WO2016199926A1 - ポリイミド前駆体組成物、及びポリイミド組成物 - Google Patents
ポリイミド前駆体組成物、及びポリイミド組成物 Download PDFInfo
- Publication number
- WO2016199926A1 WO2016199926A1 PCT/JP2016/067453 JP2016067453W WO2016199926A1 WO 2016199926 A1 WO2016199926 A1 WO 2016199926A1 JP 2016067453 W JP2016067453 W JP 2016067453W WO 2016199926 A1 WO2016199926 A1 WO 2016199926A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyimide
- polyimide precursor
- group
- film
- aromatic ring
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 530
- 239000004642 Polyimide Substances 0.000 title claims abstract description 382
- 239000000203 mixture Substances 0.000 title claims abstract description 201
- 239000002243 precursor Substances 0.000 title claims abstract description 198
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- 230000003287 optical effect Effects 0.000 claims abstract description 127
- 239000002904 solvent Substances 0.000 claims description 89
- 239000000126 substance Substances 0.000 claims description 78
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- 229920005575 poly(amic acid) Polymers 0.000 claims description 66
- 125000003118 aryl group Chemical group 0.000 claims description 62
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- 125000002723 alicyclic group Chemical group 0.000 claims description 58
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- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 30
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- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
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- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 6
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Classifications
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- 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
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
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- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
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- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
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- H—ELECTRICITY
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- B32B2307/7242—Non-permeable
-
- 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
- B32B2457/12—Photovoltaic modules
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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
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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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
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04102—Flexible digitiser, i.e. constructional details for allowing the whole digitising part of a device to be flexed or rolled like a sheet of paper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to a polyimide composition having a small retardation in the thickness direction and in-plane direction (retardation) and excellent in characteristics such as transparency, mechanical characteristics, and heat resistance, and a precursor composition thereof.
- the present invention also relates to a polyimide film, a substrate, and the like that have a small retardation in the thickness direction and in-plane direction, and are excellent in properties such as transparency, mechanical properties, and heat resistance.
- Aromatic polyimide is essentially yellowish brown due to intramolecular conjugation and the formation of charge transfer complexes. For this reason, as a means to suppress coloration, for example, introduction of fluorine atoms into the molecule, imparting flexibility to the main chain, introduction of bulky groups as side chains, etc. inhibits intramolecular conjugation and charge transfer complex formation. And the method of expressing transparency is proposed (for example, patent document 1).
- Patent Documents 2 to 5 a method for expressing transparency by using a semi-alicyclic or fully alicyclic polyimide that does not form a charge transfer complex in principle has been proposed (for example, Patent Documents 2 to 5).
- Patent Document 6 discloses a transparent polymer resin having orientation birefringence generated by the orientation of the bond chain (specifically, polystyrene, polyphenylene oxide, polycarbonate, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, polyethylene). ) And strontium carbonate fine particles produced by a specific production method dispersed in the polymer resin, and the strontium carbonate fine particles are oriented birefringence of the polymer resin in the polymer resin.
- Non-birefringent optical resin materials are disclosed that are statistically oriented to reduce More specifically, in the non-birefringent optical resin material described in Patent Document 6, by adding fine particles of strontium carbonate, which is a needle-like crystal, to the polymer film, Strontium fine particles are statistically oriented along the direction of hot stretching. Alternatively, rod-like crystal particles of strontium carbonate are added to the polymer pellets, and the polymer pellets are used in an injection molding method or an extrusion molding method, and the strontium carbonate particles are oriented by the flow during polymer melting.
- strontium carbonate which is a needle-like crystal
- Patent Documents 7 and 8 disclose fine particles of strontium carbonate having orientation birefringence that are used to reduce birefringence by being dispersed in a polymer resin having birefringence.
- Patent Document 9 5% by weight or more of a dispersant (specifically, a phosphate ester dispersant) is added to the fine particles having optical anisotropy (specifically, fine particles of strontium carbonate), and a solvent.
- a transparent polymer specifically, polycarbonate, N-methylmaleimide / isobutene copolymer
- a method for producing an optical film that forms a film is disclosed.
- Patent Document 10 discloses a method for producing a retardation film, wherein a retardation film is obtained by stretching a thermoplastic polymer film containing polyimide having a specific structure.
- the present invention provides a polyimide composition that can be easily produced, has a small retardation in the thickness direction and in-plane direction, and is excellent in transparency, mechanical properties, heat resistance, and the like, and a precursor composition thereof. With the goal.
- the present invention also provides a varnish that provides a polyimide composition that has a small retardation in the thickness direction and in-plane direction, and is excellent in transparency, mechanical properties, heat resistance, and the like, as well as in the thickness direction and in-plane direction.
- Another object of the present invention is to provide a polyimide film and a substrate that have a small phase difference and are excellent in transparency, mechanical properties, heat resistance, and the like.
- a polyimide precursor composition comprising a polyimide precursor (A1) and fine particles (B) having optical anisotropy.
- the said polyimide precursor (A1) contains at least 1 sort (s) of the repeating unit represented by following Chemical formula (1),
- item 1 characterized by the above-mentioned.
- X 1 is a tetravalent group having an aromatic ring or alicyclic structure
- Y 1 is a divalent group having an aromatic ring or alicyclic structure
- R 1 and R 2 are each independently And hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
- the content of the repeating unit represented by the chemical formula (1) in which X 1 is a tetravalent group having an alicyclic structure and Y 1 is a divalent group having an alicyclic structure is based on the total repeating units.
- the polyimide precursor composition according to item 2 wherein X 1 in chemical formula (1) is a tetravalent group having an aromatic ring, and Y 1 is a divalent group having an aromatic ring. object. 5. 3. The polyimide precursor composition according to item 2, wherein X 1 in chemical formula (1) is a tetravalent group having an alicyclic structure, and Y 1 is a divalent group having an aromatic ring. object. 6). 3. The polyimide precursor composition according to item 2, wherein X 1 in chemical formula (1) is a tetravalent group having an aromatic ring, and Y 1 is a divalent group having an alicyclic structure. object. 7). Item 7. The polyimide precursor composition according to any one of Items 1 to 6, wherein the fine particle (B) having optical anisotropy is strontium carbonate.
- a polyimide composition comprising polyimide (A2) and fine particles (B) having optical anisotropy.
- a polyimide composition comprising polyimide (A2) and fine particles (B) having optical anisotropy.
- the polyimide composition according to item 8 wherein the polyimide (A2) contains at least one repeating unit represented by the following chemical formula (7).
- Item 10 A polyimide film comprising the polyimide composition obtained from the polyimide precursor composition according to any one of Items 1 to 7 or the polyimide composition according to any one of Items 8 to 9.
- Item 12 Item 12. A polyimide film laminate comprising the polyimide film of Item 11 and at least one glass layer. 13 12. A polyimide film laminate comprising the polyimide film according to item 11 and at least one gas barrier layer. 14 12. A polyimide film laminate comprising the polyimide film according to item 11 and at least one thin film transistor. 15. Item 14. The polyimide film laminate according to Item 12 or 13, comprising the polyimide film according to Item 11 and at least one conductive layer.
- a varnish comprising a polyimide precursor (A1) or polyimide (A2), fine particles (B) having optical anisotropy, and a solvent.
- a polyimide composition obtained by using the varnish according to Item 16.
- Item 10 A display or a touch panel comprising the polyimide composition obtained from the polyimide precursor composition according to any one of Items 1 to 7 or the polyimide composition according to any one of Items 8 to 9. Or a film for a solar cell (eg, a substrate).
- a display device or a sensor device comprising the polyimide composition obtained from the polyimide precursor composition according to any one of Items 1 to 7, or the polyimide composition according to any one of Items 8 to 9. , Photoelectric conversion device, or optical device.
- X 3 is a tetravalent group having an aromatic ring or alicyclic structure
- Y 3 is a divalent group having an aromatic ring or alicyclic structure.
- a carboxyl group in the formula ( -COOH) may form a salt with the base. 22.
- X 3 is a tetravalent group having an aromatic ring or alicyclic structure
- Y 3 is a divalent group having an aromatic ring or alicyclic structure.
- a carboxyl group in the formula ( -COOH) may form a salt with the base.
- a polyimide composition that can be easily produced, has a small retardation in the thickness direction and in-plane direction, and is excellent in transparency, mechanical properties, heat resistance, and the like, and a precursor composition thereof. Can do.
- a varnish (polyimide precursor solution composition, polyimide solution composition) can be obtained that has a small retardation in the thickness direction and in-plane direction and is excellent in transparency, mechanical properties, heat resistance, and the like.
- the present invention it is possible to provide a polyimide film and a substrate that have a small retardation in the thickness direction and in-plane direction and are excellent in transparency, mechanical properties, heat resistance, and the like. Since the polyimide composition obtained from the polyimide precursor composition of the present invention or the polyimide composition of the present invention has excellent characteristics, it is suitable for forming substrates for displays, touch panels, solar cells and the like. Can be used.
- the polyimide composition obtained from the polyimide precursor composition of the present invention or the polyimide composition of the present invention can also be suitably used for substrate applications in other devices (such as semiconductor devices), and various displays and the like.
- the display device, the sensor device such as a touch panel, the photoelectric conversion device such as a solar cell, and other optical devices can be suitably used for a cover film and a color filter.
- needle-shaped or rod-shaped fine particles having optical anisotropy such as strontium carbonate are obtained by heat-stretching a polyimide composition film or by melting the polyimide composition and performing injection molding or extrusion molding. Even if it is not oriented in one direction, that is, without special fine particle orientation treatment, it is simply optical anisotropy in the varnish (ie, polyimide precursor solution composition, polyimide solution composition) used in the production of the polyimide composition. In addition to the in-plane retardation, the retardation in the thickness direction can be easily reduced.
- fine particles having optical anisotropy can be efficiently produced without performing a special operation such as stretching. It can be oriented and a good quality optical film can be easily manufactured.
- a polyimide precursor composition containing a polyimide precursor (polyamic acid) and fine particles having optical anisotropy is imidized, water molecules are desorbed during the imidation reaction, and molecular chain alignment proceeds. It is possible to orient the fine particles having anisotropy more effectively and better.
- the thickness direction and in-plane direction retardation of the resulting polyimide composition can be reduced, but in the case of the polyimide precursor having the above composition, the effect Is large and preferable.
- the polyimide film / substrate laminate or the polyimide film of the present invention is suitable using, for example, the aforementioned polyimide precursor composition and the aforementioned polyimide composition (for example, a composition of a solution in which polyimide is dissolved) as a raw material. Is obtained.
- a surface-treated fine particle powder having optical anisotropy that can be suitably used for a polyimide composition and a precursor composition thereof, fine particles having optical anisotropy, and a solvent.
- a fine particle dispersion can be provided.
- the polyimide precursor composition of the present invention includes a polyimide precursor (A1) and fine particles (B) having optical anisotropy.
- the polyimide precursor (A1) includes, for example, at least one repeating unit represented by the following chemical formula (1).
- X 1 is a tetravalent group having an aromatic ring or alicyclic structure
- Y 1 is a divalent group having an aromatic ring or alicyclic structure
- R 1 and R 2 are each independently And hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
- the polyimide precursor (A1) may be partially imidized polyamic acid or the like including a repeating unit having an imide structure in which imidization has partially progressed.
- the polyimide composition of the present invention contains polyimide (A2) and fine particles (B) having optical anisotropy.
- a polyimide (A2) contains at least 1 sort (s) of the repeating unit represented, for example by following Chemical formula (7).
