WO2014185353A1 - 透明ポリイミドおよびその前駆体 - Google Patents
透明ポリイミドおよびその前駆体 Download PDFInfo
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- WO2014185353A1 WO2014185353A1 PCT/JP2014/062474 JP2014062474W WO2014185353A1 WO 2014185353 A1 WO2014185353 A1 WO 2014185353A1 JP 2014062474 W JP2014062474 W JP 2014062474W WO 2014185353 A1 WO2014185353 A1 WO 2014185353A1
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- structural unit
- formula
- unit represented
- polyamic acid
- following formula
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- SMAKEJNOUFLEEJ-UHFFFAOYSA-N CCC1CCC(CC)CC1 Chemical compound CCC1CCC(CC)CC1 SMAKEJNOUFLEEJ-UHFFFAOYSA-N 0.000 description 2
- CFTSORNHIUMCGF-UHFFFAOYSA-N FC(C(C(F)(F)F)(c1ccccc1)c1ccccc1)(F)F Chemical compound FC(C(C(F)(F)F)(c1ccccc1)c1ccccc1)(F)F CFTSORNHIUMCGF-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N O=S(c1ccccc1)(c1ccccc1)=O Chemical compound O=S(c1ccccc1)(c1ccccc1)=O KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- ULJRYEABYHQRFP-UHFFFAOYSA-N CCC1CCC(C)(CC)CC1 Chemical compound CCC1CCC(C)(CC)CC1 ULJRYEABYHQRFP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a transparent polyimide and a polyamic acid which is a precursor thereof, and uses thereof.
- Polyimide generally has excellent heat resistance, mechanical properties, and electrical properties. For this reason, polyimide is widely used as a molding material or a composite material in various applications such as electrical / electronic materials and optical materials.
- polyimides obtained by reacting alicyclic diamines with aromatic tetracarboxylic acids have relatively high transparency, and future applications such as electrical and electronic materials and optical materials will be expanded.
- future applications such as electrical and electronic materials and optical materials will be expanded.
- Expected see, for example, Patent Document 1 and Patent Document 2).
- the polyimide resin layer is patterned using the transparency of the polyimide, exposing the photosensitive resin layer containing an ultraviolet polymerizable compound formed on the polyimide resin layer through a photomask, and then developing with an alkaline solution. It is usual to carry out by (etching) treatment. Accordingly, there is a demand for polyimide having not only light transmittance but also high ultraviolet light transmittance.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyimide that is excellent in heat resistance and colorless transparency, and also excellent in flexibility and ultraviolet transmittance.
- the present inventors have found that the above problems can be solved by a polyimide having a skeleton derived from a specific alicyclic diamine and a specific aromatic tetracarboxylic dianhydride.
- the present invention has been completed. That is, the present invention includes the following matters.
- R is a group represented by the following formula (x1), (x2), or (x3);
- R is a group represented by the following formula (x1), (x2), or (x3);
- * represents a carbon atom bonded to the carbon atom of C ⁇ O adjacent to R, and when a plurality of R are contained, these groups are Can be the same or different
- m represents the molar fraction of the structural unit represented by the formula (2a) with respect to the entire structural unit represented by the formula (2a) and the structural unit represented by the following formula (2b)
- n represents the formula The molar fraction of the structural unit represented by the formula (2b) with respect to the whole structural unit represented by the structural unit represented by (2a) and the following formula (2b) is shown, and m / n is 99.9.
- a polyimide composition comprising the polyimide according to [1] or [2] and an inorganic filler.
- a polyamic acid composition comprising the polyamic acid according to [3] or [4] and an inorganic filler.
- a diamine mixture containing bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid Tetracarboxylic dianhydride comprising an anhydride and at least one selected from 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride
- the manufacturing method of the polyamic acid as described in [3] including the process with which a product is made to react.
- R is a group represented by the following formula (x1), (x2), or (x3),
- a polyamic acid varnish comprising the polyamic acid according to [3] or [4] and a solvent.
- a flexible display substrate including the optical film according to [12].
- the polyimide obtained according to the present invention is not only excellent in heat resistance and colorless transparency, but also excellent in flexibility and ultraviolet transparency, particularly transparency of long wavelength ultraviolet rays (for example, 365 nm ultraviolet rays).
- the polyimide of the present invention includes a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (1b).
- R is a group represented by the following formula (x1), (x2), or (x3), and in the following formulas (x1), (x2), and (x3) , * Represents a carbon atom bonded to a C ⁇ O carbon atom adjacent to R in the above formulas (1a) and (1b).
- * is a carbon atom bonded to the carbon atom of C ⁇ O adjacent to R.
- these groups may be the same or different, and R contained in the above formula (1a) and the above formula (1b) The contained R may be the same or different.
- the structural unit represented by the above formula (1a) is composed of 1,4-cyclohexanediamine and bis (3,4-dicarboxyphenyl) ether dianhydride (also known as 4,4′-oxydiphthalic anhydride), 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane
- This is a structural unit obtained by reacting at least one tetracarboxylic dianhydride selected from anhydrides (also known as 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride).
- the structural unit derived from the tetracarboxylic dianhydride is formed from one single tetracarboxylic dianhydride. It may be formed from two or more kinds of tetracarboxylic dianhydrides.
- the structural unit represented by the above formula (1b) is composed of 1,4-bis (aminomethyl) cyclohexane, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′- At least one acid selected from diphenylsulfonetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride It is a structural unit obtained by reacting with an anhydride.
- the structural unit derived from the tetracarboxylic dianhydride is formed from one single tetracarboxylic dianhydride. It may be formed from two or more kinds of tetracarboxylic dianhydrides.
- the group derived from the tetracarboxylic dianhydride in the above (1a) and the group derived from the tetracarboxylic dianhydride in the above formula (1b) may be the same or different.
- the ratio of the trans isomer in the cyclohexane skeleton is within such a range, the molecular weight of the obtained polyimide can be easily increased, and a self-supporting film can be easily formed.
- the trans isomer ratio is preferably 70% to 100%, the cis isomer ratio is preferably 30% to 0%, and the trans isomer ratio is 80% to 100%. More preferably, the ratio of cis-isomer is 20% to 0%.
