WO2014098235A1 - ポリイミド前駆体及びそれを含有する樹脂組成物 - Google Patents
ポリイミド前駆体及びそれを含有する樹脂組成物 Download PDFInfo
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- WO2014098235A1 WO2014098235A1 PCT/JP2013/084331 JP2013084331W WO2014098235A1 WO 2014098235 A1 WO2014098235 A1 WO 2014098235A1 JP 2013084331 W JP2013084331 W JP 2013084331W WO 2014098235 A1 WO2014098235 A1 WO 2014098235A1
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- C—CHEMISTRY; METALLURGY
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
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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
- 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
Definitions
- the present invention relates to, for example, a polyimide precursor and a resin composition containing the polyimide precursor, a polyimide film, a manufacturing method thereof, a laminate, and a manufacturing method thereof, which are used for a substrate for a flexible device.
- a polyimide (PI) film is a polyimide resin film.
- a general polyimide resin is a solution polymerization of an aromatic dianhydride and an aromatic diamine to produce a polyimide precursor, followed by ring-closing dehydration at high temperature, thermal imidization, or chemical imidization using a catalyst. It is a highly heat-resistant resin that is manufactured.
- Polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent characteristics such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance.
- Polyimide resin is used in a wide range of fields including electronic materials such as insulating coating agents, insulating films, semiconductors, and electrode protection films for TFT-LCDs. Recently, it has been used in the field of display materials such as liquid crystal alignment films. Instead of the glass substrate that has been used, the adoption of a colorless transparent flexible substrate utilizing its lightness and flexibility is also being studied.
- Non-Patent Document 1 discloses 2,2-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB) and an acid containing a specific structure.
- TFMB 2,2-bis (trifluoromethyl) benzidine
- a polyimide having improved transmittance and hue transparency by using a dianhydride is disclosed.
- Patent Document 1 discloses that a flexible skeleton such as silicone diamine is introduced into polyimide by random copolymerization in order to lower the glass transition temperature and Young's modulus of the polyimide film.
- Patent Document 2 discloses that a flexible silicon-containing diamine is introduced by block copolymerization in order to reduce residual stress while maintaining the glass transition temperature and Young's modulus of polyimide.
- Example 11 of Patent Document 3 by copolymerizing a specific alicyclic tetracarboxylic dianhydride, a fluorine-based diamine, and a silicon-containing diamine, high Tg, transparency, high adhesion, A polyimide precursor capable of producing a polyimide exhibiting low warpage is disclosed.
- Non-Patent Document 1 in which the transmittance and hue transparency are improved by using the aforementioned 2,2-bis (trifluoromethyl) benzidine and an acid dianhydride containing a specific structure.
- the mechanical properties and thermal properties are not sufficient for use as, for example, semiconductor insulating films, TFT-LCD insulating films, electrode protective films, and heat-resistant colorless and transparent substrates for flexible displays.
- a polyimide film is usually formed on a support such as support glass, and a TFT element is usually formed on the polyimide film.
- an inorganic film such as silicon nitride or silicon dioxide is formed.
- the polyimide is colored, cloudy, or turbid, there is a problem that the image quality of the display deteriorates. It is necessary to reduce the yellowness (hereinafter also referred to as the YI value) as much as possible and increase the total light transmittance in visible light. There is also.
- Patent Document 1 it is known to introduce a flexible skeleton such as silicone diamine into polyimide by random copolymerization in order to lower the glass transition temperature and Young's modulus of the polyimide film. ing.
- the optical transparency is not impaired, there is a problem that the polyimide film is softened in the TFT element manufacturing process usually performed at 280 ° C. or more, and the performance of the TFT element is adversely affected. Therefore, the temperature is required to be higher than the temperature range in which the TFT element is manufactured.
- the Young's modulus is low, there is a problem that the mechanical strength of the flexible display is lowered and the rigidity of the display itself is lost. Therefore, a high Young's modulus is required.
- a polyimide material having a high elongation and a high tensile strength is preferable because of the puncture strength of the display.
- Patent Document 2 discloses that a flexible silicon-containing diamine is introduced by block copolymerization in order to reduce residual stress while maintaining the glass transition temperature and Young's modulus of polyimide.
- a special solvent combination normally, when a silicon-containing diamine is copolymerized, the phase separation of the silicone portion proceeds and the sea islands have different refractive indexes. It is influenced by an increase in the structure of the island portion of the structure, and the total light transmittance is lowered optically.
- Example 11 of Patent Document 3 a specific alicyclic tetracarboxylic dianhydride, a fluorine-based diamine, and a silicon-containing diamine are copolymerized to obtain a high Tg, transparency, A polyimide precursor capable of producing a polyimide that exhibits adhesion and low warpage is disclosed.
- the device including a polyimide film and an inorganic film such as silicon nitride or silicon dioxide is required to have bending resistance.
- the problem to be solved by the present invention is colorless and transparent, low residual stress generated between the inorganic film, excellent mechanical properties and thermophysical properties, and the polyimide film.
- a polyimide precursor that can produce a polyimide film, a resin composition containing the polyimide precursor, a polyimide film and a production method thereof, and a laminate and a production method thereof Is to provide.
- the inventors of the present invention have found that a polyimide obtained by imidizing a polyimide precursor having a specific structure is colorless and transparent, and a residual stress generated between the inorganic film and the polyimide. Is found to be excellent in mechanical properties and thermophysical properties, and a flexible device including the polyimide film can have excellent bending resistance, and based on this knowledge, the present invention has been completed. . That is, the present invention is as follows.
- the polyimide precursor is represented by the following general formula (C): ⁇ In the formula, a plurality of R 2 are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and a plurality of R 3 , R 4 , and R 5 are each independently a carbon number 1 to 20 monovalent organic groups, L 1 , L 2 , and L 3 are each independently an amino group, an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group, and R 6.
- R 6 is a monovalent organic group having 1 to 20 carbon atoms, j is an integer of 3 to 200, and k is an integer of 0 to 197. It is. ⁇
- the polyimide precursor as described in said [1] obtained by using the silicone compound represented by as a monomer component.
- the polyimide precursor is at least the following general formula (1): ⁇ Wherein, a plurality of R 1 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic group, X 1 is independently when a plurality of carbon A tetravalent organic group of 4 to 32, and n is an integer of 1 to 100.
- the polyimide precursor is replaced with or in addition to the unit 1 represented by the general formula (1) and the unit 2 represented by the general formula (2), and the following general formula (4): ⁇ Wherein a plurality of R 8 are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or an aromatic group, and a plurality of R 1 are each independently a hydrogen atom, a carbon number A monovalent aliphatic hydrocarbon of 1 to 20 or an aromatic group, and a plurality of R 3 and R 4 are each independently a monovalent aliphatic hydrocarbon of 1 to 3 carbon atoms or 6 carbon atoms Is an aromatic group of ⁇ 10, q is an integer of 3 to 50, and p is an integer of 1 to 100. ⁇ The polyimide precursor as described in said [5] containing the unit 2 represented by these.
- each X 3 independently represents a tetravalent organic group having 4 to 32 carbon atoms
- each R 1 independently represents a hydrogen atom or a monovalent carbon atom having 1 to 20 carbon atoms.
- An aliphatic hydrocarbon, or an aromatic group, and r is an integer of 1 to 100.
- the acid dianhydride-derived component of the unit 1 and the unit 2 is composed of a component derived from pyromellitic dianhydride (PMDA) and a component derived from biphenyltetracarboxylic acid (BPDA); Component derived from 4′-oxydiphthalic dianhydride (ODPA), component derived from 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic acid Component derived from dianhydride (CHDA), component derived from 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4′-biphenylbis (trimellitic acid monoester anhydride) A component derived from (TAHQ) and a component derived from 9,9′-bis (3,4-dicarboxyphenyl) fluorene dianhydride (FL)
- the acid dianhydride-derived component of the units 1 and 2 is a component derived from pyromellitic dianhydride (PMDA), a component derived from 4,4′-oxydiphthalic dianhydride (ODPA),
- PMDA pyromellitic dianhydride
- ODPA 4,4′-oxydiphthalic dianhydride
- the number of moles of the ODPA-derived component / is a ratio of 0.2 to 0.8.
- a resin composition comprising the polyimide precursor according to any one of [1] to [13] or a mixture thereof and a solvent.
- the resin composition according to [14] is spread on a surface of a support, and then the support and the resin composition are heated to imidize the polyimide precursor or a mixture thereof.
- the manufacturing method of the polyimide film characterized by comprising.
- a support and a polyimide film are provided, the resin composition according to [14] is spread on the surface of the support, and the polyimide precursor is heated by heating the support and the resin composition.
- a step of spreading the resin composition according to [14] on the surface of the support Heating the support and the resin composition to imidize the polyimide precursor to form a polyimide film, and obtaining a laminate composed of the support and the polyimide film;
- the manufacturing method of the laminated body characterized by comprising.
- a flexible substrate comprising a polyimide film and an inorganic film obtained by heating the resin composition according to [14] to imidize the polyimide precursor.
- the polyimide precursor according to the present invention is used, it is colorless and transparent, has low residual stress generated between the inorganic film, is excellent in mechanical properties and thermal stability, and is excellent in a flexible device including the polyimide film. It becomes possible to produce a polyimide film that can have bending resistance.
- the polyimide precursor according to the embodiment of the present invention has the following formula (A): It is obtained from the monomer component containing diamine represented by the following general formula (B): ⁇ Wherein a plurality of R 3 and R 4 are each independently a monovalent organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200. ⁇ , A polyimide precursor having a structural unit represented by the formula (1) having at least one glass transition temperature in a temperature range of 150 ° C. to 380 ° C.
- a polyimide resin which does not have a glass transition temperature in a region (excluding both ends) and has an imide group concentration of 2.00 to 3.70 mmol / g and may contain a solvent is obtained.
- the polyimide precursor obtained from the monomer component containing the diamine of the formula (A) and having the structural unit represented by the general formula (B) is a diamine represented by the formula (A) and a tetracarboxylic acid.
- the polyimide precursor which has a structural unit of general formula (B) is pointed out. Examples of the reactive derivative include an acid esterified product of the carboxylic acid and an acid chloride of the carboxylic group.
- Examples of the compound represented by the formula (A) include 2,2′-bis (trifluoromethyl) benzidine and 3,3′-bis (trifluoromethyl) benzidine, and among these, 2,2′- Bis (trifluoromethyl) benzidine is preferable from the viewpoint of the YI value and transparency of the resulting polyimide.
- a plurality of R 3 and R 4 each independently represents a monovalent organic group having 1 to 20 carbon atoms, and h represents an integer of 3 to 200.
