4.78g(22.3mmol)と(B-1)成分として両末端アミノ変性メチルフェニルシリコーン(信越化学製,X22-1660B-3,数平均分子量4,400)5.16g(1.2mmol)とを添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物5.11g(23.4mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、組成物(ポリアミック酸溶液)を得た。
上記実施例1において調製したポリアミック酸溶液(組成物)を、スピンコーターにて無アルカリガラス支持体上に、得られる塗膜の厚みが25μmになるように流延塗布し、70℃で30分、ついで120℃で30分乾燥して塗膜を得た。その後、環化(イミド化)工程として得られた塗膜をさらに250℃で2時間乾燥した。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ジメチル-4,4’-ジアミノビフェニル7.40g(34.9mmol)を添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物7.60g(34.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、ポリアミック酸溶液を得た。
温度計、攪拌機、窒素導入管、冷却管を取り付けた300mLの4つ口フラスコに(B-2)成分として2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン9.25g(22.5mmol)を添加した。次いで、フラスコ内を窒素置換した後、N,N-ジメチルアセトアミド58mlを加え均一になるまで攪拌した。得られた溶液に(A-2)成分としてピロメリット酸二無水物2.95g(13.5mmol)および4,4’-オキシジフタル酸二無水物(以下「ODPA」ともいう。)2.80g(0.9mmol)を室温で加え、そのままの温度で24時間攪拌を続けて、ポリアミック酸溶液を得た。
下記実施例18~27および比較例3で得られたポリアミック酸の重量平均分子量(Mw)、数平均分子量(Mn)および分子量分布(Mw/Mn)は、TOSOH製HLC-8220型GPC装置(ガードカラム:TSK guard colomn ALPHA カラム:TSKgelALPHA―M、展開溶剤:NMP)を用いて測定した。
下記実施例18~27および比較例3で得られたワニス(ポリイミド系膜形成用組成物)を-15℃で48時間保存後、透明で沈殿物のないものを○、不透明で沈殿物が析出したものを×として目視により評価した。
下記実施例18~27および比較例3で得られたワニス1.5gを用い、25℃でのワニス粘度を測定した。具体的には東機産業製 粘度計 MODEL RE100を用い測定した。
下記実施例18~27および比較例3で得られた真空乾燥後のガラス支持体付塗膜の中央部およびガラス支持体の中央部に標線を引き、塗膜付支持体を垂直に立て10分間放置した。塗膜に引かれた標線とガラス支持体に引かれた標線との高さが変化しなかった場合は固定化、変化した場合は流動化と判定した。
下記実施例18~27および比較例3で得られた真空乾燥後の塗膜におけるポリマー(ポリアミック酸)の濃度を下記の式に従い、算出した。
塗布したワニス重量=ワニス塗布後のガラス支持体の重量-ワニス塗布前のガラス支持体の重量
仕込み時ポリマー濃度(%)=仕込みモノマー全量/(仕込みモノマー量+仕込み溶媒全量)×100
塗布したポリマー重量=塗布したワニス重量×仕込み時ポリマー濃度(%)
真空乾燥後塗膜重量=真空乾燥後の塗膜付ガラス支持体の重量-ワニス塗布前のガラス支持体の重量
真空乾燥後のポリマー濃度(%)=(塗布したポリマー重量/真空乾燥後塗膜重量)×100
下記実施例18~27および比較例3で得られた真空乾燥後の塗膜における溶媒組成比を上記の式および下記の式に従い、算出した。
塗布した非アミド系溶媒の重量=塗布した溶媒重量×非アミド系溶媒の仕込み量(混合溶媒中の非アミド系溶媒の割合)(%)
真空乾燥後溶媒重量=真空乾燥後塗膜重量-塗布したポリマー重量
真空乾燥で蒸発した溶媒重量=塗布した溶媒重量-真空乾燥後溶媒重量
真空乾燥後の非アミド系溶媒重量=塗布した非アミド系溶媒の重量-真空乾燥で蒸発した溶媒重量
非アミド系溶媒の組成比(%)=(真空乾燥後の非アミド系溶媒重量/真空乾燥後溶媒重量×100)
アミド系溶媒の組成比(%)=100-非アミド系溶媒の組成比
(なお、真空乾燥で蒸発した溶媒は混合溶媒中の最も沸点な低い溶媒(非アミド系溶媒)と定義した。)
下記実施例18~27および比較例3で得られた1次乾燥後の塗膜を金属製スパチュラーで強くこすり、塗膜が移動しないものをタック性無し、塗膜が移動したものをタック性有とし、評価した。
下記実施例18~27および比較例3で得られた1次乾燥後および2次乾燥後のガラス支持体上に形成された塗膜それぞれについて、Haze(ヘイズ)をJIS K7105透明度試験法に準じて測定した。具体的には、スガ試験機社製SC-3H型ヘイズメーターを用い測定した。
下記実施例18~27および比較例3で得られたポリイミド系膜をガラス支持体から剥離し、剥離後のポリイミド系膜をRigaku製 Thermo Plus DSC8230(示差走査熱量測定)を用い、窒素下で、昇温速度を20℃/minとし、40~450℃の範囲で測定した。
下記実施例18~27および比較例3で得られたポリイミド系膜をガラス支持体から剥離し、剥離後のポリイミド系膜をSeiko Instrument SSC/5200を用い、昇温速度を6℃/minとし、25~350℃の範囲で測定した。測定結果から100~200℃の線膨張係数を算出した。