- the glass transition temperature (Tg) of the resulting polyimide can be increased.
- the trans isomer ratio is preferably 80% to 100% and the cis isomer ratio is preferably 20% to 0%.
- m is the molar fraction of the structural unit represented by the formula (1a) with respect to the entire structural unit represented by the formula (1a) and the structural unit represented by the following formula (1b).
- n is the mole fraction of the structural unit represented by the formula (1b) with respect to the entire structural unit represented by the formula (1a) and the structural unit represented by the following formula (1b).
- This m / n is in the range of 99.9 / 0.1 to 50.0 / 50.0.
- the resulting polyimide has not only excellent colorless transparency and ultraviolet transparency, but also has heat resistance such that Tg is 260 ° C. or higher and also has flexibility. It becomes.
- m / n is preferably in the range of 99.9 / 0.1 to 70.0 / 30.0, more preferably 99.5 / 0.5. It is in the range of ⁇ 80.0 / 20.0, more preferably in the range of 99.5 / 0.5 to 90.5 / 9.5.
- R is a group represented by (x1)
- m / n is preferably in the above range.
- Tg tends to decrease greatly, which tends to be undesirable from the viewpoint of heat resistance.
- flexibility tends to be insufficient.
- the structural unit represented by the above formula (1a) and the structural unit represented by the above formula (1b) are bonded, but there is no particular limitation on the bonding form of these structural units.
- the bonding form is random.
- a block in which a plurality of units are continuous may be used, and these coupling formats may be mixed.
- R is a group represented by (x1), that is, the structural unit derived from the tetracarboxylic dianhydride contained in the polyimide is bis (3,4- It is an embodiment that is a structural unit derived from (dicarboxyphenyl) ether dianhydride.
- the polyimide of the present invention may be composed only of the structural unit represented by the above formula (1a) and the structural unit represented by the above formula (1b), but within the range not impairing the effects of the present invention, Other structural units other than the structural unit represented by the formula (1a) and the structural unit represented by the formula (1b) may be included.
- Other structural units include, for example, 1,4-cyclohexanediamine or 1,4-bis (aminomethyl) cyclohexane, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4 Tetracarboxylic acids other than '-diphenylsulfonetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride Structural units obtained by reacting with dianhydrides, Diamines other than 1,4-cyclohexanediamine and 1,4-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (3,4-dicarboxyphenyl) ether dianhydride, 3, 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride or 2,2-bis (3,
- the said tetracarboxylic dianhydride may be used independently and may be used in combination of 2 or more type. Further, for the purpose of introducing a branch into the polyimide, a part of the tetracarboxylic dianhydride may be replaced with hexacarboxylic dianhydride or octacarboxylic dianhydride.
- the said diamine may be used independently and may be used in combination of 2 or more type.
- the content of other structural units contained in the polyimide is not particularly limited as long as the effects of the present invention are not impaired, but the total of the structural units represented by the formula (1a) and the formula (1b) The amount is usually 10 mol to 0 mol, preferably 9 mol to 0 mol, per 100 mol.
- the polyimide of the present invention is preferably dissolved in an aprotic polar solvent.
- dissolution means that polyimide is dissolved in an aprotic solvent by 10 g / l or more, preferably 100 g / l or more.
- the aprotic polar solvent include aprotic amide solvents.
- aprotic amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidi.
- N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferable.
- the Tg of the polyimide of the present invention is preferably 260 ° C. or higher, more preferably 280 ° C. or higher, from the viewpoint of improving heat resistance.
- the Tg of polyimide can be determined by TMA measurement according to the following procedure, for example. That is, a test piece made of polyimide (5 mm ⁇ 22 mm, thickness of about 10 to 50 ⁇ m) was measured at a temperature rising rate of 5 ° C./min at a temperature range of 25 to 350 ° C.
- the glass transition temperature (Tg) can be determined from the inflection point of the temperature-test piece elongation curve obtained by TMA measurement under the load 14 g / mm 2 and tensile mode measurement conditions.
- the thermal expansion coefficient of the polyimide film of the present invention is preferably 30 ppm / K or less, and more preferably 20 ppm / K or less in order to reduce warpage of the circuit board described later.
- the thermal expansion coefficient of the film can be determined from the slope in the temperature range of 100 to 200 ° C. of the temperature-test piece elongation curve obtained by the TMA measurement described above.
- the tensile modulus of elasticity of the polyimide of the present invention is preferably 100 to 200 MPa.
- Polyimide having such a tensile elastic modulus can be used for various applications including optical applications as a material having sufficient strength.
- the tensile elongation (dumbbell-shaped test piece: marked line width: 5 mm, tensile speed: 30 mm / min) of the polyimide of the present invention is 10% or more.
- the polyimide having such tensile elongation can be suitably used as an application that requires flexibility, for example, as a film, for example, as a film.
- the total light transmittance measured according to JIS K 7105 of a 30 ⁇ m thick film made of the polyimide of the present invention is preferably 80% or more, more preferably 82% or more.
- the light transmittance at a wavelength of 365 nm of a 10 ⁇ m thick film made of the polyimide of the present invention is preferably 30% or more, and more preferably 35% or more.
- the polyimide of the present invention can be suitably used for applications requiring ultraviolet irradiation (for example, curing of an ultraviolet polymerizable compound).
- the polyimide of the present invention preferably has an absolute value of b * in the L * a * b * color system specified by JIS Z 8729 (a numerical value is positive for yellow and a negative value indicates blue). 3 or less, and more preferably, the value of b * is in the range of 0-3. When the value of b * is in the above range, it is not yellow, that is, it can be suitably used as a colorless and transparent polyimide.
- the polyimide of the present invention may be used as a film.
- the film in the present invention includes a layer. That is, the film containing the polyimide of the present invention contains the polyimide of the present invention, and may further contain other components such as a cured product of a photopolymerizable compound as necessary.
- the film of the present invention may be a multilayer film including at least one layer made of the polyimide of the present invention.
- the polyamic acid of the present invention includes a structural unit represented by the following formula (2a) and a structural unit represented by the following formula (2b).