- the polyimide precursor (A1) used for the polyimide precursor composition of the present invention the polyimide (A2) used for the polyimide composition of the present invention, the polyimide precursor composition of the present invention, and the polyimide composition of the present invention.
- the fine particles (B) having optical anisotropy used in the above will be described in detail.
- the polyimide precursor (A1) includes, for example, at least one repeating unit represented by the chemical formula (1).
- X 1 in the chemical formula (1) of the polyimide precursor (A1) is a tetravalent group having an aromatic ring
- Y 1 is preferably a divalent group having an aromatic ring
- X 1 in the chemical formula (1) of the polyimide precursor (A1) is a tetravalent group having an aromatic ring
- Y 1 is preferably a divalent group having an aromatic ring.
- X 1 is a tetravalent group having an alicyclic structure
- Y 1 is a divalent group having an aromatic ring. It is preferable.
- X 1 is a tetravalent group having an alicyclic structure and Y 1 is a divalent having an alicyclic structure from the viewpoint of the properties of the resulting polyimide composition, for example, transparency, mechanical properties, or heat resistance.
- the content of the repeating unit represented by the chemical formula (1) as a group is preferably 50 mol% or less, more preferably 30 mol% or less or less than 30 mol%, more preferably 10 mol% based on all repeating units. It is preferable that it is below mol%.
- the polyimide precursor (A1) is a repeating formula (1) wherein X 1 is a tetravalent group having an aromatic ring and Y 1 is a divalent group having an aromatic ring.
- the total content of one or more units is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on all repeating units. Particularly preferred is 100 mol%.
- the polyimide precursor (A1) preferably contains a fluorine atom.
- the polyimide precursor (A1) is an aromatic compound in which X 1 is a tetravalent group having an aromatic ring containing a fluorine atom and / or Y 1 contains a fluorine atom. It is preferable that 1 type or more of the repeating unit of said Chemical formula (1) which is a bivalent group which has a ring is included.
- the polyimide precursor (A1) is a repeating compound represented by the chemical formula (1) in which X 1 is a tetravalent group having an alicyclic structure and Y 1 is a divalent group having an aromatic ring.
- the total content of one or more units is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on all repeating units. Particularly preferred is 100 mol%.
- the polyimide precursor (A1) is a repeating group represented by the chemical formula (1) in which X 1 is a tetravalent group having an aromatic ring and Y 1 is a divalent group having an alicyclic structure.
- the total content of one or more units is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on all repeating units. Particularly preferred is 100 mol%.
- the tetravalent group having an aromatic ring of X 1 is preferably a tetravalent group having an aromatic ring having 6 to 40 carbon atoms.
- Examples of the tetravalent group having an aromatic ring include the following.
- Z 1 is a direct bond or the following divalent group:
- Z 2 in the formula is a divalent organic group.
- Z 2 include an aliphatic hydrocarbon group having 2 to 24 carbon atoms and an aromatic hydrocarbon group having 6 to 24 carbon atoms.
- the tetravalent group having an aromatic ring the following are particularly preferred since both the high heat resistance and high transparency of the resulting polyimide composition can be achieved.
- Z 1 is a direct bond or a hexafluoroisopropylidene bond.
- Z 1 is more preferably a direct bond.
- Examples of the tetracarboxylic acid component that gives a repeating unit of the chemical formula (1) in which X 1 is a tetravalent group having an aromatic ring include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetra Carboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) ) Sulfone, m-terphenyl-3,4,3 ′, 4′-tetracarboxylic acid, p
- Examples of the tetracarboxylic acid component that gives a repeating unit of the chemical formula (1) in which X 1 is a tetravalent group having an aromatic ring containing a fluorine atom include 2,2-bis (3,4-dicarboxyphenyl).
- Derivatives such as hexafluoropropane, tetracarboxylic dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides thereof.
- a tetracarboxylic acid component may be used independently and can also be used in combination of multiple types.
- the tetravalent group having an alicyclic structure of X 1 is preferably a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms, more preferably at least one aliphatic 4- to 12-membered ring, more preferably an aliphatic group. More preferably, it has a 4-membered ring or an aliphatic 6-membered ring.
- the tetravalent group having an alicyclic structure of X 1 has both heat resistance and transparency, and therefore has at least one aliphatic 6-membered ring in the chemical structure and has an aromatic ring. Preferably not.
- the 6-membered ring may be a bridged ring type in which the carbon atoms constituting the ring (inside the 6-membered ring) are bonded to form a ring.
- X 1 (a tetravalent group having an alicyclic structure) having a highly symmetrical 6-membered ring structure enables dense packing of polymer chains, and the solvent resistance, heat resistance, and mechanical strength of polyimide. It is preferable because it is excellent. Further, in X 1 (a tetravalent group having an alicyclic structure), a plurality of 6-membered rings are composed of two or more common carbon atoms, and a carbon atom in which the 6-membered rings constitute the ring Bonding each other to form a ring is more preferable because good heat resistance, solvent resistance, and low linear expansion coefficient of polyimide can be easily achieved.
- Preferred examples of the tetravalent group having an aliphatic 4-membered ring or an aliphatic 6-membered ring include the following.
- R 31 to R 36 are each independently a direct bond or a divalent organic group.
- R 41 to R 47 are each independently represented by the formula: —CH 2 —, —CH ⁇ CH—, 1 type selected from the group consisting of groups represented by —CH 2 CH 2 —, —O—, and —S—.
- R 31 , R 32 , R 33 , R 34 , R 35 , R 36 specifically, a direct bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an oxygen atom (—O— ), A sulfur atom (—S—), a carbonyl bond, an ester bond, and an amide bond.
- the polyimide obtained can have both high heat resistance, high transparency, and a low linear thermal expansion coefficient.
- Examples of the tetracarboxylic acid component that gives a repeating unit of the chemical formula (1) in which X 1 is a tetravalent group having an alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxybis Phthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-3,3 ', 4,4'-tetracarboxylic acid, [1,1'-bi (Cyclohexane)]-2,3,3 ′, 4′-tetracarboxylic acid, [1,1′-bi (cyclohexane)]-2,2 ′, 3,3′-tetracarboxylic acid, 4,4′- Methylenebis (cyclohexane-1,2-dicarboxylic acid), 4,4 '-(propane-2,2-diyl) bis (cyclohex
- the divalent group having an aromatic ring of Y 1 is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms.
- Examples of the divalent group having an aromatic ring include the following.
- W 1 is a direct bond or a divalent organic group
- n 11 to n 13 each independently represents an integer of 0 to 4
- R 51 , R 52 and R 53 are each independently And an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.
- W 1 include a divalent group represented by the following formula (5) and a divalent group represented by the following formula (6).
- R 61 to R 68 in the formula (6) each independently represent any of the divalent groups represented by the formula (5).
- W 1 is a direct bond, or a formula: —NHCO—, —CONH—, —COO—, —OCO—. It is especially preferable that it is 1 type selected from the group which consists of group represented by these.
- W 1 is a group in which R 61 to R 68 are a direct bond, or one selected from the group consisting of groups represented by the formula: —NHCO—, —CONH—, —COO—, —OCO—. It is also particularly preferable that it is any of the divalent groups represented by the formula (5).
- Examples of the diamine component that gives a repeating unit of the chemical formula (1) in which Y 1 is a divalent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, and 3,3′-diamino-biphenyl.
- Examples of the diamine component that gives the repeating unit of the chemical formula (1) in which Y 1 is a divalent group having an aromatic ring containing a fluorine atom include 2,2′-bis (trifluoromethyl) benzidine, 3, 3′-bis (trifluoromethyl) benzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 ′ -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
- a diamine component may be used independently and can also be used in combination of multiple types.
- the divalent group having an alicyclic structure of Y 1 is preferably a divalent group having an alicyclic structure having 4 to 40 carbon atoms, more preferably at least one aliphatic 4- to 12-membered ring, more preferably an aliphatic group. More preferably, it has a 6-membered ring.
- divalent group having an alicyclic structure examples include the following.
- V 1 and V 2 are each independently a direct bond or a divalent organic group
- n 21 to n 26 each independently represents an integer of 0 to 4
- R 81 to R 86 Are each independently an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group
- R 91 , R 92 , and R 93 are each independently represented by the formula: —CH 2 —, (This is one selected from the group consisting of groups represented by —CH ⁇ CH—, —CH 2 CH 2 —, —O—, and —S—.)
- V 1 and V 2 include a divalent group represented by the formula (5).
- the divalent group having an alicyclic structure the following are particularly preferable because the polyimide obtained can have both high heat resistance and low linear thermal expansion coefficient.
- divalent groups having an alicyclic structure the following are preferable.
- Examples of the diamine component that gives the repeating unit of the chemical formula (1) in which Y 1 is a divalent group having an alicyclic structure include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1, 4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane 1,4-bis (
- the polyimide precursor (A1) containing at least one repeating unit represented by the chemical formula (1) can contain other repeating units other than the repeating unit represented by the chemical formula (1).
- the tetracarboxylic acid component and diamine component that give other repeating units are not particularly limited, and any other known aliphatic tetracarboxylic acids or known aliphatic diamines can be used.
- Other tetracarboxylic acid components may be used alone or in combination of two or more.
- Other diamine components may be used alone or in combination of two or more.
- the content of other repeating units other than the repeating unit represented by the chemical formula (1) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is 10 mol% or less.
- R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or an alkyl group having 3 to 9 carbon atoms.
- One of the silyl groups When R 1 and R 2 are hydrogen, polyimide tends to be easily produced.
- R 1 and R 2 can change the type of functional group and the introduction rate of the functional group by the production method described later.
- the polyimide precursor (A1) according to the present invention (polyimide precursor containing at least one repeating unit represented by the chemical formula (1)) has a chemical structure taken by R 1 and R 2 .
- the polyimide precursor (A1) of this invention can be easily manufactured with the following manufacturing methods for every classification.
- the manufacturing method of the polyimide precursor (A1) of this invention is not limited to the following manufacturing methods.
- the polyimide precursor (A1) of the present invention comprises a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent in an approximately equimolar amount, preferably a molar amount of the diamine component relative to the tetracarboxylic acid component.
- the ratio [number of moles of diamine component / number of moles of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, a relatively low temperature of 120 ° C. or less. It can obtain suitably as a polyimide precursor solution composition by reacting, suppressing imidation.
- diamine is dissolved in an organic solvent or water, and tetracarboxylic dianhydride is gradually added to this solution while stirring, and 0 to 120 ° C., preferably 5
- a polyimide precursor is obtained by stirring for 1 to 72 hours in a range of ⁇ 80 ° C.
- the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.
- the order of addition of diamine and tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor is likely to increase.
- an imidazole such as 1,2-dimethylimidazole or a base such as triethylamine is preferably 0.8 times equivalent to the carboxyl group of the resulting polyamic acid (polyimide precursor). It is preferable to add in the above amount.
- a polyimide precursor can be easily obtained by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus condensing agent or a carbodiimide condensing agent.
- the polyimide precursor obtained by this method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.
- a polyimide precursor is obtained by mixing the polyamic acid solution obtained by the method 1) and a silylating agent and stirring at 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours.
- the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.
- silylating agent not containing chlorine As the silylating agent used in the method 3) and the method 4) does not require purification of the silylated polyamic acid or the resulting polyimide, Is preferred.
- the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane.
- N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.
- an amine-based catalyst such as pyridine, piperidine, triethylamine or the like can be used to accelerate the reaction.
- This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
- the solvent (C) used for preparing the polyimide precursor (A1) is water, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl.
- An aprotic solvent such as -2-imidazolidinone and dimethyl sulfoxide is preferable, and any type of solvent can be used without any problem as long as the raw material monomer component and the resulting polyimide precursor are dissolved. It is not limited to.
- amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone , Cyclic ester solvents such as ⁇ -methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol Phenol solvents such as acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed.
- the logarithmic viscosity of the polyimide precursor (A1) is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution at a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more, more preferably 0. It is preferably 3 dL / g or more, particularly preferably 0.4 dL / g or more.
- the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the mechanical strength and heat resistance of the resulting polyimide are excellent.
- the polyimide (A2) is not particularly limited, but is obtained from the polyimide precursor (A1) and includes, for example, at least one repeating unit represented by the chemical formula (7).
- Chemical formula (7) corresponds to chemical formula (1), with X 1 corresponding to X 2 and Y 1 corresponding to Y 2 .
- Examples of X 2 and Y 2 in the chemical formula (7) include the same as X 1 and Y 1 in the chemical formula (1), and preferable ones are also the same.
- X 2 in chemical formula (7) of polyimide (A2) is a tetravalent group having an aromatic ring
- Y 2 has an aromatic ring because it is excellent in heat resistance. It is preferably a valent group.
- X 2 is a tetravalent group having an alicyclic structure
- Y 2 is a divalent group having an aromatic ring.
- X 2 is a tetravalent group having an aromatic ring
- Y 2 is a divalent group having an alicyclic structure.
- polyimide (A2) preferably contains fluorine atoms.
- a polyimide obtained from an aromatic tetracarboxylic acid component and an aromatic diamine or a polyimide obtained from an alicyclic tetracarboxylic acid component and an aromatic diamine, or an aromatic tetracarboxylic acid component and an alicyclic
- a polyimide obtained from diamine is preferred.
- the tetracarboxylic acid component includes tetracarboxylic acid and tetracarboxylic acid derivatives such as tetracarboxylic dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride.
- X 2 is a tetravalent group having an alicyclic structure
- Y 2 is a divalent group having an alicyclic structure.
- the content of the repeating unit represented by the chemical formula (7) is preferably 50 mol% or less, more preferably 30 mol% or less or less than 30 mol%, more preferably 10 mol%, based on all repeating units. The following is preferable.
- the polyimide (A2) is a repeating unit of the chemical formula (7) in which X 2 is a tetravalent group having an aromatic ring and Y 2 is a divalent group having an aromatic ring.
- the total content of one or more is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, particularly with respect to all repeating units. Preferably it is 100 mol%.
- the polyimide (A2) preferably contains a fluorine atom.
- the polyimide (A2) is an aromatic ring in which X 2 is a tetravalent group having a fluorine atom-containing aromatic ring and / or Y 2 is a fluorine atom-containing repeating unit. It is preferable that 1 type or more of the repeating unit of the said Chemical formula (7) which is a bivalent group to have is included.
- the polyimide (A2) is a repeating unit of the chemical formula (7) in which X 2 is a tetravalent group having an alicyclic structure and Y 2 is a divalent group having an aromatic ring.
- the total content of one or more is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, particularly with respect to all repeating units. Preferably it is 100 mol%.
- the polyimide (A2) is a repeating unit of the chemical formula (7) in which X 2 is a tetravalent group having an aromatic ring and Y 2 is a divalent group having an alicyclic structure.
- the total content of one or more is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, particularly with respect to all repeating units. Preferably it is 100 mol%.
- the polyimide (A2) containing at least one repeating unit represented by the chemical formula (7) may contain one or more other repeating units other than the repeating unit represented by the chemical formula (7).
- the content of other repeating units other than the repeating unit represented by the chemical formula (7) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is 10 mol% or less.
- the polyimide (A2) of the present invention can be produced by imidizing the polyimide precursor (A1) of the present invention (that is, subjecting the polyimide precursor (A1) to a dehydration ring-closing reaction).
- the imidization method is not particularly limited, and a known thermal imidation or chemical imidization method can be suitably applied.
- a manufacturing method of a polyimide (A2) it mentions later as a manufacturing method of the polyimide composition of this invention.
- Fine particles having optical anisotropy can be used without any particular limitation as long as they have optical anisotropy.
- the fine particles (B) having optical anisotropy are preferably carbonates, for example. More specifically, the fine particles (B) having optical anisotropy are preferably one or more fine particles selected from the group consisting of strontium carbonate, calcium carbonate, magnesium carbonate, cobalt carbonate, and manganese carbonate. More preferably, it is strontium carbonate.
- Examples of the carbonate form include aragonite, calcite, vaterite, and amorphous.
- the fine particle (B) having optical anisotropy preferably has an anisotropic shape such as a needle shape or a rod shape, more preferably a fine needle shape or a rod shape carbonate, It is particularly preferable to use fine needle-like or rod-like strontium carbonate.
- the fine particles (B) having optical anisotropy preferably have an average aspect ratio of 1.5 or more, more preferably 2 or more, and particularly preferably 2.2 or more.
- the upper limit of the average aspect ratio is not particularly limited, but is generally about 5.
- the aspect ratio is indicated by the ratio (length / diameter) between the length and diameter of the fine particles (B).
- the fine particles (B) having optical anisotropy preferably have an average length of the major axis of 100 nm or less, more preferably 70 nm or less, from the viewpoint of transparency of the resulting polyimide composition. Particularly preferred is 40 nm.
- the content of acicular particles having a major axis length of 200 nm or more is preferably 5% or less on a number basis, and preferably 3% or less. More preferably, it is more preferably 1% or less, and particularly preferably 0%.
- the fine particles (B) having optical anisotropy such as strontium carbonate fine particles may be surface-treated with a surface treatment agent.
- fine particles (B) having optical anisotropy that are surface-treated with a surface treatment agent described in JP-A-2014-80360, that is, the surface of the particles are polyoxyalkylene in the side chain.
- Fine particles (B) having optical anisotropy treated with a polycarboxylic acid having a group or an anhydride thereof and an amine having a polyoxyalkylene group and a hydrocarbon group can be preferably used.
- the fine particles (B) having an arbitrary optical anisotropy are not limited to the needle-shaped strontium carbonate particles having a specific shape, and are subjected to surface treatment by the method described in Japanese Patent Application Laid-Open No. 2014-80360.
- Fine particles (B) having an optical anisotropy that has been surface-treated with the surface treating agent described in Japanese Patent Publication No. Gazette.
- the surface treatment agent for the fine particles (B) having optical anisotropy preferably has a carboxylic acid as a functional group, and particularly preferably a polyamic acid.
- the fine particle powder having optical anisotropy that is surface-treated with the polyamic acid of the present invention will be described in detail.
- the fine particles (B) having optical anisotropy such as strontium carbonate fine particles used are surface-treated with a polyamic acid (A3) containing a repeating unit represented by the following chemical formula (8). It is preferably a fine particle powder having optical anisotropy.
- X 3 is a tetravalent group having an aromatic ring or alicyclic structure
- Y 3 is a divalent group having an aromatic ring or alicyclic structure.
- a carboxyl group in the formula ( -COOH) may form a salt with the base.
- the polyamic acid (A3) containing the repeating unit represented by the chemical formula (8) here is not particularly limited, but is a polyimide precursor (A1) which is a polyamic acid (R 1 in the chemical formula (1)).
- R 2 is preferably a polyimide precursor containing a repeating unit represented by the chemical formula (1) wherein hydrogen is hydrogen.
- Chemical formula (8) corresponds to chemical formula (1), with X 1 corresponding to X 3 and Y 1 corresponding to Y 3 .
- Examples of X 3 and Y 3 in the chemical formula (8) include the same as X 1 and Y 1 in the chemical formula (1), and preferable ones are also the same.
- Examples of the base that forms a salt with the carboxyl group of the chemical formula (8) include amines, alkali metal hydroxides, alkaline earth metal hydroxides, and the like. In view of volatilization by subsequent heat treatment or the like, amines are preferable, tertiary amines are more preferable, and tertiary amines having a ring structure are particularly preferable. Furthermore, since it is effective as a catalyst for imidation, pyridine and imidazole derivatives are preferable, and imidazole derivatives are more preferable.
- the fine particle powder having optical anisotropy surface-treated with the polyamic acid (A3) containing the repeating unit represented by the chemical formula (3) can be obtained, for example, as follows.
- a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component are approximately equimolar in a solvent.
- the molar ratio of the diamine component to the tetracarboxylic acid component is preferably 0.90 to 1.10, more preferably 0.95 to 1.05.
- a solution of polyamic acid (polyamic acid) (A3) is obtained.
- the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more with respect to the total amount of the solvent, the tetracarboxylic acid component and the diamine component. A proportion is preferred.
- the total amount of the tetracarboxylic acid component and the diamine component is 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. Is preferred.
- the solvent used in preparing the polyamic acid (A3) solution is not particularly limited as long as the polyamic acid (A3) dissolves, and any type of solvent can be used without any problem.
- the solvent used here include the same ones as the solvent (C) used in preparing the polyimide precursor (A1). For reasons described later, it is preferable to use water as the solvent. .
- the fine particle (B) having optical anisotropy or a dispersion (slurry) thereof and the resulting solution of polyamic acid (A3) are, for example, at 0 to 120 ° C. for 0.1 to 72 hours.
- a dispersion liquid (slurry) in which fine particles (B) having optical anisotropy surface-treated with polyamic acid are dispersed is obtained.
- the addition amount of the polyamic acid (A3) is 0 with respect to 100 parts by weight of the fine particles (B) having optical anisotropy.
- the amount of polyamic acid (A3) added is preferably 50 parts by weight or less, based on 100 parts by weight of fine particles (B) having optical anisotropy. Is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, and particularly preferably 15 parts by weight or less.
- the method of adding and dispersing the solution of polyamic acid (A3) to the fine particles (B) having optical anisotropy is not particularly limited, and any known dispersion method can be suitably applied.
- the solvent of the dispersion is not particularly limited as long as the polyamic acid (A3) is dissolved, and any type of solvent can be used without any problem. it can.
- the solvent for the dispersion include the same solvent as used for preparing the polyimide precursor (A1) (same as the solvent for the polyamic acid solution), but use water as the solvent. Is preferred.
- the solvent of the dispersion liquid of the fine particles (B) having optical anisotropy may be the same as or different from the solvent of the polyamic acid (A3) solution.
- the solvent used here that is, the solvent of the solution of the polyamic acid (A3) and the solvent of the dispersion liquid of the fine particles (B) having optical anisotropy are both water
- the surface treatment is performed with the polyamic acid (A3). Since the produced fine particles (B) having optical anisotropy are obtained as a slurry of water in production, operations such as solvent replacement can be simplified, which is preferable.
- an ordinary general dispersant may be used in combination. It is preferable to use only polyamic acid (A3) as a dispersant from the viewpoint of transparency of the polyimide composition to be obtained.
- a dispersion (slurry) in which fine particles (B) having optical anisotropy are dispersed in a solution of polyamic acid (A3), that is, a repeating unit represented by the chemical formula (8) is included.
- the fine particle dispersion of the present invention containing the polyamic acid (A3), fine particles (B) having optical anisotropy, and a solvent is used as it is for the production of a polyimide precursor composition or a polyimide composition without drying. You can also.
- the dispersion of fine particles (B) having optical anisotropy used has a polyamic acid (A3) containing a repeating unit represented by the chemical formula (8) and an optical anisotropy.
- a fine particle dispersion containing fine particles (B) having a solvent and a solvent is preferable.
- polyamic acid (A3) polyamic acid (A3) containing a repeating unit represented by the chemical formula (8) mentioned as the surface treating agent for the fine particles (B) having optical anisotropy is preferable.