下記実施例18~27および比較例3で得られたワニスを、FLX-2320(KLA社製)を用いて、シリコンウエハ板(残留応力測定用、秩父電子株式会社製、厚み=300μm、直径=4インチ)上に2次乾燥後の膜厚が30μmになるように成膜し、反りをレーザーで測定し、塗膜のストレスを下記式より算出した。
下記実施例18~27および比較例3で得られた2次乾燥後のポリイミド系膜中のポリイミドのイミド化率をFT-IR(サーモフィッシャーサイエンティック製、Thermo NICOLET6700)を用いて以下の方法で定量した。
イミド化率(%)=(1-2次乾燥後のピーク面積比/1次乾燥前のピーク面積比)×100
JISK6251の7号ダンベルを用い、下記実施例18~27および比較例3で得られた2次乾燥後のガラス支持体から剥離した膜厚30μmのポリイミド系膜を23℃下、50mm/minの速度で引張り試験を実施し、引張り伸び、引張り強度、弾性率を測定した。
下記実施例18~27および比較例3で得られた2次乾燥後のガラス支持体付30μm塗膜を幅10mm×長さ50mmにカッターで切削を行い、長さ20mmまで引き剥がした後、180度の角度で速度50mm/minでピール強度を測定した。
下記実施例18~27および比較例3で得られた2次乾燥後のガラス支持体付30μm塗膜を60mm×60mmの大きさにカッターで切削後、4つの端部の浮き上がりを測定し、平均値を算出した。
温度計、窒素導入管および攪拌羽根付三口フラスコに、25℃にて窒素気流下、m-トリジン(m-TB)45.23099g(0.21306mol)、両末端アミノ変性側鎖フェニル・メチル型シリコーンX-22-1660B-3[9.4694g(0.0021521mol)]、ワニス中のポリアミック酸の濃度が14%となるように脱水N-メチル-2-ピロリドン(NMP)307gおよび脱水シクロヘキサノン(CHN)307gを加え、m-TBおよびX-22-1660B-3が完全に溶解するまで10分間攪拌した。ピロメリット酸二無水物(PMDA)22.6498g(0.10384mol)を加え30分攪拌した後、さらにPMDA22.6498g(0.10384mol)を加え60分攪拌することで反応を終了させ、次いで、ポリテトラフルオロエチレン製フィルター(ポアサイズ1μm)を用いて精密濾過行うことで、ワニスを作成した(PMDA/(mTB+X-22-1660B-3)=0.965当量)。ワニス特性を表2に示す。
実施例18において、m-TB、X-22-1660B-3およびPMDAの使用量を表2に示すように変更した以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、m-TB、X-22-1660B-3およびPMDAの使用量を表2に示すように変更した以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、m-TB45.23099gの代わりにm-TB32.56478gおよび4,4'-ジアミノジフェニルエーテル(ODA)7.8760gを用い、X-22-1660B-3およびPMDAの使用量を表2に示すように変更した以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、アミド系溶媒としてNMPの代わりにN,N-ジメチルアセトアミド(DMAc)を用いた以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、非アミド系溶媒としてCHN307gの代わりにアセトニトリル430gを用い、NMPの使用量を表2に示すように変更した以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、X-22-1660B-3(9.4694g)の代わりに信越化学製両末端アミノ変性側鎖メチル型シリコーンKF8010(数平均分子量(4400、m=58))2.8408gとX22-1660B-3(6.6286g)とを併用した以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、NMPとCHNの使用量を表2に示すように変更した以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、CHNの代わりに、エチレングリコールモノメチルエーテルを用いた以外は実施例18と同様に行った。結果を表2に示す。
実施例18において、NMP307gおよびCHN307gの代わりにNMP614を用いた以外は実施例18と同様に行った。結果を表2に示す。
実施例27において、X-22-1660B-3を用いず、また、m-TBおよびPMDAの使用量を表2に示すように変更した以外は実施例27と同様に行った。結果を表2に示す。
Claims (10)
- 前記ポリアミック酸が、(A)テトラカルボン酸二無水物およびこの反応性誘導体からなる群より選ばれる少なくとも1種のアシル化合物を含む成分と、(B)イミノ形成化合物を含む成分と、を反応させて得られ、下記(i)および/または(ii)を満たす、請求項1に記載の基板の製造方法。
(i)前記(A)成分が、(A-1)上記式(1)で表わされる構造単位を有するアシル化合物を含む
(ii)前記(B)成分が、(B-1)上記式(1)で表わされる構造単位を有するイミノ形成化合物を含む - 前記(B)成分における前記(B-1)上記式(1)で表わされる構造単位を有するイミノ形成化合物の含有量が、前記(B)成分の合計量100質量%に対して5~70質量%である、請求項2に記載の基板の製造方法。
- 前記(B-1)上記式(1)で表わされる構造単位を有するイミノ形成化合物のアミン価から計算した数平均分子量が500~10,000である、請求項2または3に記載の基板の製造方法。
- 前記ポリアミック酸が、前記(A)成分と前記(B)成分とを、(A)成分と(B)成分とのモル比((B)成分/(A)成分)0.8~1.2の範囲で反応させて得られる、請求項2~4のいずれか1項に記載の基板の製造方法。