- Examples of the monovalent organic group having 1 to 20 carbon atoms in R 3 and R 4 include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent amino group having 1 to 20 carbon atoms, an alkoxy group, and an epoxy group. Etc.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R 3 and R 4 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. Can be mentioned.
- the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms.
- 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 monovalent alkoxy group having 1 to 20 carbon atoms in R 3 and R 4 include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group. It is done.
- a plurality of R 3 and R 4 in the general formula (B) are monovalent aliphatic hydrocarbons having 1 to 3 carbon atoms or aromatic groups having 6 to 10 carbon atoms. It is preferable from the viewpoint of combining high heat resistance and low residual stress.
- the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group
- the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.
- H in the general formula (B) is an integer of 3 to 200, preferably 10 to 200, more preferably 20 to 150, still more preferably 30 to 100, and particularly preferably an integer of 35 to 80.
- h is 2 or less, the residual stress of the polyimide obtained from the polyimide precursor may be deteriorated (increased), and when h exceeds 200, the varnish composed of the polyimide precursor and the solvent becomes cloudy or polyimide Problems such as a decrease in mechanical strength may occur.
- the polyimide precursor having the structural unit represented by the general formula (B) is represented by the following general formula (C): ⁇ In the formula, a plurality of R 2 are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and a plurality of R 3 , R 4 , and R 5 are each independently a carbon number 1 to 20 monovalent organic groups, L 1 , L 2 , and L 3 are each independently an amino group, an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group, and R 6.
- R 6 is a monovalent organic group having 1 to 20 carbon atoms, j is an integer of 3 to 200, and k is an integer of 0 to 197. It is. ⁇ Is used as a monomer component, and is a polyimide precursor described.
- each of the plurality of R 2 independently represents a single bond or a divalent organic group having 1 to 20 carbon atoms.
- the divalent organic 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.
- 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. Of these, divalent aliphatic hydrocarbons having 3 to 20 carbon atoms are preferred.
- the arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
- R 5 has the same meaning as R 3 and R 4 in formula (B), j represents an integer of 3 to 200, and k represents an integer of 0 to 197.
- L 1 , L 2 , and L 3 are each independently one group selected from the group consisting of an amino group, an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group, and R 6 .
- R 6 is a monovalent organic group having 1 to 20 carbon atoms.
- the amino group includes amino groups and reactive derivatives thereof.
- reactive derivatives include isocyanate compounds and bis (trialkylsilyl) amino.
- Specific examples of the compound in which L 1 , L 2 , and L 3 are amino groups include both-terminal amino-modified methyl phenyl silicone (manufactured by Shin-Etsu Chemical; X22-1660B-3 (number average molecular weight 4,400), X22 -9409 (number average molecular weight 1,300)), both-end amino-modified dimethyl silicone (manufactured by Shin-Etsu Chemical; X22-161A (number average molecular weight 1,600), X22-161B (number average molecular weight 3,000), KF8012 (Number average molecular weight 4,400), manufactured by Toray Dow Corning; BY16-835U (number average molecular weight 900)), manufactured by Chisso Corporation: Silaplane FM3311 (number average molecular weight 1000)).
- Examples of the acid anhydride group include acid anhydride groups and reactive derivatives thereof.
- Examples of the reactive derivative include an acid esterified product of the carboxyl group and an acid chloride of the carboxyl group.
- Specific examples where L 1 , L 2 and L 3 of the acid anhydride group are acid anhydride groups include the following formula: And at least one acyl compound represented by the formula:
- L 1 , L 2 , and L 3 are acid anhydride groups
- X22-168AS manufactured by Shin-Etsu Chemical, number average molecular weight 1,000
- X22-168A manufactured by Shin-Etsu Chemical, number average molecular weight
- X22-168B manufactured by Shin-Etsu Chemical, number average molecular weight 3,200
- X22-168-P5-8 manufactured by Shin-Etsu Chemical, number average molecular weight 4,200
- DMS-Z21 manufactured by Gerest, number And an average molecular weight of 600 to 800.
- L 1 , L 2 and L 3 are hydroxy groups
- KF-6000 manufactured by Shin-Etsu Chemical, number average molecular weight 900
- KF-6001 manufactured by Shin-Etsu Chemical, number average molecular weight 1,800
- KF-6002 manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200
- KF-6003 manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,000
- the compound having a hydroxy group is considered to react with another tetracarboxylic dianhydride monomer.
- L 1 , L 2 , and L 3 are epoxy groups
- X22-163 manufactured by Shin-Etsu Chemical, number average molecular weight 400
- KF-105 manufactured by Shin-Etsu Chemical, Number average molecular weight 980
- X22-163A manufactured by Shin-Etsu Chemical, number average molecular weight 2,000
- X22-163B manufactured by Shin-Etsu Chemical, number average molecular weight 3,500
- X22-163C manufactured by Shin-Etsu Chemical, number average molecular weight 5)
- X22-169AS manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000
- X22-169B manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400
- the like which are alicyclic epoxy types at both ends
- L 1 , L 2 , and L 3 are mercapto groups
- L 1 , L 2 , and L 3 are mercapto groups
- X22-167B manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400
- X22-167C manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4, 600.
- the compound having a mercapto group is considered to react with other tetracarboxylic dianhydride monomers.
- L 1 , L 2 , and L 3 are each independently one group selected from the group consisting of an amino group, an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group, and R 6.
- each is preferably independently one group selected from the group consisting of an amino group, an acid anhydride group, and R 6.
- each independently is an amino group.
- J and k in the general formula (C) have the same meaning as h in the general formula (B).
- polyimide precursor which concerns on embodiment of this invention, the polyimide containing the unit 1 represented by the following general formula (1), and the unit 2 represented by the following general formula (2) or general formula (4) A precursor is preferred.
- a plurality of R 1 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic group
- X 1 is independently when a plurality of carbon A tetravalent organic group of 4 to 32
- n is an integer of 1 to 100.
- R 1 s are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or an aromatic group
- a plurality of R 2 are each independently a carbon number A divalent aliphatic hydrocarbon of 3 to 20 or an aromatic group
- a plurality of R 3 and R 4 are each independently a monovalent aliphatic hydrocarbon of 1 to 3 carbon atoms or 6 carbon atoms
- X 2 s each independently represents a tetravalent organic group having 4 to 32 carbon atoms
- 1 is an integer of 3 to 50
- m is 1 An integer of ⁇ 100. ⁇ .
- a plurality of R 8 are each independently a trivalent aliphatic hydrocarbon having 3 to 20 carbon atoms or an aromatic group
- a plurality of R 1 are each independently a hydrogen atom, a carbon number A monovalent aliphatic hydrocarbon of 1 to 20 or an aromatic group
- a plurality of R 3 and R 4 are each independently a monovalent aliphatic hydrocarbon of 1 to 3 carbon atoms or 6 carbon atoms Is an aromatic group of ⁇ 10
- q is an integer of 3 to 50
- p is an integer of 1 to 100.
- the unit 1 represented by the general formula (1) is derived from 2,2′-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB) as a component derived from diamine. including a component of an acid dianhydride-derived component having an organic group X 1.
- TFMB 2,2′-bis (trifluoromethyl) benzidine
- the unit 2 shown in the general formula (2) or general formula (4) a component derived from silicon group-containing diamine as the diamine component derived from an acid dianhydride-derived component having an organic group X 2, or diamines derived
- a component derived from 2,2′-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB) and a silicon group-containing acid dianhydride as a component derived from an acid dianhydride are included.
- Unit 1 described above is a portion for expressing Tg in the range of 150 to 380 ° C. in a polyimide resin film obtained by heating and curing a polyamic acid derivative. If the repeating unit 1 and unit 2 has a random structure, Tg may be expressed between 0 ° C. and 150 ° C. Therefore, the units 1 and 2 are preferably block copolymers. However, it is not excluded that the repetition of unit 1 and unit 2 includes a small amount of random structure as long as the target Tg can be expressed.
- the imide group concentration (mmol / g) means the number of imide groups per unit weight of the polyimide when the imidization rate is assumed to be 100 mol%.
- the imide group concentration of polyimide is 2.00 to 3.70 mmol / g, preferably 2.34 to 3.70 mmol / g, from the viewpoint of bending resistance, and 2.78 to 3.39 mmol. / G is more preferable.
- the reason why the range of the imide group concentration with good bending resistance is in the above range is unclear, but it is considered that the toughness of the polyimide film is involved.
- X 1 and X 2 of the polyimide precursor represented by the general formula (1) and the general formula (2) may be the same or different.
- the acid dianhydride-derived component is specifically selected from aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms and alicyclic tetracarboxylic dianhydrides having 6 to 36 carbon atoms. Compounds are preferred.
- 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl -Cyclohexene-1,2 dicarboxylic acid anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ', 4,4 '-Benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA) 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, methylene-4,4′-diphthalic
- PMDA is preferable from the viewpoint of CTE reduction, chemical resistance improvement, glass transition temperature (Tg) improvement, and mechanical elongation improvement.
- 6FDA and ODPA are preferable from the viewpoint of lowering yellowness and improving mechanical elongation.
- BPDA is preferable from the viewpoints of reducing residual stress, improving chemical resistance, improving Tg, and improving mechanical elongation.
- CHDA is preferable from the viewpoints of reduction of residual stress and reduction of yellowness.
- tetracarboxylic dianhydride selected from the group consisting of PMDA and BPDA having a tough structure expressing high Tg and low CTE, and 6FDA, ODPA, DSDA, TAHQ, FLDA, and CHDA with low yellowness It is preferable to use in combination with a tetracarboxylic dianhydride selected from the group from the viewpoints of lowering residual stress, lowering yellowness, and improving total light transmittance.
- a preferable combination is a combination of PMDA and ODPA, and the number of moles of ODPA / (number of moles of PMDA + number of moles of ODPA) is preferably in a ratio of 0.2 to 0.8, and more preferably A ratio of 0.4 to 0.6 is most preferable from the viewpoint of a balance between a decrease in yellowness, an increase in total light transmittance, and a decrease in residual stress.
- the polyimide precursor according to the present embodiment contains a component derived from 2,2′-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB) as the diamine component in unit 1.
- TFMB 2,2′-bis (trifluoromethyl) benzidine
- the component derived from TFMB is a component of a component derived from all diamines from the viewpoint of obtaining a suitable yellowness of the polyimide film, improvement in total light transmittance, reduction in residual stress generated between the inorganic film, and high Tg and breaking strength. It is preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more.
- the polyimide precursor according to the present embodiment is a diamine having a divalent silicon-containing group having 2 to 50 silicon atoms (hereinafter also simply referred to as silicon-containing diamine) as a diamine component other than TFMB in the unit 2. .)including.