- This fine particle dispersion of the present invention prepared a solution of polyamic acid (A3) in the same manner as the method for producing fine particle powder (B) having optical anisotropy surface-treated with the polyamic acid (A3).
- the fine particles (B) having optical anisotropy or a dispersion liquid (slurry) thereof and the obtained polyamic acid (A3) solution can be mixed.
- a dispersion liquid in which a fine particle powder (B) having optical anisotropy surface-treated with the isolated polyamic acid (A3) is dispersed in a solvent is also an optically different solution containing polyamic acid (A3) as a dispersant. It becomes the fine particle dispersion of the present invention of the fine particles (B) having anisotropy.
- the method for dispersing the fine particles (B) having optical anisotropy in a solvent is not particularly limited, and any known dispersion method can be suitably applied.
- the content of polyamic acid in the fine particle dispersion of the present invention is not particularly limited, but is 0.5 to 50 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the fine particles (B) having optical anisotropy.
- the amount is preferably 30 parts by weight, more preferably 3 to 25 parts by weight, and particularly preferably 5 to 15 parts by weight.
- the polyimide precursor composition of the present invention including the polyimide precursor (A1) and the fine particles (B) having optical anisotropy, and the polyimide (A2) and the optical anisotropy.
- the polyimide composition of the present invention containing the fine particles (B) having properties will be described in detail.
- the polyimide precursor composition of the present invention contains at least one polyimide precursor (A1) and at least one fine particle (B) having optical anisotropy.
- the polyimide composition of the present invention comprises at least one type of polyimide (A2) and at least one type of fine particles (B) having optical anisotropy.
- the content of the polyimide precursor composition of the present invention and the fine particles (B) having optical anisotropy of the polyimide composition of the present invention is not particularly limited, but the polymer of the polyimide precursor (A1) or polyimide (A2)
- the amount is preferably 1 part by weight or more, more preferably 5 parts by weight or more, still more preferably 10 parts by weight or more, and particularly preferably 20 parts by weight or more with respect to 100 parts by weight of the solid content. If it is this range, the phase difference (retardation) of the thickness direction and in-plane direction of the polyimide composition obtained will fall sufficiently.
- the content of the polyimide precursor composition of the present invention and the fine particles (B) having optical anisotropy of the polyimide composition of the present invention are not particularly limited, but the polyimide precursor (A1) or the polyimide (A2).
- the polymer solid content is preferably 60 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 20 parts by weight or less with respect to 100 parts by weight of the polymer solid content. If it is this range, the polyimide composition obtained will be excellent in characteristics, such as heat resistance and transparency.
- the content of the polyimide precursor composition of the present invention and the fine particles (B) having optical anisotropy of the polyimide composition of the present invention can be determined by a known composition analysis method. Moreover, the content can also be calculated
- the polyimide precursor composition of the present invention usually contains a polyimide precursor (A1), fine particles (B) having optical anisotropy, and a solvent (C).
- the polyimide composition of the present invention contains polyimide (A2), fine particles (B) having optical anisotropy, and a solvent (C).
- it is preferable that the polyimide (A2) is soluble in the solvent (C).
- the polyimide precursor composition containing the polyimide precursor (A1) or polyimide (A2), the fine particles (B) having optical anisotropy, and the solvent (C), or the polyimide composition is also referred to as the varnish of the present invention. .
- the solvent (C) used for the varnish of the present invention containing the polyimide precursor (polyimide precursor composition of the present invention)
- the structure is not particularly limited.
- the solvent (C) used for the varnish of the present invention containing polyimide (polyimide varnish)
- the structure is not particularly limited.
- amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, Cyclic ester solvents such as ⁇ -caprolactone and ⁇ -methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4 -Phenol solvents such as chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably used.
- the solvent of the varnish of this invention is the solvent (dispersion medium) of the dispersion liquid of the solvent used when preparing a polyimide precursor (A1) or a polyimide (A2), and the microparticles
- the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, more preferably based on the total amount of the solvent, the tetracarboxylic acid component and the diamine component. Is preferably 15% by mass or more.
- the total amount of the tetracarboxylic acid component and the diamine component is 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. Is preferred.
- This concentration is a concentration that is approximately approximate to the solid content concentration resulting from the polyimide precursor or polyimide, but if this concentration is too low, for example, a polyimide film is produced. Control of the film thickness of the polyimide film obtained may be difficult.
- the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution at a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g. Above, more preferably 0.3 dL / g or more, particularly preferably 0.4 dL / g or more.
- the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the mechanical strength and heat resistance of the resulting polyimide are excellent.
- the logarithmic viscosity of the polyimide is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5 g / dL at 30 ° C. is more preferably 0.2 dL / g or more. Is preferably 0.4 dL / g or more, particularly preferably 0.5 dL / g or more. When the logarithmic viscosity is 0.2 dL / g or more, the resulting polyimide has excellent mechanical strength and heat resistance.
- the viscosity (rotational viscosity) of the varnish of the present invention is not particularly limited, but the rotational viscosity measured using an E-type rotational viscometer at a temperature of 25 ° C. and a shear rate of 20 sec ⁇ 1 is preferably 0.01 to 1000 Pa ⁇ sec. 0.1 to 100 Pa ⁇ sec is more preferable. Moreover, thixotropy can also be provided as needed. When the viscosity is in the above range, it is easy to handle when coating or forming a film, and the repelling is suppressed and the leveling property is excellent, so that a good film can be obtained.
- the varnish containing the polyimide precursor of the present invention may contain a chemical imidizing agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline), an antioxidant, or a filler (inorganic particles such as silica) as necessary. Etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), release agents and the like.
- a chemical imidizing agent an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline
- an antioxidant such as pyridine or isoquinoline
- a filler inorganic particles such as silica
- the varnish containing the polyimide of the present invention may be prepared by using an antioxidant, a filler (inorganic particles such as silica), a dye, a pigment, a coupling agent such as a silane coupling agent, a primer, a flame retardant, and an antifoam as necessary.
- a filler inorganic particles such as silica
- a dye such as silica
- a pigment such as a silane coupling agent
- a primer such as a primer, a flame retardant, and an antifoam
- an antifoam as necessary.
- the polyimide precursor composition of the present invention which is a varnish of the present invention, includes fine particles (B) having optical anisotropy in the polyimide precursor solution or solution composition obtained by the method for producing the polyimide precursor (A1). ) Or a dispersion of fine particles (B) having optical anisotropy, and mixing them.
- fine particles (B) having optical anisotropy in the polyimide precursor solution or solution composition obtained by the method for producing the polyimide precursor (A1).
- a dispersion of fine particles (B) having optical anisotropy and mixing them.
- a tetracarboxylic acid component tetracarboxylic dianhydride, etc.
- diamine component are added to a solvent to further improve the dispersibility of the fine particles (B) having optical anisotropy.
- the polyimide precursor composition of the present invention by reacting the tetracarboxylic acid component and the diamine component in the presence of the fine particles (B) having the fine particles.
- the fine particles (B) having optical anisotropy to be used are preferably those that have been surface-treated with a surface treatment agent such as polyamic acid containing a repeating unit represented by the chemical formula (8).
- a solvent may be removed or added as needed, and desired components other than the fine particles (B) having optical anisotropy may be added.
- the varnish of the present invention containing polyimide (a composition containing polyimide (A2), fine particles (B) having optical anisotropy and a solvent) is obtained by changing the polyimide precursor in the varnish from the polyimide precursor composition of the present invention. It can be prepared by imidizing (that is, dehydrating and ring-closing reaction of a polyimide precursor).
- the imidization method is not particularly limited, and a known thermal imidation or chemical imidization method can be suitably applied.
- fine particles (B) having optical anisotropy or A dispersion liquid of fine particles (B) having optical anisotropy can be added and mixed to prepare a varnish containing the polyimide of the present invention.
- the fine particles (B) having optical anisotropy may have been surface-treated with a surface treatment agent such as polyamic acid containing a repeating unit represented by the chemical formula (8).
- a solvent may be removed or added as needed, and desired components other than the fine particles (B) having optical anisotropy may be added.
- the solution or solution composition of the polyimide precursor (A1) obtained by the above method is used.
- the solution or solution composition containing the polyimide (A2) can be obtained by stirring at 80 to 230 ° C., preferably 120 to 200 ° C. for 1 to 24 hours.
- bubbling may be performed, or imidization may be performed by adding an azeotropic solvent such as toluene.
- the obtained polyimide solution is dropped in a poor solvent such as water or methanol, re-precipitated, dried, and dissolved again in a solvent that can be dissolved, and this polyimide solution is used to obtain the polyimide solution.
- a varnish containing polyimide can also be prepared.
- a solvent (dispersion medium) of a dispersion liquid of fine particles (B) having optical anisotropy used for production of the varnish of the present invention which is the varnish of the present invention or the varnish of the present invention containing polyimide.
- the polyimide precursor or polyimide dissolves, it is not particularly limited, and any type of solvent can be used without any problem.
- the solvent for the dispersion liquid of the fine particles (B) having optical anisotropy include the same solvents as those used for preparing the polyimide precursor (A1).
- the solvent of the dispersion liquid of the fine particles (B) having optical anisotropy may be the same as or different from the solvent of the polyimide precursor solution or the polyimide solution.
- a solvent can also be used in combination of multiple types.
- the dispersion liquid of the fine particles (B) having optical anisotropy is one or more kinds in order to efficiently disperse the fine particles (B) having optical anisotropy in a solvent to obtain a stable fine particle dispersion. It may contain a dispersant.
- the dispersant is not particularly limited, but a dispersant having a carboxylic acid as a functional group is preferable, and a polyamic acid is particularly preferable.
- the polyamic acid is preferably a polyamic acid containing a repeating unit represented by the chemical formula (8) mentioned as the surface treating agent for the fine particles (B) having optical anisotropy. That is, a fine particle dispersion (fine particle dispersion of the present invention) containing a polyamic acid (A3) containing a repeating unit represented by the chemical formula (8), fine particles (B) having optical anisotropy, and a solvent. And can be suitably used as a dispersion of fine particles (B) having optical anisotropy.
- the content of polyamic acid is not particularly limited, but is 100 parts by weight of fine particles (B) having optical anisotropy.
- the amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 3 to 25 parts by weight.
- the content of the fine particles (B) having optical anisotropy in the polyimide composition is such that the polyimide converted from the polyamic acid as the dispersant is also polyimide ( A2) is included and calculated.
- the surface treatment agent for acicular strontium carbonate fine powder described in JP-A-2014-80360 that is, a polycarboxylic acid having a polyoxyalkylene group in the side chain or an anhydride thereof, and a polyoxy An amine having an alkylene group and a hydrocarbon group can also be suitably used as a dispersant for the dispersion of fine particles (B) having optical anisotropy.
- the addition amount of polycarboxylic acid or its anhydride and the addition amount of amine are preferably those described in JP-A-2014-80360.
- a commonly used dispersant may not be used from the viewpoint of transparency of the obtained polyimide composition.
- the amount of the commonly used dispersant other than polyamic acid is not particularly limited, but is usually 10 parts by weight or less with respect to 100 parts by weight of fine particles (B) having optical anisotropy. Preferably there is.
- the method for dispersing the fine particles (B) having optical anisotropy in a solvent is not particularly limited, and any known dispersion method can be suitably applied.
- the dispersion for example, it is preferable to use a ball mill, a jet mill, a bead mill, an impeller disperser, a thin film swirl mixer, or the like.
- the method of mixing the polyimide precursor solution or the polyimide solution and the dispersion of the fine particles (B) having optical anisotropy is not particularly limited, and any known mixing method can be suitably applied.