- the polyamic acid of the present invention is also a precursor of the polyimide described above.
- the structural unit represented by the formula (2a) corresponds to the structural unit represented by the above formula (1a), and the structural unit represented by the formula (2a) includes 1,4-cyclohexanediamine and bis (3 , 4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, and 2,2-bis (3,4-dicarboxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane dianhydride is a structural unit obtained by reacting with at least one tetracarboxylic dianhydride selected from the group.
- the structural unit represented by the formula (2b) corresponds to the structural unit represented by the above formula (1b), and the structural unit represented by the formula (2b) is 1,4-bis (aminomethyl) cyclohexane and Bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, and 2,2-bis (3,4-dicarboxyphenyl) It is a structural unit obtained by reacting at least one acid anhydride selected from -1,1,1,3,3,3-hexafluoropropane dianhydride.
- the trans isomer ratio is preferably 70% to 100%, the cis isomer ratio is preferably 30% to 0%, the trans isomer ratio is 80% to 100%, and the cis isomer ratio is 20%. More preferably, it is ⁇ 0%.
- the trans isomer ratio is preferably 80% to 100% and the cis isomer ratio is preferably 20% to 0%.
- R and m in the formula (2a) are synonymous with R and m in the formula (1a), and R and n in the formula (2b) are synonymous with R and n in the formula (1b).
- m / n is in the range of 99.9 / 0.1 to 50.0 / 50.0, preferably in the range of 99.0 / 0.1 to 70.0 / 30.0, more preferably 99.
- the range is from 0.5 / 0.5 to 80.0 / 20.0, more preferably from 99.5 / 0.5 to 90.5 / 9.5.
- R is a group represented by (x1)
- m / n is preferably in the above range.
- the structural unit represented by the above formula (2a) and the structural unit represented by the above formula (2b) are bonded, but there is no particular limitation on the bonding form of these structural units.
- the bonding form is random.
- a block in which a plurality of units are continuous may be used, and these coupling formats may be mixed.
- One preferred embodiment of the polyamic acid of the present invention is an embodiment in which the R is a group represented by (x1), that is, the structural unit derived from the tetracarboxylic dianhydride contained in the polyamic acid is bis (3, It is an embodiment that is a structural unit derived from 4-dicarboxyphenyl) ether dianhydride.
- the polyamic acid of the present invention may be composed only of the structural unit represented by the above formula (2a) and the structural unit represented by the above formula (2b), but within the range not impairing the effects of the present invention.
- Other structural units other than the structural unit represented by the above formula (2a) and the structural unit represented by the above formula (2b) may be included.
- Other structural units include, for example, 1,4-cyclohexanediamine or 1,4-bis (aminomethyl) cyclohexane, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4 Tetracarboxylic acids other than '-diphenylsulfonetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride Structural units obtained by reacting with dianhydrides, Diamines other than 1,4-cyclohexanediamine and 1,4-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (3,4-dicarboxyphenyl) ether dianhydride, 3, 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride or 2,2-bis (3,
- the said tetracarboxylic dianhydride may be used independently and may be used in combination of 2 or more type. Further, for the purpose of introducing a branch into the polyimide, a part of the tetracarboxylic dianhydride may be replaced with hexacarboxylic dianhydride or octacarboxylic dianhydride.
- the content of other structural units contained in the polyamic acid is not particularly limited as long as the effects of the present invention are not impaired, but the structural unit represented by the formula (1a) and the structural unit represented by the formula (1b)
- the amount is generally 10 mol to 0 mol, preferably 9 mol to 0 mol, relative to the total of 100 mol.
- the logarithmic viscosity of the polyamic acid solution obtained in the present invention (solvent: N-methyl-2-pyrrolidone, concentration: 0.5 g / dl) at 35 ° C. is in the range of 0.1 to 3.0 dl / g. Is preferred.
- solvent N-methyl-2-pyrrolidone, concentration: 0.5 g / dl
- concentration 0.5 g / dl
- the polyamic acid of the present invention includes, for example, a diamine mixture containing 1,4-cyclohexanediamine and 1,4-bis (aminomethyl) cyclohexane, bis (3,4-dicarboxyphenyl) ether dianhydride, 3, 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride It can be obtained by polyaddition reaction with a tetracarboxylic dianhydride containing at least one selected from the products.
- the molar ratio of 1,4-cyclohexanediamine and 1,4-bis (aminomethyl) cyclohexane in the diamine mixture is expressed by the structural unit represented by the formula (2a) and the formula (2b) of the resulting polyamic acid. It is only necessary that the ratio m / n of the structural units to be included is within the above-mentioned desired range.
- the molar ratio of 1,4-cyclohexanediamine / 1,4-bis (aminomethyl) cyclohexane in the diamine mixture is preferably in the range of 99.9 / 0.1 to 50.0 / 50.0, more The range is preferably 99.9 / 0.1 to 70.0 / 30.0, more preferably 99.5 / 0.5 to 80.0 / 20.0, and particularly preferably 99.5 / 0. It may be in the range of 5 to 90.5 / 9.5.
- the tetracarboxylic dianhydride is bis (3,4-dicarboxyphenyl) ether dianhydride
- the diamine mixture may contain other diamines other than 1,4-cyclohexanediamine and 1,4-bis (aminomethyl) cyclohexane as long as the effects of the present invention are not impaired.
- bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetra is used within the range not impairing the effects of the present invention.
- Carboxylic dianhydrides and other tetracarboxylic dianhydrides other than 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride May be included.
- a part of the tetracarboxylic dianhydride may be replaced with hexacarboxylic dianhydride or octacarboxylic dianhydride.
- These other diamines and other tetracarboxylic dianhydrides are desirably used in such amounts that the content of other structural units contained in the polyamic acid is in the above-described range.
- the polyaddition reaction for producing polyamic acid is preferably performed in a reaction solvent.
- the reaction solvent include aprotic polar solvents and water-soluble alcohol solvents.
- aprotic polar solvent examples include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoramide.
- water-soluble alcohol solvent examples include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butane.