- silicon-containing diamine examples include, for example, the following general formula (3) in which L 1 and L 2 in the general formula (C) are amino groups: ⁇ Wherein R 2 represents a divalent hydrocarbon group, which may be the same or different, and a plurality of R 3 and R 4 represent a monovalent hydrocarbon group, which may be the same or different. , And l represents an integer of 3 to 200. ) Can be suitably used.
- R 2 in the general formula (3) examples include a methylene group, an ethylene group, a propylene group, a butylene group, and a phenylene group.
- R ⁇ 3 > and R ⁇ 4 > a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group etc. can be mentioned.
- Specific examples of the compound represented by the general formula (3) include both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400), X22-9409 (number average molecular weight).
- both-end amino-modified dimethyl silicone manufactured by Shin-Etsu Chemical Co., Ltd .: X22-161A (number average molecular weight 1600), X22-161B (number average molecular weight 3000), KF8021 (number average molecular weight 4400), Toray Dow Corning: BY16 -835U (number average molecular weight 900) manufactured by Chisso: Silaplane FM3311 (number average molecular weight 1000)).
- a double-end amine-modified methyl phenyl silicone oil is preferable from the viewpoint of improving chemical resistance and Tg.
- the copolymerization ratio of the silicon-containing diamines is preferably in the range of 2 to 30% by mass with respect to the mass of the total polyimide precursor. If it is 2% by mass or less, the effect of reducing the stress generated between the inorganic film and the effect of reducing the yellowness is small, and as a result, the residual stress and the yellowness are increased. If it is 30% by mass or more, chemical resistance is remarkably lowered, total light transmittance is lowered, and Tg is also lowered. Further, the copolymerization ratio of the silicon-containing diamines is preferably 5% by mass to 25% by mass, and 10% by mass to 20% by mass is chemical resistance, total light transmittance, yellowness, Tg, residual stress. From the viewpoint of
- the polyimide precursor according to the present embodiment may contain diamine-derived components other than TFMB and silicon-containing diamines as long as the performance is not impaired.
- diamine-derived components other than TFMB and silicon-containing diamines for example, an aromatic diamine having 6 to 30 carbon atoms can be mentioned as a preferred embodiment.
- the average number of repeating units 1 is preferably 2 to 500, more preferably 5 to 300, 10 to 200 is most preferred.
- the number of repeating units 2 is preferably 1 to 300, more preferably 1 to 200, and most preferably 1 to 100 on an average per molecule. If the number of repeating units 1 exceeds 500 and the number of repeating units 2 exceeds 300, the solubility of the polyimide precursor in the solvent is deteriorated, which is not preferable.
- the ratio defined by the value obtained by dividing the number of repetitions of unit 1 by the number of repetitions of unit 2 is preferably 0.5 to 300, although it depends on the type of raw material used and the molecular weight. 5 to 200 is more preferable.
- the polyimide resin according to the present embodiment has a glass transition temperature derived from the structure of the unit 1 in the region A of 150 ° C. to 380 ° C., and has a glass transition temperature derived from the siloxane structure contained in the unit 2 ⁇ It has a feature that it has a region B of 150 ° C. to 0 ° C., and a region C between the region A and the region B of 0 ° C. to 150 ° C. (excluding both ends) has no glass transition temperature.
- the above unit ratio value is 0.5 or more, the heat resistance of the cured polyimide resin is preferably sufficient. On the other hand, when it is 300 or less, the residual stress can be reduced.
- the glass transition temperature derived from the structure of the unit 1 is more preferably in the region A1 of 200 to 380 ° C., and more preferably in the region A2 ′ of 250 to 380 ° C.
- the glass transition temperature derived from the structure of the unit 1 is preferably 380 ° C. or less, which is preferable from the viewpoint of improving the residual stress.
- the inorganic film annealing temperature and improving the performance of the inorganic film, such as gas barrier properties when an inorganic film such as silicon nitride or silicon dioxide is formed on polyimide using CVD or sputtering.
- the glass transition temperature of polyimide is preferably 150 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 300 ° C. or higher.
- the silicone diamine has a high molecular weight (specifically, an average molecular weight of 3000 or more)
- the resulting polyimide maintains a high glass transition temperature without forming a block copolymer as described above.
- Low residual stress with the inorganic film can be expressed. This is because, in the case of a high molecular weight, the silicone unit itself has a long-chain siloxane structure and is considered to have the same function as the block structure.
- the silicone diamine has a high molecular weight
- the functional group concentration is lowered, so that the high glass transition temperature and the low residual stress can be exhibited even if the charged mole number is small.
- the polyimide of the single unit 1 (unit 2 is not copolymerized)
- the precursor can be present as a polyimide precursor mixture, i.e. in a blended state.
- each X 3 independently represents a tetravalent organic group having 4 to 32 carbon atoms
- each R 1 independently represents a hydrogen atom or a monovalent carbon atom having 1 to 20 carbon atoms.
- An aliphatic hydrocarbon, or an aromatic group, and r is an integer of 1 to 100.
- the polyimide precursor represented by these is mentioned.
- L 1 in the general formula (C) L 2 , and L 3 are each independently one group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group, and R 6. Is also considered applicable.
- the number average molecular weight of the polyimide precursor according to the present embodiment is preferably 3,000 to 1,000,000, more preferably 10,000 to 300,000.
- the molecular weight is preferably 3000 or more from the viewpoint of sufficient heat resistance and strength. It is preferable that it is 1,000,000 or less from the viewpoint of sufficient solubility in a solvent.
- the polyimide resin according to the present embodiment has a physical property that cannot be achieved with a polyimide resin randomly introduced with a siloxane structure, which can significantly reduce the residual stress with the inorganic film while maintaining a high glass transition temperature in the region A. Can be achieved. That is, the polyimide resin according to the present embodiment has a glass transition temperature on the high temperature side of 150 ° C. to 380 ° C. as heat resistance that can withstand a display manufacturing process including a TFT element device on a colorless and transparent polyimide substrate, and A polyimide resin having a residual stress with the inorganic film of 20 MPa or less can be obtained. In a more preferred embodiment, a polyimide resin having a glass transition temperature of 240 to 380 ° C.
- the glass transition temperature on the low temperature side at ⁇ 150 to 0 ° C. is below room temperature, it does not affect the heat resistance required in the actual display manufacturing process. .
- the unit 1 having a glass transition temperature of 150 to 380 ° C. starts to flow into a rubber state and starts to flow above room temperature. Because the polymer as a whole does not flow due to chemical bonding with the part derived from the product, and since a microphase separation structure is formed between the blocks, the unit derived from the micro plastic deformation of the part derived from the siloxane structure It is considered that the residual stress caused by the portion derived from 1 is relaxed, and the residual stress with the inorganic film at room temperature is reduced.
- the polyimide precursor is preferably composed of a block containing a siloxane structure and two blocks not containing a siloxane structure.
- the polyimide precursor which concerns on this Embodiment can be obtained by preparing the polyimide precursor corresponding to each block separately, mixing both after that, and attaching
- the terminal group of the polyimide precursor of one block is a carboxylic acid anhydride group so that both blocks can be subjected to a condensation reaction
- the terminal group of the polyimide precursor of the other block is an amino group. Therefore, it is necessary to adjust the molar ratio of the raw materials tetracarboxylic dianhydride and diamine, respectively.
- a polyimide precursor having a complete block property can be synthesized.
- a synthesis method using the reactivity difference between the two diamines may be possible.
- a polyimide precursor having a certain degree of blockability can be produced by simultaneously adding TFMB and silicon-containing diamines to a tetracarboxylic dianhydride prepared in advance and subjecting it to a condensation reaction. Although this method cannot synthesize a blocky polyimide precursor having complete blocking properties, it can synthesize a polyimide precursor having blocking properties.
- having a block property means that the polyimide resin after heat curing is derived from a glass transition temperature derived from a polycondensate of TFMB and tetracarboxylic acid anhydride in each of the regions A and B described above, and silicon-containing diamines.
- the glass transition temperature derived from the block 2 derived from the polycondensate of tetracarboxylic acid anhydride is indicated.
- the polyimide precursor according to the present embodiment is a polyimide resin obtained by heat curing, and has a block property such that a glass transition temperature is recognized in each of the high temperature side region A and the low temperature side region B. However, it is not essential to have a complete block property. Further, if the glass transition temperature is not recognized in the region C between the region A and the region B, units other than the block 1 and the block 2 may be contained.
- the raw material containing silicone has a high molecular weight (specifically, an average molecular weight of 3000 or more)
- the silicone unit itself has a long-chain siloxane structure without forming a block copolymer as described above. It works the same as the above block structure.
- the domain of the silicone portion in the polyimide film becomes large, and the polyimide film may become cloudy.
- the amount of the raw material containing silicone is reduced, and the raw material containing silicone is adjusted to be random in the polymer, or the number of repeating units 2 is adjusted to 1.
- silicone diamine a small amount of silicone diamine is added to a large amount of acid dianhydride, and after the reaction is completed, the remaining TFMB is added, or a small amount of silicone diamine is added to a small amount of silicone diamine. It is preferable to add the remaining TFMB after the reaction is completed and the reaction is completed.
- silicone dianhydride it is preferable to obtain a polymer by appropriately adding silicone dianhydride and other acid dianhydrides after dissolving a large amount of TFMB in a solvent.
- ester-modified polyamic acids are prepared by reacting the above-mentioned tetracarboxylic acid anhydride with one equivalent of monohydric alcohol in advance with respect to the acid anhydride group, and then using a dehydrating condensing agent such as thionyl chloride or dicyclohexylcarbodiimide. After the reaction, it can also be obtained by a condensation reaction with diamines.
- the polyimide precursor which concerns on this Embodiment as mentioned above is used as a resin composition (varnish) which melt
- the resin composition is prepared by reacting an acid dianhydride component and a diamine component by dissolving them in a solvent, for example, an organic solvent. It can be produced as a solution.
- the conditions during the reaction are not particularly limited.
- the reaction temperature is ⁇ 20 to 150 ° C.
- the reaction time is 2 to 48 hours.
- an inert atmosphere such as argon or nitrogen is preferable during the reaction.
- the solvent is not particularly limited as long as it is a solvent that dissolves polyamic acid.
- a known reaction solvent one or more selected from m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, and diethyl acetate
- NMP N-methyl-2-pyrrolidone
- DMF dimethylformamide
- DMAc dimethylacetamide
- DMSO dimethyl sulfoxide
- acetone acetone
- diethyl acetate diethyl acetate
- polar solvents are useful. Of these, NMP and DMAc are preferable.
- a low-boiling solution such as tetrahydrofuran (THF) or chloroform, or a low-absorbing solvent such as ⁇ -butyrolactone may be used.