- the polyimide composition of the present invention includes polyimide (A2) and fine particles (B) having optical anisotropy, and includes a polyimide precursor (A1) and fine particles (B) having optical anisotropy. It can be obtained from the polyimide precursor composition of the present invention. More specifically, the polyimide precursor composition of the present invention is obtained by heating the polyimide precursor composition of the present invention to imidize the polyimide precursor (that is, dehydrating and ring-closing the polyimide precursor). Can do.
- the imidization method is not particularly limited, and a known thermal imidation or chemical imidization method can be suitably applied.
- the polyimide precursor composition of the present invention (polyimide precursor varnish) is cast on a substrate, and the polyimide precursor composition on this substrate is, for example, 100 to 500 ° C., preferably 200 to 500 ° C. More preferably, a polyimide composition such as a polyimide film can be suitably produced by heat treatment at a temperature of about 250 to 450 ° C. to remove the solvent and imidize the polyimide precursor.
- a heating profile is not specifically limited, It can select suitably.
- the polyimide precursor composition of the present invention (polyimide precursor varnish) is cast on a substrate, and preferably dried in a temperature range of 180 ° C. or less to form a film of the polyimide precursor composition on the substrate.
- the polyimide precursor composition film thus obtained is peeled off from the substrate, and the end of the film is fixed, or the end of the film is not fixed, for example, at 100 to 500 ° C.
- a polyimide composition such as a polyimide film can be suitably produced by heat-treating at a temperature of preferably about 200 to 500 ° C., more preferably about 250 to 450 ° C. to imidize the polyimide precursor. .
- the polyimide composition of the present invention such as a polyimide film (polyimide composition not containing a solvent) comprises the varnish of the present invention containing polyimide (polyimide (A2), fine particles (B) having optical anisotropy, and a solvent. It can also be obtained by removing the solvent by heating or the like.
- the varnish of the present invention containing polyimide is cast on a substrate, and the solvent is removed by heat treatment at a temperature of, for example, 80 to 500 ° C., preferably 100 to 500 ° C., more preferably 150 to 450 ° C.
- a temperature of, for example, 80 to 500 ° C., preferably 100 to 500 ° C., more preferably 150 to 450 ° C.
- polyimide compositions such as a polyimide film, can be manufactured suitably.
- the heating profile is not particularly limited and can be selected as appropriate.
- a needle-like material having optical anisotropy such as strontium carbonate is obtained by hot-stretching a polyimide composition film, or by melting and injecting the polyimide composition and performing injection molding or extrusion molding.
- the varnish (polyimide precursor solution composition, polyimide solution composition) may be optically different from the varnish (polyimide precursor solution composition, polyimide solution composition) as in the above production method without aligning rod-shaped fine particles in one direction, that is, without special fine particle alignment treatment. By adding the fine particles having directionality, not only the in-plane direction retardation but also the thickness direction retardation can be easily reduced.
- the form of the polyimide composition (fine particle-containing polyimide having optical anisotropy) of the present invention is preferably a film, a laminate of a polyimide film and another substrate, a coating film, powder, beads, a molded body, a foamed body, etc. Can be listed.
- the polyimide composition obtained from the polyimide precursor composition of the present invention and the polyimide composition of the present invention are not particularly limited, but are 100 ° C. when formed into a film having a thickness of 5 ⁇ m to 250 ⁇ m, preferably a film having a thickness of 10 ⁇ m.
- the linear thermal expansion coefficient from 1 to 250 ° C. can be preferably 60 ppm / K or less, more preferably 50 ppm / K or less. When the linear thermal expansion coefficient is large, the difference in the linear thermal expansion coefficient with a conductor such as metal is large, which may cause problems such as an increase in warpage when a circuit board is formed.
- the polyimide composition obtained from the polyimide precursor composition of the present invention and the polyimide composition of the present invention are not particularly limited, but the total light transmittance in a film having a thickness of 5 ⁇ m to 250 ⁇ m, preferably a film having a thickness of 10 ⁇ m.
- the (average light transmittance at a wavelength of 380 nm to 780 nm) is preferably 68% or more, more preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more.
- the polyimide composition obtained from the polyimide precursor composition of the present invention and the polyimide composition of the present invention are not particularly limited, but the 5% weight reduction temperature, which is an index of heat resistance of the polyimide film, is preferably 400 ° C. or higher. More preferably, it is 430 degreeC or more, More preferably, it is 450 degreeC or more.
- the 5% weight reduction temperature which is an index of heat resistance of the polyimide film
- the polyimide composition obtained from the polyimide precursor composition of the present invention and the polyimide composition of the present invention are not particularly limited, but the thickness of the polyimide film is a film having a thickness of 5 ⁇ m to 250 ⁇ m, preferably a film having a thickness of 10 ⁇ m.
- the directional phase difference is preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 700 nm or less, and particularly preferably 680 nm or less.
- the thickness direction retardation of the polyimide film is preferably 75 nm or less.
- the in-plane retardation of the polyimide film is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 10 nm or less, and even more preferably 5 nm or less.
- the in-plane retardation of the polyimide film may be preferably 4 nm or less, more preferably 3 nm or less.
- the polyimide composition obtained from the polyimide precursor composition of the present invention or the film comprising the polyimide composition of the present invention depends on the use, but the thickness of the film is preferably 0.1 ⁇ m to 250 ⁇ m, more The thickness is preferably 1 ⁇ m to 150 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and particularly preferably 1 ⁇ m to 30 ⁇ m.
- the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance may be lowered.
- the polyimide composition obtained from the polyimide precursor composition of the present invention and the polyimide composition of the present invention are used, for example, in applications of a transparent substrate for display, a transparent substrate for touch panel, or a substrate for solar cell, and other optical components. It can be suitably used in applications of substrates for devices and semiconductor devices.
- the varnish (polyimide precursor composition) of the present invention is cast on a substrate such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat-resistant plastic film (polyimide film, etc.), etc.
- a substrate such as ceramic (glass, silicon, alumina, etc.), metal (copper, aluminum, stainless steel, etc.), heat-resistant plastic film (polyimide film, etc.), etc.
- a vacuum in an inert gas such as nitrogen, or in the air, drying is performed in a temperature range of 20 to 180 ° C., preferably 20 to 150 ° C. using hot air or infrared rays.
- a polyimide film / substrate laminate or a polyimide film can be produced by heating imidization in air using hot air or infrared rays, for example, at a temperature of about 200 to 500 ° C., more preferably about 250 to 450 ° C. it can.
- the thickness of the polyimide film here is preferably 1 to 250 ⁇ m, more preferably 1 to 150 ⁇ m, because of the transportability in the subsequent steps.
- the imidization reaction of the polyimide precursor instead of the heat imidation by the heat treatment as described above, contains a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It is also possible to carry out by chemical treatment such as immersion in a solution. In addition, these dehydration cyclization reagents are previously charged and stirred in a varnish (polyimide precursor composition), and then cast onto a substrate and dried to obtain a partially imidized polyimide precursor. A polyimide film / base material laminate or a polyimide film can be obtained by further heat treatment as described above.
- a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It is also possible to carry out by chemical treatment such as immersion in a solution.
- these dehydration cyclization reagents are previously charged and
- a flexible conductive substrate can be obtained by forming a conductive layer on one side or both sides of the polyimide film / base laminate or the polyimide film obtained in this way.
- a flexible conductive substrate can be obtained, for example, by the following method. That is, as a first method, the polyimide film / substrate laminate is not peeled off from the substrate, and the surface of the polyimide film is sputtered, vapor-deposited, printed, etc. by a conductive substance (metal or metal oxide). A conductive layer of conductive layer / polyimide film / base material is produced. Then, if necessary, a transparent and flexible conductive substrate comprising the conductive layer / polyimide film laminate can be obtained by peeling the conductive layer / polyimide film laminate from the substrate.
- a transparent and flexible conductive substrate comprising the conductive layer / polyimide film laminate can be obtained by peeling the conductive layer / polyimide film laminate from the substrate.
- the polyimide film is peeled off from the substrate of the polyimide film / substrate laminate to obtain a polyimide film, and a conductive substance (metal or metal oxide, conductive organic substance, A conductive layer of conductive carbon, etc.) is formed in the same manner as in the first method, and a transparent and flexible conductive layer comprising a conductive layer / polyimide film laminate or a conductive layer / polyimide film / conductive layer laminate.
- a conductive substrate can be obtained.
- a gas barrier layer such as water vapor or oxygen, light adjustment by sputtering, vapor deposition or gel-sol method, etc.
- An inorganic layer such as a layer may be formed.
- the gas barrier layer is not limited as long as it has a lower permeability of oxygen and / or water vapor or the like than the polyimide film, for example, an inorganic layer, an organic layer, or an inorganic / organic hybrid layer, preferably Inorganic oxide films such as silicon oxide, aluminum oxide, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon nitride, and silicon nitride oxide.
- the gas barrier layer may be composed of only one kind of composition or may be a film in which two or more kinds of compositions are mixed.
- the conductive layer is preferably formed with a circuit by a method such as a photolithography method, various printing methods, or an ink jet method.
- substrate of this invention obtained is a gas barrier layer as needed on the surface of the polyimide composition comprised by the polyimide composition obtained from the polyimide precursor composition of this invention, or the polyimide composition of this invention. And a circuit of a conductive layer through an inorganic layer.
- substrate is flexible and can be used suitably as a board
- vapor deposition, various printing methods, ink jet methods, and the like are further used for transistors (here, materials used for semiconductors include oxides such as amorphous silicon, low-temperature polysilicon, ZnO, SnO, and IGZO).
- a flexible thin film transistor is manufactured, and is suitably used as a liquid crystal element, an EL element, or a photoelectric element for a display device.
- the polyimide film laminated body which has a polyimide film and at least 1 layer of glass layer is obtained in a manufacturing process.
- a gas barrier layer is formed, a polyimide film laminate having a polyimide film and at least one gas barrier layer (for example, an inorganic layer, an organic layer, or an inorganic / organic hybrid layer having a lower oxygen permeability than the polyimide film) Is obtained in the manufacturing process.
- gas barrier layer for example, an inorganic layer, an organic layer, or an inorganic / organic hybrid layer having a lower oxygen permeability than the polyimide film
- a laminate in which a thin film transistor (inorganic transistor or organic transistor) is formed that is, a polyimide film, a polyimide film laminate having at least one thin film transistor, and a laminate in which a conductive layer is formed, that is, a polyimide film
- a polyimide film laminate having at least one conductive layer is also an embodiment of the polyimide film laminate of the present invention.
- the polyimide composition obtained from the polyimide precursor composition of the present invention and the polyimide composition of the present invention are also, for example, an organic EL display, a liquid crystal display, an electrophoretic display, a plasma display, a plasma addressed liquid crystal display, and an inorganic EL display. It can also be suitably used for display devices such as field emission displays or surface electric field displays, sensor devices such as touch panels, photoelectric conversion devices such as solar cells, optical devices such as optical waveguides, and other semiconductor devices.
- Total light transmittance Using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation), the light transmittance at a total light transmittance (average transmittance at 380 nm to 780 nm) of a 10 ⁇ m-thick polyimide film was measured.
- Linear thermal expansion coefficient (CTE) A polyimide film is cut into a strip of 4 mm in width to make a test piece, and TMA / SS6100 (manufactured by SII Nano Technology Co., Ltd.) is used. The temperature rose. The linear thermal expansion coefficient from 100 ° C. to 250 ° C. was determined from the obtained TMA curve.