- 前記有機溶媒が、N,N’-ジメチルイミダゾリジノン、γ-ブチロラクトン、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、テトラヒドロフラン、シクロヘキサノン、アセトニトリルおよびエチレングリコールモノエチルエーテルからなる群より選ばれる少なくとも1種の溶媒を有機溶媒全量に対して50重量%以上含む、請求項1~5のいずれか1項に記載の基板の製造方法。
- 前記ポリイミド系膜を構成するポリイミドの示差走査熱量測定(DSC、昇温速度20℃/分)で測定したガラス転移温度が350℃以上である、請求項1~6のいずれか1項に記載の基板の製造方法。
- 前記工程(b)における加熱を、200~350℃の範囲で行い、かつ、ポリイミド系膜のガラス転移温度以下で行う、請求項1~7のいずれか1項に記載の基板の製造方法。
- 前記支持体がシリコンウエハもしくは無アルカリガラスである、請求項1~8のいずれか1項に記載の基板の製造方法。
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- 2011-02-28 WO PCT/JP2011/054489 patent/WO2011122199A1/ja active Application Filing
- 2011-02-28 JP JP2012508152A patent/JPWO2011122198A1/ja active Pending
- 2011-02-28 KR KR1020127028255A patent/KR101848522B1/ko active IP Right Grant
- 2011-02-28 CN CN2011800161864A patent/CN102822238A/zh active Pending
- 2011-02-28 WO PCT/JP2011/054488 patent/WO2011122198A1/ja active Application Filing
- 2011-03-22 TW TW100109697A patent/TW201139519A/zh unknown
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WO2014098235A1 (ja) * | 2012-12-21 | 2014-06-26 | 旭化成イーマテリアルズ株式会社 | ポリイミド前駆体及びそれを含有する樹脂組成物 |
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JP2017020039A (ja) * | 2013-03-18 | 2017-01-26 | 旭化成株式会社 | 樹脂前駆体及びそれを含有する樹脂組成物、樹脂フィルム及びその製造方法、並びに、積層体及びその製造方法 |
JP2015136868A (ja) * | 2014-01-23 | 2015-07-30 | 旭化成イーマテリアルズ株式会社 | 所定構造を有するフレキシブル電子デバイスに適用される基板及びその作製方法 |
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US10544266B2 (en) | 2015-03-05 | 2020-01-28 | Lg Chem, Ltd. | Composition for the production of polyimide film for flexible board of photoelectronic device |
JP2017052877A (ja) * | 2015-09-09 | 2017-03-16 | 富士ゼロックス株式会社 | ポリイミド前駆体組成物、ポリイミド前駆体組成物の製造方法、及びポリイミド成形体の製造方法 |
US11248098B2 (en) | 2017-05-24 | 2022-02-15 | Lg Chem, Ltd. | Polyimide laminated film roll body and method for manufacturing same |
JP2020506081A (ja) * | 2017-05-24 | 2020-02-27 | エルジー・ケム・リミテッド | ポリイミド積層フィルムロール体及びその製造方法 |
JPWO2019065164A1 (ja) * | 2017-09-26 | 2020-09-03 | 東レ株式会社 | ポリイミド前駆体樹脂組成物、ポリイミド樹脂組成物、ポリイミド樹脂膜、積層体の製造方法、カラーフィルタの製造方法、液晶素子の製造方法および有機el素子の製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
JPWO2011122198A1 (ja) | 2013-07-08 |
TW201139519A (en) | 2011-11-16 |
JPWO2011122199A1 (ja) | 2013-07-08 |
CN102822238A (zh) | 2012-12-12 |
KR20130080432A (ko) | 2013-07-12 |
KR101848522B1 (ko) | 2018-04-12 |
TWI502003B (zh) | 2015-10-01 |
WO2011122198A1 (ja) | 2011-10-06 |
TW201139523A (en) | 2011-11-16 |
JP5725017B2 (ja) | 2015-05-27 |
KR20130080433A (ko) | 2013-07-12 |
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