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 5000 or more and 1000000 or less, more preferably 50000 or more and 500000 or less, and further preferably 70000 or more and 250,000 or less.
- Mw weight average molecular weight
- the weight average molecular weight is 5000 or more, the strength and elongation of the resin layer obtained using the resin composition is improved, and the mechanical properties are excellent.
- the weight average molecular weight is 1,000,000 or less, coating can be performed without bleeding at a desired film thickness during processing such as coating.
- the molecular weight is preferably 50,000 or more.
- the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard.
- the solution After preparing the above-described polyamic acid varnish, the solution is heated at 130 to 200 ° C. for 5 minutes to 2 hours, so that a part of the polymer is dehydrated and imidized to such an extent that the polymer does not precipitate. Good.
- the imidization rate By controlling the temperature and time, the imidization rate can be controlled. By performing partial imidization, the viscosity stability of the resin solution during storage at room temperature can be improved.
- the range of the imidization rate is preferably 5% to 70% from the viewpoints of solubility in a solution and storage stability.
- the polyimide film according to the present embodiment develops the resin composition containing the polyimide precursor and the solvent according to the present embodiment on the surface of the support, and then heats the support and the resin composition. It is formed by imidizing a polyimide precursor. More specifically, as described above, a polyamic acid solution obtained by dissolving and reacting an acid dianhydride component and a diamine component in an organic solvent can be used.
- the support is, for example, an inorganic substrate such as a glass substrate such as an alkali-free glass substrate, but is not particularly limited. More specifically, the polyimide precursor solution described above is spread and dried on the adhesive layer formed on the main surface of the inorganic substrate, and cured at a temperature of 230 to 500 ° C. in an inert atmosphere. A polyimide film can be formed.
- examples of the developing method include known coating methods such as spin coating, slit coating, and blade coating.
- the heat treatment is performed by spreading the polyamic acid solution on the adhesive layer, and then heat-treating at a temperature of 300 ° C. or lower for 1 to 300 minutes mainly for the purpose of solvent removal, and further at 230 ° C. to 550 under an inert atmosphere such as nitrogen.
- the polyamic acid is converted into a polyimide by heat treatment at a temperature of 1 ° C. for 1 to 300 minutes.
- the thickness of the polyimide film according to the present embodiment is not particularly limited, and is preferably in the range of 10 to 200 ⁇ m, more preferably 10 to 50 ⁇ m.
- the laminate according to the present embodiment includes a support and a polyimide film, the resin composition according to the present embodiment is developed on the surface of the support, and the support and the resin composition are heated to obtain a polyimide precursor. It is obtained by imidizing the body to form a polyimide film.
- This laminated body is used for manufacturing a flexible device, for example. More specifically, a semiconductor device can be formed on a polyimide film, and then a support can be peeled off to obtain a flexible device including a flexible transparent substrate made of a polyimide film.
- the flexible substrate according to the present embodiment includes a polyimide film and an inorganic film.
- the inorganic film include films containing SiO 2 , SiN, and the like.
- the flexible substrate is formed on the polyimide film after the resin composition according to the present embodiment is developed on the surface of the support, and the polyimide precursor is imidized by heating the support and the resin composition to form a polyimide film.
- a film containing SiO 2 , SiN, or the like is formed on the substrate by plasma CVD or sputtering, and then a target semiconductor device such as a TFT is provided, followed by laser irradiation to peel off the polyimide film and the inorganic film from the support. Can be obtained.
- the polyimide film produced from the polyimide precursor according to the present embodiment is colorless and transparent, has a low yellowness, and the phase separation of the silicone part is appropriately controlled, so that the total light transmittance is It has a practical glass transition temperature that can withstand the TFT fabrication process, and is low by being relaxed by the silicone part phase-separated to such an extent that the residual stress generated between the inorganic film and the inorganic film is not optically disturbed. Since it has excellent physical properties, it is suitable for use on a transparent substrate of a flexible display.
- a flexible substrate is formed thereon using a glass substrate as a support, and a TFT or the like is formed thereon.
- the process of forming the TFT on the substrate is typically performed at a wide range of temperatures of 150 to 650 ° C., but in order to actually realize the desired performance, an inorganic substance is used at around 250 ° C. to 350 ° C.
- a material is used to form a TFT-IGZO (InGaZnO) oxide semiconductor or a TFT (a-Si-TFT, poly-Si-TFT).
- the polyimide film according to the present embodiment preferably has a residual stress generated between the polyimide film and the glass of 20 MPa or less based on the film thickness of 10 ⁇ m.
- the polyimide film according to the present embodiment has a yellowness of 10 or less on the basis of the film thickness of 20 ⁇ m, and the transmittance was measured with an ultraviolet spectrophotometer based on the film thickness of 20 ⁇ m.
- the transmittance at 550 nm is preferably 85% or more.
- the polyimide film according to the present embodiment is excellent in breaking strength when handling a flexible substrate, so that the breaking strength is 200 MPa or more on the basis of the film thickness of 20 ⁇ m from the viewpoint of improving the yield. More preferred.
- the polyimide film according to the present embodiment satisfying the above physical properties is used as a colorless transparent substrate for flexible displays, in particular, the use of which is limited by the yellow color of existing polyimide films. Furthermore, for example, it can be used in a field where colorless transparency is required, such as a protective film or a light-diffusing sheet and a coating film (for example, TFT-LCD interlayer, gate insulating film, liquid crystal alignment film) in TFT-LCD. It is.
- the polyimide according to the present embodiment is applied as the liquid crystal alignment film, it contributes to an increase in aperture ratio, and a TFT-LCD with a high contrast ratio can be manufactured.
- the polyimide film and laminate produced using the polyimide precursor according to the present embodiment are particularly suitable as a substrate for the production of, for example, semiconductor insulation films, TFT-LCD insulation films, electrode protection films, and flexible devices.
- the flexible device include a flexible display, a flexible solar cell, flexible lighting, and a flexible battery.
- the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.
- GPC gel permeation chromatography
- N N-dimethylformamide
- 24.8 mmol / L lithium bromide monohydrate manufactured by Wako Pure Chemical Industries, Ltd.
- Purity 99.5% 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
- a calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). Column: Shodex KD-806M (made by Showa Denko) Flow rate: 1.0 mL / min Column temperature: 40 ° C Pump: PU-2080 Plus (manufactured by JASCO) Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)
- Polyamic acid is applied to a non-alkali glass substrate (thickness 0.7 mm) with a bar coater, leveled at room temperature for 5 to 10 minutes, heated in a hot air oven at 140 ° C. for 60 minutes, and further in a nitrogen atmosphere And heated at 350 ° C. for 60 minutes to prepare a laminate.
- the film thickness of the resin composition of the laminate was 20 ⁇ m. After curing at 350 ° C. (curing treatment), the laminate was allowed to stand at room temperature for 24 hours, and the polyimide film was peeled off from the glass to isolate the film.
- this polyimide film cured at 350 ° C. was used as a sample.
- the oxygen concentration in the cure was in the range of 20 to 120 ppm.
- the polyimide film cured at 350 ° C. and having a thickness of 20 ⁇ m was measured for yellowness (YI value) and total light transmittance using a D65 light source manufactured by Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600).
- Tg (1) glass transition temperature
- CTE linear expansion coefficient
- the polyimide tape was heated with a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation.
- TMA-50 thermomechanical analyzer
- the test piece elongation was measured in a temperature range of 50 to 450 ° C under a load of 5 g, a heating rate of 10 ° C / min, under a nitrogen atmosphere (flow rate 20 ml / min), and the inflection point as the glass transition temperature.
- the CTE of the polyimide film at 100 to 250 ° C. was obtained.
- Tg (2) glass transition temperature below the room temperature region
- the obtained polyimide tape is subjected to dynamic viscoelasticity in the range of ⁇ 150 ° C. to 400 ° C.
- the inflection point in the temperature region below room temperature of E prime was measured by a measuring device (Orientec Co., Ltd., RHEOVIBRON MODEL RHEO-1021), and the inflection point was determined as the glass transition temperature at low temperature.
- Number of moles of imide group (mol): Number of moles of acid anhydride monomer or amine monomer (if any is small, the number of moles) ⁇ 2
- the polyimide film with SiN film was peeled off from the glass wafer.
- a bending test was performed using the obtained polyimide film with SiN film.
- the test conditions were an inscribed circle diameter of 15 mm and a push bending angle of 180 °.
- the push-bending operation was repeated 10 times each for bending the SiN film inside and bending outside.
- the polyimide film with SiN film was observed with an optical microscope. Evaluation was based on the following criteria: ⁇ : Neither crack nor peeling is observed after the bending test. ⁇ : Crack is observed after the bending test. ⁇ : After the bending test, peeling is observed on the crack, the polyimide film and the SiN film. Table 5 below shows the evaluation results in which peeling is observed in the crack, the polyimide film, and the SiN film.
- Example 1 While introducing nitrogen gas into a 3 L separable flask equipped with a stir bar equipped with an oil bath, 12.25 g of both-end amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) 2822 g of NMP was added, followed by 124.1 g (0.4 mol) of 4,4′-oxydiphthalic dianhydride (ODPA) and stirred at room temperature for 30 minutes.
- ODPA 4,4′-oxydiphthalic dianhydride
- Example 2 A varnish was obtained in the same manner as in Example 1 except that ODPA was changed to 93.06 g (0.3 mol), NMP was changed to 2749 g, and PMDA was changed to 43.62 g (0.2 mol).
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 3 A varnish was obtained in the same manner as in Example 1 except that ODPA was changed to 77.55 g (0.25 mol), NMP was changed to 2711 g, and PMDA was changed to 54.33 g (0.25 mol).
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 4 A varnish was obtained in the same manner as in Example 1 except that ODPA was changed to 62.04 g (0.2 mol), NMP was changed to 2675 g, and PMDA was changed to 65.44 g (0.3 mol).
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 5 A varnish was obtained in the same manner as in Example 1 except that ODPA was changed to 31.02 g (0.1 mol), NMP was changed to 2601 g, and PMDA was changed to 87.25 g (0.4 mol).