- strontium carbonate dispersion (1) As a strontium carbonate dispersion (1), a dispersion (solvent: NMP) using strontium carbonate described in JP-A-2014-80360 was prepared. In the dispersion (1), the content of strontium carbonate was 10% by mass, the average major axis was 36.7 nm, the average aspect ratio was 2.3, and the content of particles having a major axis of 200 nm or more was 0%.
- Strontium carbonate dispersion (2) Strontium carbonate was dispersed in NMP by a known dispersion method without using a dispersant.
- the content of strontium carbonate was 10% by mass
- the average major axis was 36.7 nm
- the average aspect ratio was 2.3
- the content of particles having a major axis of 200 nm or more was 0%.
- Strontium carbonate dispersion (3) As a strontium carbonate dispersion (3), a dispersion (solvent: water) using strontium carbonate described in JP-A No. 2014-80360 was prepared. In the dispersion (3) (water slurry), the content of strontium carbonate: 5.5% by mass, the average major axis was 31.7 nm, the average aspect ratio was 2.4, and the content of particles having a major axis of 200 nm or more was 0%.
- the average major axis, average aspect ratio, and the content ratio (number basis) of particles having a major axis of 200 nm or more were determined from the SEM image by image analysis.
- Example S-1 In a reaction vessel purged with nitrogen gas, 9.09 g (0.04 mol) of DABAN, 5.41 g (0.05 mol) of PPD and 3.68 g (0.01 mol) of BAPB were placed, and N-methyl-2- Pyrrolidone was added in an amount of 509.58 g so that the total monomer weight (total of diamine component and carboxylic acid component) was 10% by mass and stirred at room temperature for 1 hour. To this solution, 38.44 g (0.10 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor (polyamic acid) solution.
- Example S-2 Into a reaction vessel substituted with nitrogen gas, 11.42 g (0.100 mol) of 1,4-tra-DACH was charged, and water was added, so that the total monomer mass (total of diamine component and carboxylic acid component) was 15% by mass. An amount of 231.37 g was added and stirred at room temperature for 1 hour. To this solution, 21.15 g (0.220 mol) of 1,2-dimethylimidazole was added and stirred at room temperature for 1 hour. To this solution, 28.67 g (0.0975 mol) of s-BPDA and 0.74 g (0.0025 mol) of a-BPDA were gradually added.
- Table 1-1 shows the structural formulas of the tetracarboxylic acid components used in Examples and Comparative Examples
- Table 1-2 shows the structural formulas of diamine components used in Examples and Comparative Examples.
- Example 1 In a reaction vessel purged with nitrogen gas, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were placed, and N-methyl-2- Pyrrolidone was added in an amount of 24.13 g so that the total monomer weight (total of diamine component and carboxylic acid component) was 19% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. To the obtained polyimide precursor solution, 5.66 g of strontium carbonate dispersion (1) was added and stirred at room temperature for 1 hour.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 2 In a reaction vessel substituted with nitrogen gas, 2.83 g of the strontium carbonate dispersion (1) and 25.08 g of N-methyl-2-pyrrolidone were added and stirred at room temperature for 1 hour. To this solution, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were added and stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 3 11.32 g of the strontium carbonate dispersion (1) and 17.44 g of N-methyl-2-pyrrolidone were added to the reaction vessel substituted with nitrogen gas, and the mixture was stirred at room temperature for 1 hour. To this solution, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were added and stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 4 28.3 g of strontium carbonate dispersion (1) and 2.16 g of N-methyl-2-pyrrolidone were added to the reaction vessel substituted with nitrogen gas, and the mixture was stirred at room temperature for 1 hour. To this solution, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were added and stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 5 In a reaction vessel substituted with nitrogen gas, 2.83 g of the strontium carbonate dispersion (2) and 25.08 g of N-methyl-2-pyrrolidone were added and stirred at room temperature for 1 hour. To this solution, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were added and stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 6 In a reaction vessel purged with nitrogen gas, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were placed, and N-methyl-2- Pyrrolidone was added in an amount of 24.13 g so that the total monomer weight (total of diamine component and carboxylic acid component) was 19% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. To the obtained polyimide precursor solution, 7.08 g of strontium carbonate dispersion (4) was added and stirred at room temperature for 1 hour.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 7 In a reaction vessel purged with nitrogen gas, 7.08 g of the strontium carbonate dispersion (4) and 24.13 g of N-methyl-2-pyrrolidone were added and stirred at room temperature for 1 hour. To this solution, 0.91 g (0.004 mol) of DABAN, 0.54 g (0.005 mol) of PPD and 0.37 g (0.001 mol) of BAPB were added and stirred at room temperature for 1 hour. To this solution, 3.84 g (0.010 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- a polyimide precursor solution is applied to a glass substrate and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 410 ° C. as it is to imidize the material in a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 8 In a reaction vessel substituted with nitrogen gas, 5.1 g of strontium carbonate dispersion (5), 18.54 g of water and 2.11 g (0.0220 mol) of 1,2-dimethylimidazole were added, and the mixture was stirred at room temperature for 1 hour. To this solution, 1.14 g (0.0100 mol) of 1,4-tra-DACH was added and stirred at room temperature for 1 hour. To this solution, 2.87 g (0.00975 mol) of s-BPDA and 0.07 g (0.00025 mol) of a-BPDA were gradually added. The mixture was stirred at room temperature for 12 hours to obtain a viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is, and thermally imidized to form a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- a polyimide precursor solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is, and thermally imidized to form a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 9 In a reaction vessel substituted with nitrogen gas, 20.02 g (0.100 mol) of 4,4′-ODA was put, N, N-dimethylacetamide was charged, and the total monomer mass (total of diamine component and carboxylic acid component) was 207.21 g of an amount of 17% by mass was added and stirred at room temperature for 1 hour. To this solution, 22.41 g (0.100 mmol) of PMDA-HS was gradually added. Stir at room temperature for 12 hours. 30 g of toluene was added to this solution and heated at 180 ° C. for 8 hours to perform imidization. This solution was re-precipitated in a large amount of water, filtered and dried.
- a polyimide solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is to thermally imidize a colorless transparent polyimide film / glass laminate. Obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 10 In a reaction vessel substituted with nitrogen gas, 20.02 g (0.100 mol) of 4,4′-ODA was put, N, N-dimethylacetamide was charged, and the total monomer mass (total of diamine component and carboxylic acid component) was 207.21 g of an amount of 17% by mass was added and stirred at room temperature for 1 hour. To this solution, 22.41 g (0.100 mmol) of PMDA-HS was gradually added. Stir at room temperature for 12 hours. 30 g of toluene was added to this solution and heated at 180 ° C. for 8 hours to perform imidization. This solution was re-precipitated in a large amount of water, filtered and dried.
- a polyimide solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is to thermally imidize a colorless transparent polyimide film / glass laminate. Obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- a polyimide solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is to thermally imidize a colorless transparent polyimide film / glass laminate. Obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 11 7.20 g of the strontium carbonate dispersion (1) and 22.30 g of N-methyl-2-pyrrolidone were added to the reaction vessel substituted with nitrogen gas, and the mixture was stirred at room temperature for 1 hour. 3.20 g (0.010 mol) of TFMB was placed in a reaction vessel substituted with nitrogen gas, and stirred at room temperature for 1 hour. To this solution, 0.88 g (0.0030 mol) of s-BPDA and 6FDA 3.11 (0.0070 mol) were gradually added. Stir at room temperature for 12 hours. To this solution, 0.96 g (0.010 mol) of 1,2-dimethylimidazole was added and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution.
- a polyimide precursor solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is, and thermally imidized to form a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- a polyimide precursor solution is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 350 ° C. as it is, and thermally imidized to form a colorless transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film having a film thickness of about 10 ⁇ m.
- Example 12 In a reaction vessel substituted with nitrogen gas, 2.13 g of strontium carbonate dispersion (1) and 31.24 g of N-methyl-2-pyrrolidone were added and stirred at room temperature for 1 hour. To this solution, 2.12 g (0.01 mol) of m-TD was added and stirred at room temperature for 1 hour. To this solution, 0.38 g (0.001 mol) of CpODA and 1.76 g (0.009 mol) of CBDA were gradually added. Stir at room temperature for 12 hours. To this solution, 0.10 g (0.001 mol) of 1,2-dimethylimidazole was added and stirred at room temperature for 1 hour to obtain a viscous polyimide precursor solution.
- the polyimide precursor solution was applied to a glass substrate so that the final film thickness was about 80 ⁇ m, and pre-dried on a hot plate at 80 ° C.
- the obtained film was peeled off from the glass substrate, and only the upper and lower sides were fixed to the pin tenter, and heated from room temperature to 260 ° C. in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize, and colorless.
- a transparent polyimide film was obtained.
- the film thickness of the obtained polyimide film was about 80 ⁇ m.
- the polyimide precursor solution was applied to a glass substrate so that the final film thickness was about 80 ⁇ m, and pre-dried on a hot plate at 80 ° C.
- the obtained film was peeled off from the glass substrate, and only the upper and lower sides were fixed to the pin tenter, and heated from room temperature to 260 ° C. in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to thermally imidize, and colorless.
- a transparent polyimide film was obtained.
- the film thickness of the obtained polyimide film was about 80 ⁇ m.
- a polyimide composition that can be easily produced, has a small retardation in the thickness direction and in-plane direction, and is excellent in transparency, mechanical properties, heat resistance, and the like, and a precursor composition thereof. Can do.
- This polyimide composition is excellent in transparency, mechanical properties, heat resistance, and the like, and has a small retardation in the thickness direction and in-plane direction, so that it forms substrates for displays, touch panels, solar cells and the like. Therefore, it can be used suitably.