- Diol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 1,2,6- Examples include hexanetriol and diacetone alcohol.
- reaction solvents may be used alone or in combination of two or more.
- reaction solvents aprotic polar solvents are preferred, and N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and mixtures thereof are more preferred.
- the atmosphere for polymerizing the polyamic acid is not limited as long as the polymerization is not inhibited, but a nitrogen atmosphere is desirable.
- the solid content concentration of the obtained polyimide is about 30% by weight.
- the molar ratio of the diamine mixture to the tetracarboxylic dianhydride is usually about 0.9 to 1.1.
- the polymerization time depends on the polymerization temperature, it is usually about 1 to 50 hours. In order to accelerate the reaction, the polymerization solution may be heated.
- the polymerization temperature is usually 40 to 120 ° C, preferably 60 to 100 ° C.
- the polyamic acid varnish can be prepared by dissolving the polyamic acid thus obtained in a solvent.
- the solvent for the polyamic acid varnish is preferably an aprotic polar solvent.
- the aprotic polar solvent include the same compounds as the aprotic polar solvent used as a reaction solvent used in the production of polyamic acid, and preferred compounds are also the same.
- the concentration of the polyamic acid contained in the polyamic acid varnish is not particularly limited. Increasing the concentration tends to facilitate removal of the solvent by drying. Therefore, the concentration of the polyamic acid is preferably 15% by weight or more. On the other hand, when the concentration is too high, it tends to be difficult to apply the polyamic acid varnish.
- the concentration of the polyamic acid is preferably 50% by weight or less.
- the polyamic acid varnish may contain additives to be described later such as a photosensitizing component (such as a photopolymerizable compound and a photopolymerization initiator) and an inorganic filler.
- the dry film containing the polyamic acid of the present invention can be produced by applying the above-mentioned polyamide varnish to a base material such as a carrier film and removing the residual solvent.
- a base material such as a carrier film
- the heating temperature is usually about 80 to 150 ° C.
- the carrier film for example, when the dry film has photosensitivity, it may be desired to have transparency so that the dry film can be exposed and to have low moisture permeability. Therefore, the carrier film is preferably a transparent film such as polyethylene terephthalate, polyethylene, or polypropylene.
- the amount of residual solvent in the dry film is preferably adjusted to a certain level or less.
- the residual solvent amount of the dry film is preferably 3 to 20% by mass and more preferably 10% by mass or less in order to make the solubility in an alkaline aqueous solution in an appropriate range.
- the amount of residual solvent in the dry film is large, the dissolution rate in the alkaline aqueous solution tends to increase.
- the amount of residual solvent in the dry film is measured, for example, by gas chromatography (GC) measurement, and the area of the peak corresponding to the solvent in the obtained chart is calculated and collated with a previously prepared calibration curve for the solvent. Can be obtained.
- GC gas chromatography
- the GC measurement is performed by, for example, an electric furnace type pyrolysis furnace (for example, PYR-2A manufactured by Shimadzu Corporation), a gas chromatograph mass spectrometer (for example, Shimadzu) in which the injector temperature and detector temperature are set to 200 ° C., and the column temperature is set to 170 ° C.
- GC-8A manufactured by Seisakusho was connected, and after the dry film was put into an electric furnace type pyrolysis furnace, it was immediately heated to 320 ° C. to generate volatile components. Volatile components can be analyzed by analyzing with a gas chromatograph mass spectrometer.
- the thickness of the dry film depends on the application, it is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m when used for an interlayer insulating layer of a circuit board.
- the surface of the dry film may be further protected with a cover film.
- the cover film is not particularly limited as long as it is a film having low moisture permeability.
- the dry film may contain additives to be described later such as a photosensitizing component (photopolymerizable compound, photopolymerization initiator, etc.) and an inorganic filler.
- a photosensitizing component photopolymerizable compound, photopolymerization initiator, etc.
- an inorganic filler such as a photosensitizing component (photopolymerizable compound, photopolymerization initiator, etc.) and an inorganic filler.
- the polyimide of the present invention described above can be produced, for example, by imidizing (dehydrating condensation reaction) the polyamic acid obtained as described above.
- the imidization means is not particularly limited, and may be performed, for example, thermally or chemically as follows. (1) A method of imidizing a polyamic acid in a solvent by heating to, for example, about 100 to 400 ° C.
- the polyimide of the present invention is 1,4-cyclohexanediamine and bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, and 2,2-bis (3 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride is reacted with a tetracarboxylic dianhydride containing at least one selected from the following formula (3a):
- R is a group represented by the following formula (x1), (x2), or (x3),
- the molar ratio of the structural unit represented by the formula (3a) / the structural unit represented by the formula (3b) is preferably in the range of 99.9 / 0.1 to 70.0 / 30.0, more preferably 99 The range is from 0.5 / 0.5 to 80.0 / 20.0, more preferably from 99.5 / 0.5 to 90.5 / 9.5.
- R in the above formulas (3a) and (3b) is a group represented by the formula (x1)
- the structural unit represented by the formula (3a) / the structural unit represented by the formula (3b) The molar ratio is preferably in the above range.
- the production conditions for the polyamic acid (1) and the polyamic acid (2) are the same as the production conditions for the polyamic acid of the present invention. Moreover, the said imidation can be performed on the same conditions as the imidation mentioned above.
- the polyimide resin composition may be made by further adding various additives to the polyimide of the present invention as necessary.
- additives include inorganic fillers, organic fillers, wear resistance improvers, flame retardant improvers, tracking resistance improvers, acid resistance improvers, thermal conductivity improvers, antifoaming agents, leveling agents, and surface tension.
- examples thereof include a regulator and a coloring agent.
- the inorganic filler examples include metal oxides such as titanium oxide, zinc oxide, magnesium oxide, alumina, and silica; calcium carbonate, magnesium carbonate, barium titanate, barium sulfate, calcium sulfate, magnesium sulfate, aluminum sulfate, and magnesium chloride.
- Inorganic metal salts such as basic magnesium carbonate, precipitated barium sulfate and precipitated barium carbonate; metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; talc, natural mica, synthetic mica, kaolin, etc. And clay minerals.