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 7 A varnish was obtained in the same manner as in Example 3 except that PMDA was changed to 73.56 g (0.25 mol) of BPDA and NMP was changed to 2864 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 8 Varnish was obtained in the same manner as in Example 3 except that ODPA was changed to 56.04 g (0.25 mol) of CHDA, PMDA was changed to 73.56 g (0.25 mol), and NMP was changed to 2540 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 10 A varnish was obtained in the same manner as in Example 3 except that ODPA was changed to 49.03 g (0.25 mol) of CBDA and PMDA was changed to 73.56 g (0.25 mol) of NBP.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 11 A varnish was obtained in the same manner as in Example 3 except that ODPA was changed to 49.03 g (0.25 mol) of CBDA and NMP was changed to 2636 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 12 A varnish was obtained in the same manner as in Example 3, except that ODPA was changed to 111.06 g (0.25 mol) of 6FDA and PMDA was changed to 73.56 g (0.25 mol) NMP of 3132 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 13 A varnish was obtained in the same manner as in Example 3 except that ODPA was changed to 111.06 g (0.25 mol) of 6FDA and NMP was changed to 2980 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 14 A varnish was obtained in the same manner as in Example 3, except that ODPA was changed to 155.11 g (0.5 mol), and NMP was changed to 2896 g without adding PMDA.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 15 A varnish was obtained in the same manner as in Example 14 except that ODPA was changed to 6FDA 222.12 g (0.5 mol) and NMP was changed to 3432 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 16 A varnish was obtained in the same manner as in Example 14 except that ODPA was changed to 98.06 g (0.5 mol) of CBDA and NMP was changed to 2440 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 17 Varnish was obtained in the same manner as in Example 14 except that ODPA was changed to 112.08 g (0.5 mol) of CHDA and NMP was changed to 2552 g.
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 1 A varnish was obtained in the same manner as in Example 1 except that NMP was changed to 2528 g without adding ODPA and PMDA to be added was changed to 109.06 g (0.5 mol).
- the composition here is shown in Table 1 below.
- Table 2 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 18 A varnish was prepared in the same manner as in Example 1 except that both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3206 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 19 A varnish was prepared in the same manner as in Example 2 except that both terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3123 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 20 A varnish was prepared in the same manner as in Example 3 except that the amine-modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3079 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 21 A varnish was prepared in the same manner as in Example 4 except that the amine-modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3039 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 22 A varnish was prepared in the same manner as in Example 5 except that both terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 2956 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 23 A varnish was prepared in the same manner as in Example 7 except that both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3254 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 24 A varnish was prepared in the same manner as in Example 8 except that both terminal amine-modified methyl phenyl silicone oils (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) were changed to 55.00 g and NMP was changed to 3059 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 25 A varnish was prepared in the same manner as in Reference Example 9 except that both terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 2884 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 26 A varnish was prepared in the same manner as in Example 12 except that both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3557 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 27 A varnish was prepared in the same manner as in Example 13 except that both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3383 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 28 A varnish was prepared in the same manner as in Example 14 except that both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3290 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 29 A varnish was prepared in the same manner as in Example 15 except that both terminal amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 3897 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 30 A varnish was prepared in the same manner as in Example 17, except that both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g and NMP was changed to 2900 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 31 A varnish was prepared in the same manner as in Example 17 except that 94.96 g of both-terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 94.96 g and NMP was changed to 3441 g. Obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 32 ODPA was changed to 89.57 g (0.25 mol) of DSDA, both ends amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g, and NMP was changed to 3188 g.
- a varnish was obtained in the same manner as in Example 3 except that.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- ODPA is 89.57 g (0.25 mol) of DSDA
- PMDA is 73.56 g (0.25 mol) of BPDA
- both ends are amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400 ))
- NMP was changed to 3362 g to obtain a varnish in the same manner as in Example 3.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 34 ODPA was changed to 179.14 g (0.5 mol) of DSDA, double-ended amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g, and NMP was changed to 3507 g.
- a varnish was obtained in the same manner as in Example 14 except that.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 35 ODPA was changed to TAHQ 114.58 g (0.25 mol), both-end amine-modified methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g, and NMP was changed to 3415 g.
- a varnish was obtained in the same manner as in Example 3 except that. The composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 36 ODPA in TAHQ (114.58 g, 0.25 mol), PMDA in BPDA (73.56 g, 0.25 mol), amine-modified methylphenylsilicone oil (X22-1660B-3 (manufactured by Shin-Etsu Chemical Co., Ltd.) (number average molecular weight: 4400) )) was changed to 55.00 g and NMP was changed to 3589 g to obtain a varnish in the same manner as in Example 3.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 37 ODPA was changed to TAHQ 229.17 g (0.5 mol), both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g, and NMP was changed to 3961 g.
- a varnish was obtained in the same manner as in Example 14 except that.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 38 ODPA was changed to 114.61 g (0.25 mol) of FLDA, both ends amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was changed to 55.00 g, and NMP was changed to 3415 g.
- a varnish was obtained in the same manner as in Example 3 except that.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- ODPA is FLDA 114.61 g (0.25 mol)
- PMDA is BPDA 73.56 g (0.25 mol)
- both terminal amine-modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400 ))
- NMP was changed to 3589 g to obtain a varnish in the same manner as in Example 3.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 40 Changed ODPA to FLDA 229.21 g (0.5 mol), double-ended amine-modified methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) to 55.00 g, and NMP to 3961 g
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 41 While introducing nitrogen gas into a 3 L separable flask equipped with a stir bar equipped with an oil bath, 157.81 g (0.493 mol) of TFMB and 3101 g of NMP were added, followed by acid anhydride-modified methylphenyl silicone oil (Shin-Etsu). 52.5 g of Chemical Co., Ltd. (X22-168-P5-B (number average molecular weight 4200)) was added, and the mixture was stirred at room temperature for 30 minutes.
- X22-168-P5-B number average molecular weight 4200
- Example 42 NMP changed to 3275 g, ODPA 77.55 g (0.25 mol) and PMDA 54.35 g (0.25 mol) changed to ODPA 77.55 g (0.25 mol) and BPDA 73.56 g (0.25 mol)
- a varnish was obtained in the same manner as in Example 41 except that.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 43 Except that NMP was changed to 3311 g and ODPA 77.55 g (0.25 mol) and PMDA 54.35 g (0.25 mol) were changed to ODPA 155.11 g (0.5 mol), the same as in Example 41 A varnish was obtained.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 44 12.25 g of both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was added to both-end epoxy-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-163-C ( Number average molecular weight 5400)) 67.50 g and varnish was obtained in the same manner as in Example 3 except that NMP was changed to 3193 g.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 45 12.25 g of both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was added to both-end epoxy-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-163-C ( Number average molecular weight 5400)) 67.50 g and varnish was obtained in the same manner as in Example 7 except that NMP was changed to 3367 g.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 46 12.25 g of both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) was added to both-end epoxy-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-163-C ( Number average molecular weight 5400)) 67.50 g, NMP was changed to 3403 g, and varnish was obtained in the same manner as in Example 14.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 50 12.25 g of both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) and both-end mercapto-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-167-C ( Number average molecular weight 4600)) 57.50 g, NMP was changed to 3102 g, and varnish was obtained in the same manner as in Example 3.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 51 12.25 g of both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) and both-end mercapto-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-167-C ( Number average molecular weight 4600)) 57.50 g, NMP was changed to 3276 g, and varnish was obtained in the same manner as in Example 7.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 52 12.25 g of both-end amine-modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) and both-end mercapto-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-167-C ( Number average molecular weight 4600)) 57.50 g, and varnish was obtained in the same manner as in Example 14 except that NMP was changed to 3312 g.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid in the obtained varnish and the test results of the film cured at 350 ° C.
- Example 53 The polyimide precursor was synthesized in the same manner as in Example 20. Subsequently, the NMP solution of polyamic acid was heated to 150 ° C., stirred for 10 minutes, then returned to room temperature by removing the oil bath, and partially imidized polyamide An NMP solution of acid was obtained. From the imide group peak (1780 cm ⁇ 1 ) determined by IR measurement, it was confirmed that the imidization ratio was 10%.
- the composition here is shown in Table 3 below.
- Table 4 below shows the weight average molecular weight (Mw) of the polyamic acid partially imidized in the obtained varnish and the test results of the film cured at 350 ° C.
- Comparative Examples 3 to 7 and 9 to 11 have high yellowness and total light transmittance but high residual stress. Moreover, as shown in Table 5, a SiN film was formed on a polyimide film, and a bending test of the laminated film was performed. It was confirmed that the example has sufficient bending resistance in the test. On the other hand, in Comparative Examples 1 to 8 and 11 to 13, cracks and peeling of the polyimide film and the SiN film were observed, and the bending resistance was insufficient. From this result, the polyimide obtained from the polyimide precursor according to the present invention is colorless and transparent, has low residual stress generated between the inorganic film, excellent mechanical properties and thermophysical properties, and further provides the polyimide film. It was confirmed that the polyimide film which the flexible device containing can have the outstanding bending tolerance can be manufactured. In addition, this invention is not limited to the said embodiment, It can be implemented in various changes.
- a polyimide film obtained by imidizing a polyimide resin using a polyimide precursor according to the present invention can be suitably used as a substrate material in the production of, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible display. is there.