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Abstract
Description
1. ポリイミド前駆体(A1)と、光学異方性を有する微粒子(B)とを含むことを特徴とするポリイミド前駆体組成物。
2. 前記ポリイミド前駆体(A1)が、下記化学式(1)で表される繰り返し単位の少なくとも1種を含むことを特徴とする前記項1に記載のポリイミド前駆体組成物。
(式中、X1は芳香族環または脂環構造を有する4価の基であり、Y1は芳香族環または脂環構造を有する2価の基であり、R1、R2はそれぞれ独立に水素、炭素数1~6のアルキル基、または炭素数3~9のアルキルシリル基である。)
3. X1が脂環構造を有する4価の基であり、Y1が脂環構造を有する2価の基である化学式(1)で表される繰り返し単位の含有量が、全繰り返し単位に対して、50モル%以下であることを特徴とする前記項2に記載のポリイミド前駆体組成物。
4. 化学式(1)中のX1が芳香族環を有する4価の基であり、Y1が芳香族環を有する2価の基であることを特徴とする前記項2に記載のポリイミド前駆体組成物。
5. 化学式(1)中のX1が脂環構造を有する4価の基であり、Y1が芳香族環を有する2価の基であることを特徴とする前記項2に記載のポリイミド前駆体組成物。
6. 化学式(1)中のX1が芳香族環を有する4価の基であり、Y1が脂環構造を有する2価の基であることを特徴とする前記項2に記載のポリイミド前駆体組成物。
7. 前記光学異方性を有する微粒子(B)が、炭酸ストロンチウムであることを特徴とする前記項1~6のいずれかに記載のポリイミド前駆体組成物。
9. 前記ポリイミド(A2)が、下記化学式(7)で表される繰り返し単位の少なくとも1種を含むことを特徴とする前記項8に記載のポリイミド組成物。
(式中、X2は芳香族環または脂環構造を有する4価の基であり、Y2は芳香族環または脂環構造を有する2価の基である。)
10. 前記項1~7のいずれかに記載のポリイミド前駆体組成物から得られることを特徴とするポリイミド組成物。
11. 前記項1~7のいずれかに記載のポリイミド前駆体組成物から得られるポリイミド組成物、又は前記項8~9のいずれかに記載のポリイミド組成物からなることを特徴とするポリイミドフィルム。
13. 前記項11記載のポリイミドフィルムと、少なくとも1層のガスバリヤ層を有することを特徴とするポリイミドフィルム積層体。
14. 前記項11記載のポリイミドフィルムと、少なくとも1層の薄膜トランジスタを有することを特徴とするポリイミドフィルム積層体。
15. 前記項11記載のポリイミドフィルムと、少なくとも1層の導電層を有すること特徴とする前記項12または13に記載のポリイミドフィルム積層体。
17. 前記項16に記載のワニスを用いて得られたことを特徴とするポリイミド組成物。
18. 前記項16に記載のワニスを用いて得られたことを特徴とするポリイミドフィルム。
20. 前記項1~7のいずれかに記載のポリイミド前駆体組成物から得られるポリイミド組成物、又は前記項8~9のいずれかに記載のポリイミド組成物を含むことを特徴とする表示デバイス、センサーデバイス、光電変換デバイス、または光学デバイス。
(式中、X3は芳香族環または脂環構造を有する4価の基であり、Y3は芳香族環または脂環構造を有する2価の基である。ただし、式中のカルボキシル基(-COOH)は、塩基と塩を形成していてもよい。)
22. 下記化学式(8)で表される繰り返し単位を含むポリアミック酸(A3)と、光学異方性を有する微粒子(B)と、溶媒(C)とを含む微粒子分散液。
(式中、X1は芳香族環または脂環構造を有する4価の基であり、Y1は芳香族環または脂環構造を有する2価の基であり、R1、R2はそれぞれ独立に水素、炭素数1~6のアルキル基、または炭素数3~9のアルキルシリル基である。)
ポリイミド前駆体(A1)は、例えば、前記化学式(1)で表される繰り返し単位の少なくとも1種を含むものである。
(式中、R31~R36は、それぞれ独立に直接結合、または、2価の有機基である。R41~R47は、それぞれ独立に 式:-CH2-、-CH=CH-、-CH2CH2-、-O-、-S-で表される基よりなる群から選択される1種を示す。)
(式中、W1は直接結合、または、2価の有機基であり、n11~n13は、それぞれ独立に0~4の整数を表し、R51、R52、R53は、それぞれ独立に炭素数1~6のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基である。)
(式中、V1、V2は、それぞれ独立に直接結合、または、2価の有機基であり、n21~n26は、それぞれ独立に0~4の整数を表し、R81~R86は、それぞれ独立に炭素数1~6のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基であり、R91、R92、R93は、それぞれ独立に 式:-CH2-、-CH=CH-、-CH2CH2-、-O-、-S-で表される基よりなる群から選択される1種である。)
1)ポリアミド酸(R1及びR2が水素)、
2)ポリアミド酸エステル(R1及びR2の少なくとも一部がアルキル基)、
3)4)ポリアミド酸シリルエステル(R1及びR2の少なくとも一部がアルキルシリル基)、
に分類することができる。そして、本発明のポリイミド前駆体(A1)は、この分類ごとに、以下の製造方法により容易に製造することができる。ただし、本発明のポリイミド前駆体(A1)の製造方法は、以下の製造方法に限定されるものではない。
本発明のポリイミド前駆体(A1)は、溶媒中でテトラカルボン酸成分としてのテトラカルボン酸二無水物とジアミン成分とを略等モル、好ましくはテトラカルボン酸成分に対するジアミン成分のモル比[ジアミン成分のモル数/テトラカルボン酸成分のモル数]が好ましくは0.90~1.10、より好ましくは0.95~1.05の割合で、例えば120℃以下の比較的低温度でイミド化を抑制しながら反応することによって、ポリイミド前駆体溶液組成物として好適に得ることができる。
テトラカルボン酸二無水物を任意のアルコールと反応させ、ジエステルジカルボン酸を得た後、塩素化試薬(チオニルクロライド、オキサリルクロライドなど)と反応させ、ジエステルジカルボン酸クロライドを得る。このジエステルジカルボン酸クロライドとジアミンを-20~120℃、好ましくは-5~80℃の範囲で1~72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。また、ジエステルジカルボン酸とジアミンを、リン系縮合剤や、カルボジイミド縮合剤などを用いて脱水縮合することでも、簡便にポリイミド前駆体が得られる。
あらかじめ、ジアミンとシリル化剤を反応させ、シリル化されたジアミンを得る。必要に応じて、蒸留等により、シリル化されたジアミンの精製を行う。そして、脱水された溶剤中にシリル化されたジアミンを溶解させておき、攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、0~120℃、好ましくは5~80℃の範囲で1~72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
1)の方法で得られたポリアミド酸溶液とシリル化剤を混合し、0~120℃、好ましくは5~80℃の範囲で1~72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
ポリイミド(A2)は、特に限定されるわけではないが、ポリイミド前駆体(A1)から得られ、例えば、前記化学式(7)で表される繰り返し単位の少なくとも1種を含むものである。
光学異方性を有する微粒子(B)は、光学異方性を有するものであれば特に限定されず使用することができる。
本発明のある実施態様においては、用いる炭酸ストロンチウム微粒子等の光学異方性を有する微粒子(B)は、下記化学式(8)で表される繰り返し単位を含むポリアミック酸(A3)で表面処理されている光学異方性を有する微粒子粉末であることが好ましい。
本発明のある実施態様においては、用いる光学異方性を有する微粒子(B)の分散液は、前記化学式(8)で表される繰り返し単位を含むポリアミック酸(A3)と、光学異方性を有する微粒子(B)と、溶媒とを含む微粒子分散液であることが好ましい。
本発明のポリイミド前駆体組成物は、少なくとも1種のポリイミド前駆体(A1)と、少なくとも1種の光学異方性を有する微粒子(B)とを含むものである。本発明のポリイミド組成物は、少なくとも1種のポリイミド(A2)と、少なくとも1種の光学異方性を有する微粒子(B)とを含むものである。ポリイミドに光学異方性を有する微粒子(B)を加えることにより、ポリイミド本来の特性を保ちつつ、厚み方向及び面内方向の位相差を低下させることができる。
[フィルムの面内方向位相差(Re)、厚み方向位相差(Rth)]
膜厚10μmのポリイミドフィルムを試験片とし、王子計測器社製 位相差測定装置(KOBRA-WR)を用い、Re、Rthを測定した。Rth入射角を40°としてフィルムの位相差測定を行った。得られた位相差より、膜厚10μmのフィルムの厚み方向の位相差を求めた。
紫外可視分光光度計/V-650DS(日本分光製)を用いて、膜厚10μmのポリイミドフィルムの全光透過率(380nm~780nmにおける平均透過率)における光透過率を測定した。
ポリイミドフィルムをIEC-540(S)規格のダンベル形状に打ち抜いて試験片(幅:4mm)とし、ORIENTEC社製TENSILONを用いて、チャック間長30mm、引張速度2mm/分で、初期の引張弾性率、破断点伸度、破断点強度を測定した。
ポリイミドフィルムを幅4mmの短冊状に切り取って試験片とし、TMA/SS6100 (エスアイアイ・ナノテクノロジー株式会社製)を用い、チャック間長15mm、荷重2g、昇温速度20℃/分で500℃まで昇温した。得られたTMA曲線から、100℃から250℃までの線熱膨張係数を求めた。
ポリイミドフィルムを試験片とし、TAインスツルメント社製 熱重量測定装置(Q5000IR)を用い、窒素気流中、昇温速度10℃/分で25℃から600℃まで昇温した。得られた重量曲線から、5%重量減少温度を求めた。
BAPB: 4,4’-ビス(4-アミノフェノキシ)ビフェニル〔純度:99.93%(HPLC分析)〕
PPD: p-フェニレンジアミン〔純度:99.9%(GC分析)〕
DABAN: 4,4’-ジアミノベンズアニリド〔純度:99.90%(GC分析)〕
1,4-tra-DACH:トランス-1,4-ジアミノシクロヘキサン〔純度:99.1%(GC分析)〕
4,4’-ODA: 4,4’-オキシジアニリン〔純度:99.9%(GC分析)〕
TFMB: 2,2’-ビス(トリフルオロメチル)ベンジジン〔純度:99.83%(GC分析)〕
m-TD: 2,2’-ジメチル-4,4’-ジアミノビフェニル〔純度:99.85%(GC分析)〕
[テトラカルボン酸成分]
CpODA: ノルボルナン-2-スピロ-α-シクロペンタノン-α’-スピロ-2’’-ノルボルナン-5,5’’,6,6’’-テトラカルボン酸二無水物
s-BPDA: 3,3’,4,4’-ビフェニルテトラカルボン酸二無水物〔純度99.9%(H-NMR分析)〕
a-BPDA: 2,3,3’,4’-ビフェニルテトラカルボン酸二無水物〔純度99.6%(H-NMR分析)〕
H-PMDA: 1R,2S,4S,5R-シクロヘキサンテトラカルボン酸二無水物〔純度:99.9%(GC分析)〕
6FDA: 4,4’-(2,2-ヘキサフルオロイソプロピレン)ジフタル酸二無水物〔純度:99.77%(H-NMR分析)〕
CBDA: 1,2,3,4-シクロブタンテトラカルボン酸二無水物〔純度:99.9%(GC分析)〕
[溶媒]
NMP: N-メチル-2-ピロリドン
水: 純水
炭酸ストロンチウム分散液(1): 炭酸ストロンチウム分散液(1)として、特開2014-80360号公報に記載の炭酸ストロンチウムを用いた分散液(溶媒:NMP)を用意した。分散液(1)は、炭酸ストロンチウムの含有量:10質量%、平均長径36.7nm、平均アスペクト比2.3、長径200nm以上の粒子の含有率 0%であった。
窒素ガスで置換した反応容器中にDABAN 9.09g(0.04モル)とPPD 5.41g(0.05モル)とBAPB 3.68g(0.01モル)を入れ、N-メチル-2-ピロリドンを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 10質量%となる量の509.58gを加え、室温で1時間攪拌した。この溶液にCpODA 38.44g(0.10モル)を徐々に加えた。室温で12時間撹拌し、均一で粘稠なポリイミド前駆体(ポリアミック酸)溶液を得た。得られたポリイミド前駆体溶液 10gと炭酸ストロンチウム分散液(2) 40gをフリッチュ社の遊星型ボールミル(プレミアムラインP-7)を用いて、0.3mmのZrO2 50gを用いて、90分間処理し、炭酸ストロンチウム分散液(4)を得た。
窒素ガスで置換した反応容器中に1,4-tra-DACH 11.42g(0.100モル)を入れ、水を仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 15質量%となる量の231.37gを加え、室温で1時間攪拌した。この溶液に1,2-ジメチルイミダゾール 21.15g(0.220モル)を加え、室温で1時間攪拌した。この溶液にs-BPDA 28.67g(0.0975モル)とa-BPDA 0.74g(0.0025モル)を徐々に加えた。室温で12時間撹拌し、均一で粘稠なポリイミド前駆体(ポリアミック酸)溶液を得た。得られたポリイミド前駆体溶液 15gを分散剤として使用し、炭酸ストロンチウム分散液(3) 300gを分散させ、炭酸ストロンチウム分散液(5)(粒子径D50 79nm、D90 130nm、レーザ回折粒度分布測定装置測定)を得た。
窒素ガスで置換した反応容器中にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、N-メチル-2-ピロリドンを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 19質量%となる量の24.13gを加え、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、均一で粘稠なポリイミド前駆体溶液を得た。得られたポリイミド前駆体溶液に炭酸ストロンチウム分散液(1) 5.66gを加え、室温で1時間攪拌した。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(1) 2.83gとN-メチル-2-ピロリドン 25.08gを加え、室温で1時間攪拌した。この溶液にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(1) 11.32gとN-メチル-2-ピロリドン 17.44gを加え、室温で1時間攪拌した。この溶液にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、粘稠なポリイミド前駆体溶液を得た。