- the particle shape of the inorganic filler is not particularly limited, and may be needle-shaped, plate-shaped, or spherical.
- the average particle size of the inorganic filler is preferably 0.05 ⁇ m to 5 ⁇ m, more preferably 0.05 ⁇ m to 2 ⁇ m.
- the inorganic filler is contained in an amount of preferably 10 to 500 parts by weight, more preferably 20 to 400 parts by weight with respect to 100 parts by weight of polyimide. Within this range, for example, when a film made of polyimide is used as the light reflecting plate, the light reflectivity is sufficient, and the film strength is hardly lowered.
- organic filler examples include fine particles such as epoxy resin, melamine resin, urea resin, acrylic resin, polyimide, tetrafluoroethylene resin, polyethylene, polyester, polyamide and the like (however, insoluble in a solvent used for varnish) Some).
- the colorant may be organic, inorganic, or fluorescent dye agent.
- a coloring agent there is no restriction
- the light reflectance can be increased by blending a white agent such as a fluorescent brightening agent.
- Such a polyimide resin composition can be prepared by preparing a polyamic acid resin composition containing the polyamic acid of the present invention and various additives and imidizing it. Moreover, after adding various additives further to the mixture of the polyamic acid (1) and polyamic acid (2) mentioned above, it can also produce by imidating this.
- a film (polyimide film) containing the polyimide or the polyimide resin composition of the present invention can have high transparency, heat resistance, ultraviolet transparency and flexibility. Therefore, the film containing the polyimide or polyimide composition of the present invention can also be used as an optical film.
- the optical film examples include a polarizing plate protective film, a retardation film, an antireflection film, an electromagnetic wave shielding film, and a transparent conductive film.
- the optical film can be used as a transparent substrate for a panel for use in an image display device.
- the transparent panel substrate examples include a flexible display substrate, a flat panel display substrate, a liquid crystal display substrate, and an inorganic / organic substrate. Examples include an EL display substrate, a touch panel substrate, and an electronic paper substrate.
- Functional films such as a smooth layer, a hard coat layer, a gas barrier layer, a transparent conductive layer, or other optical films may be further laminated on the polyimide film used as a transparent substrate for a panel for use in an image display device.
- the glass transition temperature (Tg), thermal expansion coefficient and total light transmittance of the film are preferably in the same ranges as described above. .
- polyimide films were prepared and various physical properties were measured by the following methods.
- Total light transmittance Total T The total light transmittance of the produced polyimide film was measured by a method according to JIS K 7105 with a light source D65 using a Nippon Denshoku Haze Meter NDH2000 equipped with an integrating sphere.
- Tensile strength TS and tensile elongation EL A dumbbell punched specimen is prepared from the polyimide film obtained above and measured with a tensile tester (manufactured by Shimadzu Corporation, EZ-S) under the conditions of a marked line width of 5 mm, a sample length of 30 mm, and a tensile speed of 30 mm / min. went. From the obtained stress / strain curve, the strength and elongation at the point of fracture were taken as tensile strength and tensile elongation, respectively, and the average value of the five measurements was taken as tensile strength TS and tensile elongation EL.
- ODPA bis (3,4-dicarboxyphenyl) ether dianhydride
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 2 Changed CHDA charge from 11.3g to 10.9g (0.095mol), 14BAC charge from 0.140g to 0.710g (0.005mol), DMAc charge from 223g to 224g
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 3 The CHDA charge was changed from 11.3 g to 10.3 g (0.090 mol), the 14BAC charge was changed from 0.140 g to 1.42 g (0.010 mol), and the DMAc charge was changed from 223 g to 224 g.
- a polyamic acid solution was prepared in the same manner as in Example 1 except that. Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 4 Changed CHDA charge from 11.3 g to 9.14 g (0.080 mol), 14BAC charge from 0.140 g to 2.84 g (0.020 mol), and DMAc charge from 223 g to 226 g
- a polyamic acid solution was prepared in the same manner as in Example 1 except that.
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 5 Change CHCH charge from 11.3g to 5.71g (0.050mol), 14BAC charge from 0.140g to 7.11g (0.050mol), DMAc charge from 223g to 230g
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 1 As in Example 1 except that 14BAC was not used as the diamine, the CHDA charge was changed from 11.3 g to 11.4 g (0.100 mol), and the DMAc charge was changed from 223 g to 224 g. A solution was made. Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 2 As in Example 1, except that CHDA was not used as the diamine, the amount of 14BAC was changed from 0.140 g to 14.2 g (0.100 mol), and the amount of DMAc was changed from 223 g to 238 g. A solution was made. Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Comparative Example 3 Except for changing the amount of DMAc charged from 224 g to 189 g and ODPA 31.0 g to 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) 35.8 g (0.100 mol), As in Comparative Example 1, a polyamic acid solution was prepared. Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Comparative Example 4 A polyamic acid solution was prepared in the same manner as in Comparative Example 2, except that the amount of DMAc charged was changed from 238 g to 200 g and ODPA 31.0 g was changed to DSDA 35.8 g (0.100 mol).
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained polyamic acid solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained mixed solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- Example 7 Example 6 except that the amount of the polyamic acid solution obtained in Comparative Example 1 was changed from 50.4 g to 48.3 g, and the amount of the polyamic acid solution obtained in Comparative Example 2 was changed from 2.83 g to 5.09 g.
- a mixed solution was prepared in the same manner as described above.
- Table 1 summarizes the varnish physical properties ( ⁇ ) of the obtained mixed solution and the physical properties (Tg, T% @ 365 nm, b *, Total T, TS, EL) of the film obtained according to the above-described film preparation method.
- the CHDA / 14BAC ratio (namely, m / n) in the obtained liquid mixture is 91/9.
- the polyimide obtained by the present invention not only has excellent heat resistance and colorless transparency, but also has excellent flexibility and ultraviolet transparency, and particularly excellent transparency to long wavelength ultraviolet rays (for example, 365 nm ultraviolet rays). It is useful for various applications such as electrical / electronic materials such as flexible circuit boards and optical materials.