Abstract
Description
このようなポリイミドの透明性を向上する課題に対して、以下の非特許文献1には、2,2-ビス(トリフルオロメチル)ベンジジン(以下、TFMBとも記す。)と特定の構造を含む酸二無水物を用いることで、透過率及び色相の透明度を向上させたポリイミドが開示されている。
また、以下の特許文献2には、ポリイミドのガラス転移温度やヤング率を維持したまま、残留応力を低減する目的で柔軟なケイ素含有ジアミンをブロック共重合で導入することが開示されている。
さらに、以下の特許文献3の実施例11には、特定の脂環式テトラカルボン酸二無水物とフッ素系ジアミン、ケイ素含有ジアミンを共重合することにより、高Tg、透明性、高密着性、低そり性を発現するポリイミドを生成しうるポリイミド前駆体が開示されている。
また、ポリイミドに色づきや曇り、濁りがあると、ディスプレイの画質が低下するという問題があり、黄色度(以下、YI値とも記す。)をできるだけ低くし、可視光における全光線透過率を上げる必要もある。
一般に、CTEを下げるには強直なポリイミド構造を採用することが知られているが、分子を強直にすると、分子内、分子間の電荷移動錯体の形成が進み、黄色度が上がり、無色透明性が損なわれるという問題があった。
また、特許文献2の実施例に記載されるように、ガラス転移温度が450℃以上である場合、残留応力低減の効果が充分に得られないという問題があった。さらに、目標とする残留応力の低下効果を得るために、シリコーン部分の導入量を増やすと、シリコーン部分の相分離が進み、結果として全光線透過率が下がるという問題もあった。
すなわち、本発明は、以下の通りのものである。
{式中、複数あるR8は、それぞれ独立に、炭素数3~20の三価の脂肪族炭化水素、又は芳香族基であり、複数あるR1は、それぞれ独立に、水素原子、炭素数1~20の一価の脂肪族炭化水素、又は芳香族基であり、複数あるR3とR4は、それぞれ独立に、炭素数1~3の一価の脂肪族炭化水素、又は炭素数6~10の芳香族基であり、qは3~50の整数であり、そしてpは、1~100の整数である。}で表されるユニット2を含有する、前記[5]に記載のポリイミド前駆体。
該支持体及び該樹脂組成物を加熱して前記ポリイミド前駆体をイミド化してポリイミドフィルムを形成する工程と、
該ポリイミドフィルムを該支持体から剥離して該ポリイミドフィルムを得る工程と、
を具備することを特徴とするポリイミドフィルムの製造方法。
該支持体及び該樹脂組成物を加熱して前記ポリイミド前駆体をイミド化してポリイミド膜を形成して、該支持体及び該ポリイミド膜で構成された積層体を得る工程と、
を具備することを特徴とする積層体の製造方法。
本発明の実施の形態に係るポリイミド前駆体は、下記式(A):
前記式(A)のジアミンを含むモノマー成分より得られ、かつ、前記一般式(B)で表される構造単位を有するポリイミド前駆体とは、式(A)で表されるジアミンと、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反応させて得られるポリイミド前駆体であって、一般式(B)の構造単位を有するポリイミド前駆体を指す。反応性誘導体としては、該カルボン酸の酸エステル化物、該カルボン基の酸クロライドなどが挙げられる。
前記一般式(B)において複数のR3とR4は、それぞれ独立に、炭素数1~20の一価の有機基を示し、hは、3~200の整数を示す。
R3とR4における炭素数1~20の一価の有機基としては、炭素数1~20の一価の炭化水素基、炭素数1~20の一価のアミノ基、アルコキシ基、エポキシ基等を挙げることができる。R3とR4における炭素数1~20の一価の炭化水素基としては、炭素数1~20のアルキル基、炭素数3~20のシクロアルキル基、炭素数6~20のアリール基等が挙げられる。炭素数1~20のアルキル基としては、炭素数1~10のアルキル基であることが好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t-ブチル基、ペンチル基、ヘキシル基等が挙げられる。前記炭素数3~20のシクロアルキル基としては、炭素数3~10のシクロアルキル基であることが好ましく、具体的には、シクロペンチル基、シクロヘキシル基等が挙げられる。前記炭素数6~20のアリール基としては、炭素数6~12のアリール基であることが好ましく、具体的には、フェニル基、トリル基、ナフチル基等が挙げられる。前記R3、R4における炭素数1~20の一価のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロピルオキシ基、ブトキシ基、フェノキシ基、プロペニルオキシ基およびシクロヘキシルオキシ基等が挙げられる。
折り曲げ耐性が良好なイミド基濃度の範囲が上記範囲である理由は不明確であるが、ポリイミド膜の靭性が関与していると考えられる。
以下、ユニット1に含まれる有機基X1を有する酸二無水物由来成分と、ユニット2に含まれる有機基X2を有する酸二無水物由来成分について説明する。
上記一般式(1)及び一般式(2)で表されるポリイミド前駆体のX1とX2は、同一でも、相違してもよい。酸二無水物由来成分は、具体的には、炭素数が8~36の芳香族テトラカルボン酸二無水物、及び炭素数が6~36の脂環式テトラカルボン酸二無水物から選択される化合物が好ましい。
また、本実施の形態に係るポリイミド前駆体は、ユニット1において、ジアミン成分として、2,2’-ビス(トリフルオロメチル)ベンジジン(以下、TFMBとも記す。)由来の成分を含有する。TFMB由来の成分は、ポリイミドフィルムの好適な黄色度、全光線透過率の向上、無機膜との間に生じる残留応力の低下、及び高Tg、破断強度を得る観点から、全ジアミン由来の成分の60モル%以上であることが好ましく、70モル%以上であることがより好ましく、80モル%以上であることがさらに好ましい。
具体的には、4,4’-(又は3,4’-、3,3’-、2,4’-)ジアミノジフェニルエーテル、4,4’-(又は3,3’-)ジアミノジフェニルスルフォン、4,4’-(又は3,3’-)ジアミノジフェニルスルフィド、4,4’-ベンゾフェノンジアミン、3,3’-ベンゾフェノンジアミン、4,4’-ジ(4-アミノフェノキシ)フェニルスルフォン、4,4’-ジ(3-アミノフェノキシ)フェニルスルフォン、4,4’-ビス(4-アミノフェノキシ)ビフェニル、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、2,2-ビス{4-(4-アミノフェノキシ)フェニル}プロパン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、2,2’-ビス(4-アミノフェニル)プロパン、2,2’,6,6’-テトラメチル-4,4’-ジアミノビフェニル、2,2’,6,6’-テトラトリフルオロメチル-4,4’-ジアミノビフェニル、ビス{(4-アミノフェニル)-2-プロピル}1,4-ベンゼン、9,9-ビス(4-アミノフェニル)フルオレン、9,9-ビス(4-アミノフェノキシフェニル)フルオレン、3,3’-ジメチルベンチジン、3,3’-ジメトキシベンチジン、3,5-ジアミノ安息香酸などの芳香族ジアミン、2,6-ジアミノピリジン、2,4-ジアミノピリジン、ビス(4-アミノフェニル-2-プロピル)-1,4-ベンゼン、3,3’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル(3,3’-TFDB)、2,2’-ビス[3(3-アミノフェノキシ)フェニル]ヘキサフルオロプロパン(3-BDAF)、2,2’-ビス[4(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン(4-BDAF)、2,2’-ビス(3-アミノフェニル)ヘキサフルオロプロパン(3,3’-6F)、2,2’-ビス(4-アミノフェニル)ヘキサフルオロプロパン(4,4’-6F)から選ばれる1種以上が挙げられる。
すなわち本実施の形態に係るポリイミド樹脂によって、無色透明ポリイミド基板上にTFT素子装置を備えたディスプレイ製造工程に耐えうる耐熱性として高温側のガラス転移温度が150℃~380℃を有し、かつ、無機膜との残留応力が20MPa以下のポリイミド樹脂が得ることができる。また、より好適な態様においては、ガラス転移温度が240~380℃で無機膜との残留応力が15MPa以下のポリイミド樹脂を得ることができる。本実施の形態に係るポリイミド樹脂においては、-150~0℃に有する低温側のガラス転移温度は室温以下であるために、実際のディスプレイ製造工程で必要とされる耐熱性には影響を与えない。
一方、シリコーンを含む原料が高分子量(具体的には、平均分子量3000以上)である場合、上記のようなブロック共重合体を形成しなくても、シリコーン単位自体が長鎖シロキサン構造をとっており、上記ブロック構造と同じ働きをする。更には、上述のようにブロック構造を作る合成法を採用すると、ポリイミド膜中でのシリコーン部分のドメインが大きくなり、ポリイミド膜が白濁する場合がある。その場合は、シリコーンを含む原料の使用量を削減し、ポリマー中で、シリコーンを含む原料がランダムとなるように、又はユニット2の繰り返し数が1となるように調整する。具体的には、シリコーンジアミンを使用する際には、大量の酸二無水物の中に少量のシリコーンジアミンを加えて、反応が終了した後に、残りのTFMBを加えるか、少量のシリコーンジアミンに大量の酸二無水物を加え、反応が終了した後に、残りのTFMBを加える方法が好ましい。シリコーン酸二無水物を使用する際には、大量のTFMBを溶媒に溶解した後に、シリコーン酸二無水物および他の酸二無水物を適宜添加して、ポリマーを得るのが好ましい。
上述のような本実施の形態に係るポリイミド前駆体は、これを溶媒に溶解した樹脂組成物(ワニス)として用いられる。
より好ましい態様としては、樹脂組成物は、酸二無水物成分及びジアミン成分を、溶媒、例えば有機溶媒に溶解して反応させ、ポリイミド前駆体の一態様であるポリアミド酸及び溶媒を含有するポリアミド酸溶液として製造することができる。ここで、反応時の条件は、特に限定されないが、例えば、反応温度は-20~150℃、反応時間は2~48時間である。ケイ素基含有ジアミン類との反応を十分に進めるために、120℃で30分程度を加熱することが好ましい。また、反応時、アルゴンや窒素などの不活性雰囲気であることが好ましい。
本実施の形態に係るポリイミドフィルムは、本実施の形態に係るポリイミド前駆体及び溶媒を含有する樹脂組成物を、支持体の表面上に展開し、次いで、支持体及び樹脂組成物を加熱してポリイミド前駆体をイミド化して形成される。より具体的には、上述のように、酸二無水物成分及びジアミン成分を有機溶媒中に溶解して反応させて得られるポリアミド酸溶液を用いることができる。
ここで、支持体は、例えば、無アルカリガラス基板などのガラス基板のような無機基板であるが、特に限定されるものではない。
より具体的には、上述のポリイミド前駆体溶液を、無機基板の主面上に形成された接着層上に展開・乾燥し、不活性雰囲気下で230~500℃の温度にて硬化して、ポリイミドフィルムを形成することができる。
また、本実施の形態に係るポリイミドフィルムの厚さは、特に限定されず、10~200μmの範囲であることが好ましく、より好ましくは10~50μmである。
本実施の形態に係る積層体は、支持体及びポリイミド膜を具備し、支持体の表面上に本実施の形態に係る樹脂組成物を展開し、支持体及び樹脂組成物を加熱してポリイミド前駆体をイミド化してポリイミド膜を形成して得られる。
この積層体は、例えば、フレキシブルデバイスの製造に用いられる。より具体的には、ポリイミド膜の上に半導体デバイスを形成し、その後、支持体を剥離してポリイミド膜からなるフレキシブル透明基板を具備するフレキシブルデバイスを得ることができる。
本実施の形態に係るフレキシブル基板は、ポリイミド膜及び無機膜を具備する。無機膜としては具体的にはSiO2、SiN等を含む膜が挙げられる。
当該フレキシブル基板は、支持体の表面上に本実施の形態に係る樹脂組成物を展開し、支持体及び樹脂組成物を加熱してポリイミド前駆体をイミド化してポリイミド膜を形成後、ポリイミド膜上にプラズマCVD法やスパッタ法によりSiO2、SiN等を含む膜を形成し、その後、TFTなど目的とする半導体装置を具備した後に、レーザー照射等し、ポリイミド膜及び無機膜を支持体から剥離することにより得られる。
この際、フレキシブル基板とポリイミド膜に生じる残留応力が高ければ、高温のTFT工程で膨張した後、常温冷却時に収縮する際、ガラス基板の反りや破損、フレキシブル基板のガラス基板からの剥離などの問題が生じる。一般的に、ガラス基板の熱膨張係数は樹脂に比較して小さいため、フレキシブル基板との間に残留応力が発生する。本実施の形態に係るポリイミドフィルムは、この点を考慮して、フィルムの厚さ10μmを基準として、ポリイミドフィルムとガラスとの間に生じる残留応力が20MPa以下であることが好ましい。
また、本実施の形態に係るポリイミドフィルムは、フレキシブル基板を取り扱う際に破断強度に優れることにより、歩留まりを向上させる観点から、フィルムの厚さ20μmを基準として、破断強度が200MPa以上であることがより好ましい。
実施例及び比較例における各種評価は次の通り行った。
重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)にて、下記の条件により測定した。溶媒としては、N,N-ジメチルホルムアミド(和光純薬工業社製、高速液体クロマトグラフ用)を用い、測定前に24.8mmol/Lの臭化リチウム一水和物(和光純薬工業社製、純度99.5%)及び63.2mmol/Lのリン酸(和光純薬工業社製、高速液体クロマトグラフ用)を加えたものを使用した。また、重量平均分子量を算出するための検量線は、スタンダードポリスチレン(東ソー社製)を用いて作成した。
カラム:Shodex KD-806M(昭和電工社製)
流速:1.0mL/分
カラム温度:40℃
ポンプ:PU-2080Plus(JASCO社製)
検出器:RI-2031Plus(RI:示差屈折計、JASCO社製)
UV‐2075Plus(UV-VIS:紫外可視吸光計、JASCO社製)
ポリアミド酸をバーコーターで無アルカリガラス基板(厚さ0.7mm)に塗工し、室温で5分間~10分間レベリングを行い、熱風オーブンにて140℃にて60分間加熱し、さらに窒素雰囲気下で350℃にて60分間加熱し積層体を作製した。積層体の樹脂組成物の膜厚は、20μmとした。350℃キュア(硬化処理)した後、積層体を室温に24時間静置し、ポリイミドフィルムをガラスから剥離しフィルムを単離した。以下の破断強度、黄色度、全光線透過率及びガラス転移温度、線膨張係数の評価では、この350℃でキュアしたポリイミドフィルムをサンプルとして用いた。尚、キュア中の酸素濃度(東レエンジニアリング社製:Oxygen analyzer LC700Lを用いて測定)は、20~120ppmの範囲であった。