〔実施例4〕
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(1) 28.3gとN-メチル-2-ピロリドン 2.16gを加え、室温で1時間攪拌した。この溶液にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(2) 2.83gとN-メチル-2-ピロリドン 25.08gを加え、室温で1時間攪拌した。この溶液にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、N-メチル-2-ピロリドンを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 19質量%となる量の24.13gを加え、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、均一で粘稠なポリイミド前駆体溶液を得た。得られたポリイミド前駆体溶液に炭酸ストロンチウム分散液(4)を 7.08gを加え、室温で1時間攪拌した。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(4) 7.08gとN-メチル-2-ピロリドン 24.13gを加え、室温で1時間攪拌した。この溶液にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中にDABAN 0.91g(0.004モル)とPPD 0.54g(0.005モル)とBAPB 0.37g(0.001モル)を入れ、N-メチル-2-ピロリドンを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 19質量%となる量の24.13gを加え、室温で1時間攪拌した。この溶液にCpODA 3.84g(0.010モル)を徐々に加えた。室温で12時間撹拌し、均一で粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(5) 5.1gと水 18.54g と1,2-ジメチルイミダゾール 2.11g(0.0220モル)を加え、室温で1時間攪拌した。この溶液に1,4-tra-DACH 1.14g(0.0100モル)を入れ、室温で1時間攪拌した。この溶液にs-BPDA 2.87g(0.00975モル)とa-BPDA 0.07g(0.00025モル)を徐々に加えた。室温で12時間撹拌し、粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中に1,4-tra-DACH 11.42g(0.100モル)を入れ、水を仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 15質量%となる量の231.37gを加え、室温で1時間攪拌した。この溶液に1,2-ジメチルイミダゾール 21.15g(0.220モル)を加え、室温で1時間攪拌した。この溶液にs-BPDA 28.67g(0.0975モル)とa-BPDA 0.74g(0.0025モル)を徐々に加えた。50℃で12時間撹拌し、均一で粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中に4,4’-ODA 20.02g(0.100モル)を入れ、N,N-ジメチルアセトアミドを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 17質量%となる量の207.21gを加え、室温で1時間攪拌した。この溶液にPMDA-HS 22.41g(0.100ミリモル)を徐々に加えた。室温で12時間撹拌した。この溶液にトルエン30g加え、180℃で8時間加熱し、イミド化を行った。この溶液を大量の水に再沈殿させ、ろ過、乾燥した。得られた固体(ポリイミド) 10gをN-メチル-2-ピロリドン 40gに加え、室温で3時間攪拌し、均一で粘稠なポリイミド溶液を得た。この溶液に炭酸ストロンチウム分散液(2) 5.0gを加え、室温で1時間攪拌し、ポリイミド溶液を得た。
窒素ガスで置換した反応容器中に4,4’-ODA 20.02g(0.100モル)を入れ、N,N-ジメチルアセトアミドを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 17質量%となる量の207.21gを加え、室温で1時間攪拌した。この溶液にPMDA-HS 22.41g(0.100ミリモル)を徐々に加えた。室温で12時間撹拌した。この溶液にトルエン30g加え、180℃で8時間加熱し、イミド化を行った。この溶液を大量の水に再沈殿させ、ろ過、乾燥した。得られた固体(ポリイミド) 10gをN-メチル-2-ピロリドン 25gに加え、室温で3時間攪拌し、均一で粘稠なポリイミド溶液を得た。この溶液に炭酸ストロンチウム分散液(2) 20.0gを加え、室温で1時間攪拌し、ポリイミド溶液を得た。
窒素ガスで置換した反応容器中に4,4’-ODA 20.02g(0.100モル)を入れ、N,N-ジメチルアセトアミドを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 17質量%となる量の207.21gを加え、室温で1時間攪拌した。この溶液にPMDA-HS 22.41g(0.100ミリモル)を徐々に加えた。室温で12時間撹拌した。この溶液にトルエン30g加え、180℃で8時間加熱し、イミド化を行った。この溶液を大量の水に再沈殿させ、ろ過、乾燥した。得られた固体(ポリイミド) 10gをN-メチル-2-ピロリドン 40gに加え、室温で3時間攪拌し、均一で粘稠なポリイミド溶液を得た。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(1) 7.20gとN-メチル-2-ピロリドン 22.30gを加え、室温で1時間攪拌した。窒素ガスで置換した反応容器中にTFMB 3.20g(0.010モル)を入れ、室温で1時間攪拌した。この溶液にs-BPDA 0.88g(0.0030モル)と6FDA 3.11(0.0070モル)を徐々に加えた。室温で12時間撹拌した。この溶液に1,2-ジメチルイミダゾール 0.96g(0.010モル)を加え、室温で1時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中にTFMB 32.02g(0.100モル)を入れ、N-メチル-2-ピロリドンを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 20質量%となる量の287.79gを加え、室温で1時間攪拌した。この溶液にs-BPDA 8.83g(0.030モル)と6FDA 31.10(0.070モル)を徐々に加えた。室温で12時間撹拌した。この溶液に1,2-ジメチルイミダゾール 0.96g(0.010モル)を加え、室温で1時間攪拌し、均一で粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中に炭酸ストロンチウム分散液(1) 2.13gとN-メチル-2-ピロリドン 31.24gを加え、室温で1時間攪拌した。この溶液にm-TD 2.12g(0.01モル)を入れ、室温で1時間攪拌した。この溶液にCpODA 0.38g(0.001モル)とCBDA 1.76g(0.009モル)を徐々に加えた。室温で12時間撹拌した。この溶液に1,2-ジメチルイミダゾール 0.10g(0.001モル)を加え、室温で1時間攪拌し、粘稠なポリイミド前駆体溶液を得た。
窒素ガスで置換した反応容器中にm-TD 2.12g(0.010モル)を入れ、DMAcを、仕込みモノマー総質量(ジアミン成分とカルボン酸成分の総和)が 12質量%となる量の31.24gを加え、室温で1時間攪拌した。この溶液にCBDA 1.76g(0.009モル)とCpODA 0.38g(0.001モル)を徐々に加えた。室温で12時間撹拌した。この溶液に、1,2-ジメチルイミダゾール 0.1g(0.001モル)を加え、室温で1時間攪拌し均一で粘稠なポリイミド前駆体溶液を得た。
Claims (19)
- ポリイミド前駆体(A1)と、光学異方性を有する微粒子(B)とを含むことを特徴とするポリイミド前駆体組成物。
- X1が脂環構造を有する4価の基であり、Y1が脂環構造を有する2価の基である化学式(1)で表される繰り返し単位の含有量が、全繰り返し単位に対して、50モル%以下であることを特徴とする請求項2に記載のポリイミド前駆体組成物。
- 化学式(1)中のX1が芳香族環を有する4価の基であり、Y1が芳香族環を有する2価の基であることを特徴とする請求項2に記載のポリイミド前駆体組成物。
- 化学式(1)中のX1が脂環構造を有する4価の基であり、Y1が芳香族環を有する2価の基であることを特徴とする請求項2に記載のポリイミド前駆体組成物。
- 化学式(1)中のX1が芳香族環を有する4価の基であり、Y1が脂環構造を有する2価の基であることを特徴とする請求項2に記載のポリイミド前駆体組成物。
- 前記光学異方性を有する微粒子(B)が、炭酸ストロンチウムであることを特徴とする請求項1~6のいずれかに記載のポリイミド前駆体組成物。
- ポリイミド(A2)と、光学異方性を有する微粒子(B)とを含むことを特徴とするポリイミド組成物。
- 請求項1~7のいずれかに記載のポリイミド前駆体組成物から得られることを特徴とするポリイミド組成物。
- 請求項1~7のいずれかに記載のポリイミド前駆体組成物から得られるポリイミド組成物、又は請求項8~9のいずれかに記載のポリイミド組成物からなることを特徴とするポリイミドフィルム。
- 請求項11記載のポリイミドフィルムと、少なくとも1層のガラス層を有することを特徴とするポリイミドフィルム積層体。
- 請求項11記載のポリイミドフィルムと、少なくとも1層のガスバリヤ層を有することを特徴とするポリイミドフィルム積層体。
- 請求項11記載のポリイミドフィルムと、少なくとも1層の薄膜トランジスタを有することを特徴とするポリイミドフィルム積層体。
- 請求項11記載のポリイミドフィルムと、少なくとも1層の導電層を有すること特徴とする請求項12または13に記載のポリイミドフィルム積層体。
- 請求項1~7のいずれかに記載のポリイミド前駆体組成物から得られるポリイミド組成物、又は請求項8~9のいずれかに記載のポリイミド組成物を含むことを特徴とするディスプレイ用、タッチパネル用、または太陽電池用のフィルム。
- 請求項1~7のいずれかに記載のポリイミド前駆体組成物から得られるポリイミド組成物、又は請求項8~9のいずれかに記載のポリイミド組成物を含むことを特徴とする表示デバイス、センサーデバイス、光電変換デバイス、または光学デバイス。
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JPWO2017150377A1 (ja) * | 2016-03-03 | 2018-12-27 | 大日本印刷株式会社 | ポリイミドフィルム、ポリイミドフィルムの製造方法、及びポリイミド前駆体樹脂組成物 |
WO2017150377A1 (ja) * | 2016-03-03 | 2017-09-08 | 大日本印刷株式会社 | ポリイミドフィルム、ポリイミドフィルムの製造方法、及びポリイミド前駆体樹脂組成物 |
JP2018158535A (ja) * | 2017-03-23 | 2018-10-11 | 宇部興産株式会社 | ポリイミドフィルムとハードコート層とを含む積層体 |
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JPWO2018190179A1 (ja) * | 2017-04-10 | 2020-05-14 | 大日本印刷株式会社 | ポリイミドフィルム、積層体、及びディスプレイ用表面材 |
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JP7196384B2 (ja) | 2017-09-06 | 2022-12-27 | 大日本印刷株式会社 | ポリイミドフィルム、光学フィルムおよび画像表示装置 |
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CN110198972B (zh) * | 2017-11-03 | 2021-12-21 | 株式会社Lg化学 | 用于显示器基底的聚酰亚胺膜 |
US11873371B2 (en) | 2017-11-03 | 2024-01-16 | Lg Chem, Ltd. | Polyimide film for display substrate |
JPWO2019198709A1 (ja) * | 2018-04-10 | 2021-04-15 | 三菱瓦斯化学株式会社 | ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム |
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JP7371621B2 (ja) | 2018-04-10 | 2023-10-31 | 三菱瓦斯化学株式会社 | ポリイミド樹脂、ポリイミドワニス及びポリイミドフィルム |
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TW201710321A (zh) | 2017-03-16 |
CN107849352A (zh) | 2018-03-27 |
CN107849352B (zh) | 2021-05-28 |
US20180171077A1 (en) | 2018-06-21 |
JP6919564B2 (ja) | 2021-08-18 |
KR20180018667A (ko) | 2018-02-21 |
TWI772260B (zh) | 2022-08-01 |
JPWO2016199926A1 (ja) | 2018-04-05 |
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