Abstract
Description
mは、式(1a)で表される構造単位および式(1b)で表される構造単位の全体に対する、式(1a)で表される構造単位のモル分率を示し、nは、式(1a)で表される構造単位および式(1b)で表される構造単位の全体に対する、式(1b)で表される構造単位のモル分率を示し(m+n=100%)、かつm/nが99.9/0.1~50.0/50.0であり、式(1a)で表される構造単位と式(1b)で表される構造単位とは結合しており、その結合方式は、ランダムでもブロックでもよく、
上記式(1a)におけるシクロヘキサン骨格(y)は、60%~100%の下記式(y1)で表されるトランス体と、40%~0%の下記式(y2)で表されるシス体とからなり(トランス体+シス体=100%)、
mは、式(2a)で表される構造単位および下記式(2b)で表される構造単位の全体に対する、式(2a)で表される構造単位のモル分率を示し、nは、式(2a)で表される構造単位および下記式(2b)で表される構造単位の全体に対する、式(2b)で表される構造単位のモル分率を示し、かつm/nが99.9/0.1~50.0/50.0の範囲にあり、式(2a)で表される構造単位と式(2b)で表される構造単位とは結合しており、その結合方式は、ランダムでもブロックでもよく、
上記式(2a)におけるシクロヘキサン骨格(y)は、60%~100%の下記式(y1)で表されるトランス体と、40%~0%の下記式(y2)で表されるシス体とからなり(トランス体+シス体=100%)、
1,4-ビス(アミノメチル)シクロヘキサンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から選ばれる少なくとも1つを含むテトラカルボン酸二無水物とを反応させて下記式(3b)で表される構造単位を含むポリアミド酸(2)を製造する工程、
ポリアミド酸(1)とポリアミド酸(2)とを、下記式(3a)で表される構造単位/下記式(3b)で表される構造単位のモル比が99.9/0.1~50.0/50.0の範囲となるように混合してポリアミド酸混合物を製造する工程、および
上記ポリアミド酸混合物のイミド化を行う工程を含む[1]に記載のポリイミドの製造方法。
[9] [3]または[4]に記載のポリアミド酸と溶媒とを含むポリアミド酸ワニス。
1,4-シクロヘキサンジアミンおよび1,4-ビス(アミノメチル)シクロヘキサン以外のジアミンと1,4-ビス(アミノメチル)シクロヘキサンと、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、または2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物とを反応させて得られる構造単位、
1,4-シクロヘキサンジアミンおよび1,4-ビス(アミノメチル)シクロヘキサン以外のジアミンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物以外のテトラカルボン酸二無水物とを反応させて得られる構造単位などが挙げられる。上記テトラカルボン酸二無水物は単独で用いてもよく、2種以上組み合わせて用いてもよい。また、ポリイミドに分岐を導入することなどを目的に、上記テトラカルボン酸二無水物の一部を、ヘキサカルボン酸三無水物またはオクタカルボン酸四無水物などに置き換えてもよい。上記ジアミンは単独で用いてもよく、2種以上組み合わせて用いてもよい。
1,4-シクロヘキサンジアミンおよび1,4-ビス(アミノメチル)シクロヘキサン以外のジアミンと1,4-ビス(アミノメチル)シクロヘキサンと、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、または2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物とを反応させて得られる構造単位、
1,4-シクロヘキサンジアミンおよび1,4-ビス(アミノメチル)シクロヘキサン以外のジアミンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物以外のテトラカルボン酸二無水物とを反応させて得られる構造単位などが挙げられる。上記テトラカルボン酸二無水物は単独で用いてもよく、2種以上組み合わせて用いてもよい。また、ポリイミドに分岐を導入することなどを目的に、上記テトラカルボン酸二無水物の一部を、ヘキサカルボン酸三無水物またはオクタカルボン酸四無水物などに置き換えてもよい。
(1)溶媒中のポリアミド酸を、例えば100~400℃程度に加熱して、イミド化する方法(熱イミド化)
(2)溶媒中のポリアミド酸を、無水酢酸などのイミド化剤を用いて化学的にイミド化する方法(化学イミド化)
(3)溶媒中のポリアミド酸を、触媒存在下または不存在下、共沸脱水用溶媒の存在下においてイミド化する方法(共沸脱水閉環法)
また、上述したポリアミド酸ワニスから作製されたドライフィルムを、20℃~400℃、好ましくは150℃~350℃、さらに好ましくは200℃~300℃で、1秒~5時間程度加熱することによりイミド化を行い、ポリイミドを作製することもできる。
1,4-シクロヘキサンジアミンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から選ばれる少なくとも1つを含むテトラカルボン酸二無水物とを反応させて下記式(3a)で表される構造単位を含むポリアミド酸(1)を製造する工程、
1,4-ビス(アミノメチル)シクロヘキサンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から選ばれる少なくとも1つを含むテトラカルボン酸二無水物とを反応させて下記式(3b)で表される構造単位を含むポリアミド酸(2)を製造する工程、
ポリアミド酸(1)とポリアミド酸(2)とを、下記式(3a)で表される構造単位/下記式(3b)で表される構造単位のモル比が99.9/0.1~50.0/50.0の範囲となるように混合してポリアミド酸混合物を製造する工程、および
上記ポリアミド酸混合物のイミド化を行う工程を含む製造方法によっても製造できる。
式(3a)で表される構造単位/式(3b)で表される構造単位のモル比は、好ましくは99.9/0.1~70.0/30.0の範囲、より好ましくは99.5/0.5~80.0/20.0の範囲、さらに好ましくは99.5/0.5~90.5/9.5の範囲である。特に、上記式(3a)および(3b)のRが式(x1)であらわされる基である場合には、式(3a)で表される構造単位/式(3b)で表される構造単位のモル比が上記範囲であることが望ましい。
各実施例および比較例で得られたポリアミド酸溶液(ワニス)を、ドクターブレードにてガラス基板上に流延した。このガラス基板を、オーブンにて窒素気流中、2時間かけて50℃から280℃まで昇温し、次いで280℃で2時間保持して、流延膜をイミド化させた。得られた流延膜をガラス基板から剥離することで、厚みが10μm~14μmの範囲にあるポリイミドフィルムを得た。
得られたポリアミド酸溶液(ワニス)を、固形分濃度が0.5g/dlとなるようにN,N-ジメチルアセトアミド(DMAc)を加えて調整し、その固有対数粘度(dl/g)をウベローデ粘度計を用いて35℃にて測定した。