350℃でキュアした、サンプル長5×50mm、厚み20μmのポリイミドフィルムを引張り試験機(株式会社エーアンドディ製:RTG-1210)を用いて、速度100mm/minで引張り、引張伸度及び破断強度を測定した。
350℃でキュアした、厚み20μmのポリイミドフィルムを、日本電色工業(株)製(Spectrophotometer:SE600)にてD65光源を用い、黄色度(YI値)及び全光線透過率を測定した。
室温領域以上におけるガラス転移温度(以下、Tg(1)という。)及び線膨張係数(CTE)の測定に関しては、該ポリイミドテープを島津製作所製熱機械分析装置(TMA-50)を用いて、熱機械分析により、荷重5g、昇温速度10℃/分、窒素雰囲気下(流量20ml/分)、温度50~450℃の範囲における試験片伸びの測定を行い、その変曲点をガラス転移温度として求め、100~250℃のポリイミドフィルムのCTEを求めた。
室温領域以下におけるガラス転移温度(以下、Tg(2)という。)の測定に関しては上記の方法では不可能であるため、得られたポリイミドテープを-150℃~400℃の範囲で動的粘弾性測定装置(オリエンテック社製、RHEOVIBRON MODEL RHEO‐1021)によりEプライムの室温以下の温度領域での変曲点を測定し、その変曲点を低温でのガラス転移温度として求めた。
残留応力測定装置(テンコール社製、型式名FLX-2320)を用いて、予め「反り量」を測定しておいた、厚み625μm±25μmの6インチシリコンウェハ上に、ポリアミド酸を、バーコーターを利用して、塗布、プリベークした後、縦型キュア炉(光洋リンドバーグ社製、型式名VF-2000B)を用いて、窒素雰囲気下、350℃1時間の加熱硬化処理を施し、硬化後膜厚10μmのポリイミド膜のついたシリコンウェハを作製した。このウェハの反り量を前述の残留応力測定装置を用いて測定し、シリコンウェハとポリイミド膜の間に生じた残留応力を評価した。
イミド化率が100モル%であると仮定して、モノマー1モルあたり、2つのイミド基を有するため、下記式を用いて、実施例及び比較例のイミド基濃度(イミド化率が100モル%であると仮定した場合の理論値)を求めた。結果を以下の表5に示す。
イミド基モル数(mol):酸無水物モノマー又はアミンモノマーのモル数(いずれかが少ない場合はそのモル数)×2
ポリイミド重量(g)=酸無水物モノマー又はアミンモノマーの総重量-イミド基モル数×水の分子量
イミド基濃度(mmol/g)=イミド基モル数×1000/ポリイミド重量
フレキシブルデバイス(例えば、フレキシブルディスプレイ)の基材としてポリイミドを用いる場合、ポリイミドフィルム上にTFT素子等を形成した上で、折り曲げ耐性を有することが求められる。そこで、簡易試験として、ポリイミドフィルム上にSiN膜を形成し、その積層フィルムの折り曲げ試験を行った。
具体的には、ガラスウェハー上に実施例及び比較例のポリイミド前駆体を、キュア後(キュア条件:350℃、2時間)膜厚が5μmなるようにポリイミドフィルムを形成し、その上にプラズマCVDにより100nm厚のSiN成膜を形成した。その後、ガラスウェハーからSiN膜付ポリイミドフィルムを剥離した。得られたSiN膜付ポリイミドフィルムを用いて折り曲げ試験を行った。試験条件は、内接円直径15mm、押し曲げ角度180°とした。押し曲げ動作は、SiN膜が内側になる折り曲げ、外側になる折り曲げ、各10回繰り返し行った。押し曲げ動作後、SiN膜付ポリイミドフィルムを、光学顕微鏡で観察した。評価は下記基準で行った:
○:折り曲げ試験後、クラックも剥離も観察されない
△:折り曲げ試験後、クラックが観察される
×:折り曲げ試験後、クラックとポリイミドフィルムとSiN膜に剥離が観察される
××:5回以下の折り曲げ動作で、クラックとポリイミドフィルムとSiN膜に剥離が観察される
評価結果を以下の表5に示す。
オイルバスを備えた撹拌棒付き3Lセパラブルフラスコに、窒素ガスを導入しながら、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25g、NMPを2822g加え、続いて4,4’-オキシジフタル酸二無水物(ODPA)を124.1g(0.4モル)加えて、室温で30分撹拌した。その後、2,2′‐ビス(トリフルオロメチル)ベンジジン(TFMB)を152.99g(0.478モル)投入して溶解したことを確認した後、ピロメリット酸二無水物(PMDA)を21.8g(0.1モル)加えて、室温で3時間撹拌した後、80℃に昇温し、4時間撹拌した後、オイルバスを外して室温に戻し、ポリアミド酸のNMP溶液(以下、ワニスともいう)を得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを93.06g(0.3モル)、NMPを2749g、PMDAを43.62g(0.2モル)に変更した以外は、実施例1と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを77.55g(0.25モル)、NMPを2711g、PMDAを54.33g(0.25モル)に変更した以外は、実施例1と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを62.04g(0.2モル)、NMPを2675g、PMDAを65.44g(0.3モル)に変更した以外は、実施例1と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを31.02g(0.1モル)、NMPを2601g、PMDAを87.25g(0.4モル)に変更した以外は、実施例1と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端アミン変性ジメチルシリコーンオイル(チッソ社製 サイラプレーンFM3311(数平均分子量1000))49g、NMPを2578g、TFMBを141.23g(0.449モル)に変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
PMDAを、BPDA73.56g(0.25モル)に、NMPを2864gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAをCHDA56.04g(0.25モル)に、PMDAを、BPDA73.56g(0.25モル)に、NMPを2540gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAをCHDA56.04g(0.25モル)に、NMPを2692gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAをCBDA49.03g(0.25モル)に、PMDAをBPDA73.56g(0.25モル)NMPを2484gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAをCBDA49.03g(0.25モル)に、NMPを2636gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを6FDA111.06g(0.25モル)に、PMDAをBPDA73.56g(0.25モル)NMPを3132gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを6FDA111.06g(0.25モル)に、NMPを2980gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを155.11g(0.5モル)に、PMDAを添加せずにNMPを2896gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを6FDA222.12g(0.5モル)に、NMPを3432gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAをCBDA98.06g(0.5モル)に、NMPを2440gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAをCHDA112.08g(0.5モル)に、NMPを2552gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを添加せずに、NMPを2528gに変更し、添加するPMDAを109.06g(0.5モル)に変更した以外は、実施例1と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
PMDAをBPDA 147.11g(0.5モル)、NMPを2832gに変更した以外は、比較例1と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
オイルバスを備えた撹拌棒付き3Lセパラブルフラスコに、窒素ガスを導入しながら、NMPを2486g加え、2,2′‐ビス(トリフルオロメチル)ベンジジン(TFMB)を156.92g(0.49モル)投入して、溶解したことを確認した後、続いて4,4’-オキシジフタル酸二無水物(ODPA)を155.11g(0.5モル)加えて、室温で30分撹拌した。その後、80℃に昇温し、4時間撹拌した後、オイルバスを外して室温に戻し、ポリアミド酸のNMP溶液(以下、ワニスともいう。)を得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを6FDA222.12g(0.5モル)、NMPを3032gに変更した以外は、比較例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを77.55g(0.25モル)、PMDAを新たに54.53g(0.25モル)ODPAと同時に加え、NMPを2312gに変更した以外は、比較例3と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
ODPAを124.1g(0.4モル)、PMDAを21.8g(0.1モル)NMPを2452gに変更した以外は、比較例5と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
PMDAをBPDA73.56g(0.25モル)NMPを2464gに変更した以外は、比較例5と同様にしてワニスを得た。ここでの組成を以下の表1に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表2に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3206gに変更した以外は、実施例1と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3123gに変更した以外は、実施例2と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3079gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3039gに変更した以外は、実施例4と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを2956gに変更した以外は、実施例5と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3254gに変更した以外は、実施例7と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3059gに変更した以外は、実施例8と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを2884gに変更した以外は、参考例9と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3557gに変更した以外は、実施例12と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3383gに変更した以外は、実施例13と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3290gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3897gに変更した以外は、実施例15と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを2900gに変更した以外は、実施例17と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を94.96gに、NMPを3441gに変更した以外は、実施例17と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをDSDA89.57g(0.25モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3188gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをDSDA89.57g(0.25モル)に、PMDAをBPDA73.56g(0.25モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3362gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをDSDA179.14g(0.5モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3507gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをTAHQ114.58g(0.25モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3415gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをTAHQ114.58g(0.25モル)に、PMDAをBPDA73.56g(0.25モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3589gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをTAHQ229.17g(0.5モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3961gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをFLDA114.61g(0.25モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3415gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをFLDA114.61g(0.25モル)に、PMDAをBPDA73.56g(0.25モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3589gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをFLDA229.21g(0.5モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3961gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