作製したポリイミドフィルムの試験片(標線幅5mm・試料長20mm)を、測定装置TMA-50(島津製作所製)を用いて、25~350℃の温度範囲で、昇温速度5℃/分、荷重14g/mm2、引張りモードの条件でTMA測定した。得られた温度・伸度曲線の変曲点からガラス転移温度(Tg)を求めた。
作製したポリイミドフィルムをMultiSpec-1500(島津製作所製)を用いて、紫外・可視スペクトルを測定した。この時の波長365nmにおける光線透過率を計測した。
作製したポリイミドフィルムについて、色彩式差計(測定ヘッド:CM-2500d コニカミノルタ社製)を用いて、C光源・2°視野・SCIモードの条件で、校正白色板の上で、黄色味の指標となる値の測定を行った。3回の測定値の平均値をb*とした。
作製したポリイミドフィルムの全光線透過率を、積分球を備えた日本電色工業製ヘーズメーターNDH2000を用いて、光源D65にてJIS K 7105に準じた方法で測定した。
上記で得たポリイミドフィルムよりダンベル型打ち抜き試験片を作製し、引張試験機(島津製作所製、EZ-S)にて、標線幅5mm、試料長30mm、引張速度30mm/分の条件で測定を行った。得られた応力・歪曲線より、破断に至った点における強度および伸度をそれぞれ引張強度および引張伸度とし、5回の測定値の平均値を、引張強度 TS、引張伸度 ELとした。
1H NMR(溶媒CDCl3)測定より、所定磁場範囲におけるシグナルの強度比より、シス体/トランス体比率を算出した。すなわち、シス体由来のNH2CH2(2.61ppm、ダブレット)と、トランス体由来のNH2CH2(2.53ppm、ダブレット)との比率から算出したところ、トランス体比率84%であった。
(実施例1)
温度計、攪拌機、窒素導入管を備えた500mLの5口セパラブルフラスコに、撹拌条件下、1,4-ジアミノシクロヘキサン(以下、CHDAと称する;岩谷瓦斯社製、トランス体比率:99%以上)11.3g(0.099モル)と、1,4-ビス(アミノメチル)シクロヘキサン(以下、14BACと称する;トランス体比率:84%、)0.140g(0.001モル)と、有機溶媒であるN,N‐ジメチルアセトアミド(以下、DMAcと称する)223gとを加え、ジアミン混合物の溶液を作製した。さらに撹拌条件下、その溶液に、ビス(3,4-ジカルボキシフェニル)エーテル二無水物(以下、ODPAと称する)31.0g(0.100モル)を粉状のまま投入した後、得られた液を、90℃に保持したオイルバス中に1時間浴して反応させた。液は、当初は不均一であったが、反応の進行に従って透明な溶液に変化し、粘性のあるポリアミド酸溶液を得た。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
CHDAの仕込み量を11.3gから10.9g(0.095モル)に、14BACの仕込み量を0.140gから0.710g(0.005モル)に、DMAcの仕込み量を223gから224gに変更する以外は実施例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
CHDAの仕込み量を11.3gから10.3g(0.090モル)に、14BACの仕込み量を0.140gから1.42g(0.010モル)に、DMAcの仕込み量を223gから224gに変更する以外は実施例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
CHDAの仕込み量を11.3gから9.14g(0.080モル)に、14BACの仕込み量を0.140gから2.84g(0.020モル)に、DMAcの仕込み量を223gから226gに変更する以外は実施例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
CHDAの仕込み量を11.3gから5.71g(0.050モル)に、14BACの仕込み量を0.140gから7.11g(0.050モル)に、DMAcの仕込み量を223gから230gに変更する以外は実施例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
ジアミンとして14BACを用いずに、CHDAの仕込み量を11.3gから11.4g(0.100モル)に、DMAcの仕込み量を223gから224gに変更する以外は実施例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
ジアミンとしてCHDAを用いずに、14BACの仕込み量を0.140gから14.2g(0.100モル)に、DMAcの仕込み量を223gから238gに変更する以外は実施例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
DMAcの仕込み量を224gから189gに、ODPA31.0gを3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物(DSDA)35.8g(0.100モル)に変更する以外は、比較例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
DMAcの仕込み量を238gから200gに、ODPA31.0gをDSDA35.8g(0.100モル)に変更する以外は、比較例2と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
DMAcの仕込み量を224gから231gに、ODPA31.0gを3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(BPDA)29.4g(0.100モル)に変更する以外は、比較例1と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
DMAcの仕込み量を238gから247gに、ODPA31.0gを3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(BPDA)29.4g(0.100モル)に変更する以外は、比較例2と同様に、ポリアミド酸溶液を作製した。得られたポリアミド酸溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
(実施例6)
温度計、攪拌機、窒素導入管を備えた200mLの5口セパラブルフラスコに、撹拌条件下、比較例1で得たポリアミド酸溶液(CHDA/14BAC比率が100/0、濃度16wt%)50.4gと、比較例2で得たポリアミド酸溶液(CHDA/14BAC比率が0/100、濃度16wt%)2.83gとを加え混合溶液を作製した。混合溶液中のCHDA/14BAC比率(すなわち、m/n)は95/5である。該混合溶液を60℃に保持したオイルバス中で1時間、さらに室温で12時間撹拌した。得られた混合溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。
比較例1で得たポリアミド酸溶液の仕込み量を50.4gから48.3gに、比較例2で得たポリアミド酸溶液の仕込み量を2.83gから5.09g変更する以外は、実施例6と同様に混合溶液を作製した。得られた混合溶液のワニス物性(η)、および上記フィルム作成方法に従って得られたフィルムの各物性(Tg、T%@365nm、b*、Total T、TS、EL)を表1にまとめる。なお得られた混合液中のCHDA/14BAC比率(すなわち、m/n)は91/9である。
Claims (13)
- 下記式(1a)で表される構造単位と下記式(1b)で表される構造単位とを含むポリイミド。