オイルバスを備えた撹拌棒付き3Lセパラブルフラスコに、窒素ガスを導入しながら、TFMB157.81g(0.493モル)、NMPを3101g加え、続いて両末端酸無水物変性メチルフェニルシリコーンオイル(信越化学社製:X22-168-P5-B(数平均分子量4200))を52.5g加えて、室温で30分撹拌した。その後、ODPA77.55g(0.25モル)及び、PMDA54.35g(0.25モル)を投入し、溶解したことを確認した後、室温で3時間撹拌した後、80℃に昇温し、4時間撹拌した後、オイルバスを外して室温に戻し、ポリアミド酸のワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
NMPを3275gに変更し、ODPA77.55g(0.25モル)及び、PMDA54.35g(0.25モル)をODPA77.55g(0.25モル)及び、BPDA73.56g(0.25モル)に変更した以外は、実施例41と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
NMPを3311gに変更し、ODPA77.55g(0.25モル)及び、PMDA54.35g(0.25モル)をODPA155.11g(0.5モル)に変更した以外は、実施例41と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端エポキシ変性ジメチルシリコーンオイル(信越化学社製:X22-163-C(数平均分子量5400))67.50g、NMPを3193gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端エポキシ変性ジメチルシリコーンオイル(信越化学社製:X22-163-C(数平均分子量5400))67.50g、NMPを3367gに変更した以外は、実施例7と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端エポキシ変性ジメチルシリコーンオイル(信越化学社製:X22-163-C(数平均分子量5400))67.50g、NMPを3403gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端ヒドロキシ変性ジメチルシリコーンオイル(信越化学社製:KF-6003(数平均分子量5100))63.66g、NMPを3158gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端ヒドロキシ変性ジメチルシリコーンオイル(信越化学社製:KF-6003(数平均分子量5100))63.66g、NMPを3332gに変更した以外は、実施例7と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端ヒドロキシ変性ジメチルシリコーンオイル(信越化学社製:KF-6003(数平均分子量5100))63.66g、NMPを3368gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端メルカプト変性ジメチルシリコーンオイル(信越化学社製:X22-167-C(数平均分子量4600))57.50g、NMPを3102gに変更した以外は、実施例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端メルカプト変性ジメチルシリコーンオイル(信越化学社製:X22-167-C(数平均分子量4600))57.50g、NMPを3276gに変更した以外は、実施例7と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))12.25gを、両末端メルカプト変性ジメチルシリコーンオイル(信越化学社製:X22-167-C(数平均分子量4600))57.50g、NMPを3312gに変更した以外は、実施例14と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ポリイミド前駆体の合成は実施例20と同様に行い、続けて、ポリアミド酸のNMP溶液を150℃に昇温し、10分間撹拌後オイルバスを外して室温に戻し、一部がイミド化したポリアミド酸のNMP溶液を得た。IR測定によるイミド基のピーク(1780cm-1)からイミド化率が10%であることを確認した。ここでの組成を以下の表3に示す。また、得られたワニス中の一部がイミド化したポリアミド酸の重量平均分子量(Mw)、並びに、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをCBDA5.12g(0.0261モル)に、TFMBを7.9g(0.0245モル)に、両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-9409(数平均分子量1300))を2.03gに、NMPを136gに変更した以外は、比較例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。尚、比較例8は、先行技術文献の欄に挙げた特許文献3の実施例11に相当する。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを2873gに変更した以外は、比較例1と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
両末端アミン変性メチルフェニルシリコーンオイル(信越化学社製:X22-1660B-3(数平均分子量4400))を55.00gに、NMPを3217gに変更した以外は、比較例2と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをDSDA179.14g(0.5モル)に、NMPを3045gに変更した以外は、比較例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをTAHQ229.17g(0.5モル)に、NMPを3498gに変更した以外は、比較例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
ODPAをFLDA229.21g(0.5モル)に、NMPを3498gに変更した以外は、比較例3と同様にしてワニスを得た。ここでの組成を以下の表3に示す。また、得られたワニス中のポリアミド酸の重量平均分子量(Mw)、及び、350℃キュアしたフィルムの試験結果を以下の表4に示す。
(1)残留応力が20MPa以下
(2)黄色度が10以下
(3)室温温度以上の温度領域におけるガラス転移温度が250℃以上380℃以下
(4)全光線透過率が85%以上
(5)破断強度が200MPa以上、引張伸度20%以上
これに対し、比較例1では、PMDA成分の増加により黄色度が高くなり、全光線透過率も白濁して低い。比較例2も同様の傾向にある。比較例3~7、及び9~11は、黄色度や全光線透過率は高いが、残留応力が高い。
また、表5に示すように、ポリイミドフィルム上にSiN膜を形成し、その積層フィルムの折り曲げ試験を行ったが、実施例は当該試験で十分な折り曲げ耐性を有することが確認された。
これに対し、比較例1~8、及び11~13は、クラックやポリイミドフィルムとSiN膜に剥離が観察され、折り曲げ耐性が不十分であった。
この結果から、本発明に係るポリイミド前駆体から得られるポリイミドは、無色透明であると共に、無機膜との間に発生する残留応力が低く、機械的物性及び熱物性に優れ、さらに当該ポリイミドフィルムを含むフレキシブルデバイスが優れた曲げ耐性を有しうる、ポリイミドフィルムを製造することができることが確認された。
なお、本発明は上記実施の形態に限定されず、種々変更して実施することが可能である。
Claims (20)
- 前記一般式(C)におけるL1とL2が、それぞれ独立に、アミノ基又は酸無水物基であり、そしてL3はR6である、請求項1又は2に記載のポリイミド前駆体。
- 前記一般式(C)におけるL1とL2が共にアミノ基である、請求項3に記載のポリイミド前駆体。
- 前記ポリイミド前駆体が、少なくとも下記一般式(1):
- 加熱硬化させた場合、20μm膜厚での黄色度が10以下であるポリイミド樹脂が得られる、請求項1~7のいずれか1項に記載のポリイミド前駆体又はその混合物。
- 前記ユニット1及び前記ユニット2の酸二無水物由来成分が、ピロメリット酸二無水物(PMDA)由来の成分、及びビフェニルテトラカルボン酸(BPDA)由来の成分からなる群と、4,4’-オキシジフタル酸二無水物(ODPA)由来の成分、4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物(6FDA)由来の成分、シクロヘキサン-1,2,4,5-テトラカルボン酸二無水物(CHDA)由来の成分、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物(DSDA)由来の成分、4,4’-ビフェニルビス(トリメリット酸モノエステル酸無水物)(TAHQ)由来の成分、及び9,9’-ビス(3,4-ジカルボキシフェニル)フルオレン二無水物(FLDA)由来の成分からなる群とから、それぞれ一つ以上選ばれる組み合わせを含み、かつ、該組み合わせが、前記ユニット1及び前記ユニット2の酸二無水物由来成分の総量に対し60モル%以上で含まれる、請求項5~8のいずれか1項に記載のポリイミド前駆体又はその混合物。
- 前記ユニット1及び前記ユニット2の酸二無水物由来成分が、ピロメリット酸二無水物(PMDA)由来の成分と、4,4’-オキシジフタル酸二無水物(ODPA)由来の成分との組み合わせであり、該ODPA由来成分のモル数/(該PMDA由来成分のモル数+該ODPA由来成分のモル数)が0.2~0.8の割合である、請求項9に記載のポリイミド前駆体又はその混合物。
- 前記ポリイミド前駆体の一部がイミド化されている、請求項1~10のいずれか1項に記載のポリイミド前駆体又はその混合物。
- 溶媒に溶解して支持体の表面に展開した後、窒素雰囲気下350℃でイミド化した場合、20μm膜厚での黄色度が10以下、破断強度が200MPa以上であり、かつ、10μm膜厚で残留応力が20MPa以下であるポリイミド樹脂が得られる、請求項1~11のいずれか1項に記載のポリイミド前駆体又はその混合物。
- フレキシブルデバイスの製造に用いられる、請求項1~12のいずれかに1項に記載のポリイミド前駆体又はその混合物。
- 請求項1~13のいずれか1項に記載のポリイミド前駆体又はその混合物と、溶媒とを含有する樹脂組成物。
- 請求項14に記載の樹脂組成物を、支持体の表面上に展開し、次いで、該支持体及び該樹脂組成物を加熱して前記ポリイミド前駆体又はその混合物をイミド化して形成されることを特徴とするポリイミドフィルム。
- 請求項14に記載の樹脂組成物を、支持体の表面上に展開する工程と、
該支持体及び該樹脂組成物を加熱して前記ポリイミド前駆体をイミド化してポリイミドフィルムを形成する工程と、
該ポリイミドフィルムを該支持体から剥離して該ポリイミドフィルムを得る工程と、
を具備することを特徴とするポリイミドフィルムの製造方法。 - 支持体及びポリイミド膜を具備し、該支持体の表面上に請求項14に記載の樹脂組成物を展開し、該支持体及び該樹脂組成物を加熱して前記ポリイミド前駆体をイミド化してポリイミド膜を形成して得られることを特徴とする積層体。
- 支持体の表面上に請求項14に記載の樹脂組成物を展開する工程と、
該支持体及び該樹脂組成物を加熱して前記ポリイミド前駆体をイミド化してポリイミド膜を形成して、該支持体及び該ポリイミド膜で構成された積層体を得る工程と、
を具備することを特徴とする積層体の製造方法。 - 請求項14に記載の樹脂組成物を加熱して前記ポリイミド前駆体をイミド化して得られるポリイミド膜及び無機膜を具備するフレキシブル基板。
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JP (1) | JP5948545B2 (ja) |
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WO2021241763A1 (ja) * | 2020-05-28 | 2021-12-02 | 旭化成株式会社 | 樹脂組成物 |
JPWO2021241763A1 (ja) * | 2020-05-28 | 2021-12-02 | ||
CN111635525A (zh) * | 2020-07-03 | 2020-09-08 | 浙江中科玖源新材料有限公司 | 一种低介电常数疏水聚酰亚胺薄膜及其制备方法 |
CN114573810A (zh) * | 2020-11-30 | 2022-06-03 | 旭化成株式会社 | 聚酰亚胺前体及聚酰亚胺树脂组合物 |
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KR20210014751A (ko) | 2021-02-09 |
JPWO2014098235A1 (ja) | 2017-01-12 |
KR102116229B1 (ko) | 2020-05-28 |
KR20200096319A (ko) | 2020-08-11 |
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