mは、式(1a)で表される構造単位および式(1b)で表される構造単位の全体に対する、式(1a)で表される構造単位のモル分率を示し、nは、式(1a)で表される構造単位および式(1b)で表される構造単位の全体に対する、式(1b)で表される構造単位のモル分率を示し(m+n=100%)、かつm/nが99.9/0.1~50.0/50.0であり、式(1a)で表される構造単位と式(1b)で表される構造単位とは結合しており、その結合方式は、ランダムでもブロックでもよく、
上記式(1a)におけるシクロヘキサン骨格(y)は、60%~100%の下記式(y1)で表されるトランス体と、40%~0%の下記式(y2)で表されるシス体とからなり(トランス体+シス体=100%)、
- 上記式(1a)および(1b)において、Rが(x1)で表される基である請求項1に記載のポリイミド。
- 下記式(2a)で表される構造単位と下記式(2b)で表される構造単位とを含むポリアミド酸。
mは、式(2a)で表される構造単位および下記式(2b)で表される構造単位の全体に対する、式(2a)で表される構造単位のモル分率を示し、nは、式(2a)で表される構造単位および下記式(2b)で表される構造単位の全体に対する、式(2b)で表される構造単位のモル分率を示し、かつm/nが99.9/0.1~50.0/50.0の範囲にあり、式(2a)で表される構造単位と式(2b)で表される構造単位とは結合しており、その結合方式は、ランダムでもブロックでもよく、
上記式(2a)におけるシクロヘキサン骨格(y)は、60%~100%の下記式(y1)で表されるトランス体と、40%~0%の下記式(y2)で表されるシス体とからなり(トランス体+シス体=100%)、
- 上記一般式(2a)および(2b)において、Rが(x1)で表される基である請求項3に記載のポリアミド酸。
- 請求項1に記載のポリイミドと無機フィラーとを含むポリイミド組成物。
- 請求項3に記載のポリアミド酸と無機フィラーとを含むポリアミド酸組成物。
- 1,4-シクロヘキサンジアミンと1,4-ビス(アミノメチル)シクロヘキサンとを1,4-シクロヘキサンジアミン/1,4-ビス(アミノメチル)シクロヘキサンのモル比が99.9/0.1~50.0/50.0の範囲となるように含むジアミン混合物と、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から選ばれる少なくとも1つを含むテトラカルボン酸二無水物とを反応させる工程を含む請求項3に記載のポリアミド酸の製造方法。
- 1,4-シクロヘキサンジアミンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から選ばれる少なくとも1つを含むテトラカルボン酸二無水物とを反応させて下記式(3a)で表される構造単位を含むポリアミド酸(1)を製造する工程、
1,4-ビス(アミノメチル)シクロヘキサンとビス(3,4-ジカルボキシフェニル)エーテル二無水物、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物から選ばれる少なくとも1つを含むテトラカルボン酸二無水物とを反応させて下記式(3b)で表される構造単位を含むポリアミド酸(2)を製造する工程、
ポリアミド酸(1)とポリアミド酸(2)とを、下記式(3a)で表される構造単位/下記式(3b)で表される構造単位のモル比が99.9/0.1~50.0/50.0の範囲となるように混合してポリアミド酸混合物を製造する工程、および
上記ポリアミド酸混合物のイミド化を行う工程を含む請求項1に記載のポリイミドの製造方法。
- 請求項3に記載のポリアミド酸と溶媒とを含むポリアミド酸ワニス。
- 請求項3に記載のポリアミド酸を含むドライフィルム。
- 請求項1に記載のポリイミド組成物を含むフィルム。
- 請求項11に記載のフィルムを含む光学フィルム。
- 請求項12に記載の光学フィルムを含むフレキシブルディスプレイ用基板。
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US10707491B2 (en) | 2016-02-10 | 2020-07-07 | Nec Corporation | Binder for secondary battery |
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JPWO2018016561A1 (ja) * | 2016-07-22 | 2019-03-14 | 三井化学株式会社 | 医療用フィルム及びその製造方法、医療用コーティング組成物、医療用具及びその製造方法 |
US11198280B2 (en) | 2016-07-22 | 2021-12-14 | Mitsui Chemicals, Inc. | Medical film and method for producing same, medical coating composition, medical device and method for producing same |
JP2018197822A (ja) * | 2017-05-24 | 2018-12-13 | 三井化学株式会社 | 液晶素子及びその製造方法 |
WO2019074047A1 (ja) * | 2017-10-12 | 2019-04-18 | 三菱瓦斯化学株式会社 | ポリイミドワニス組成物、その製造方法、及びポリイミドフィルム |
JPWO2019074047A1 (ja) * | 2017-10-12 | 2020-09-17 | 三菱瓦斯化学株式会社 | ポリイミドワニス組成物、その製造方法、及びポリイミドフィルム |
JP7230820B2 (ja) | 2017-10-12 | 2023-03-01 | 三菱瓦斯化学株式会社 | ポリイミドワニス組成物、その製造方法、及びポリイミドフィルム |
JP2019105830A (ja) * | 2017-12-08 | 2019-06-27 | 住友化学株式会社 | 光学積層体 |
JP2020059785A (ja) * | 2018-10-09 | 2020-04-16 | 三井化学株式会社 | ポリアミド酸およびこれを含むワニス、ならびにポリイミドフィルムの製造方法 |
WO2022004857A1 (ja) * | 2020-07-02 | 2022-01-06 | 住友化学株式会社 | 光学フィルム |
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US9850346B2 (en) | 2017-12-26 |
CN105143309A (zh) | 2015-12-09 |
KR20150132533A (ko) | 2015-11-25 |
CN105143309B (zh) | 2017-05-03 |
US20160115276A1 (en) | 2016-04-28 |
JPWO2014185353A1 (ja) | 2017-02-23 |
JP5931286B2 (ja) | 2016-06-08 |
TW201446840A (zh) | 2014-12-16 |
KR101787862B1 (ko) | 2017-11-15 |
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