WO2012033213A1 - ポリイミドおよびポリイミドフィルム - Google Patents
ポリイミドおよびポリイミドフィルム Download PDFInfo
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- WO2012033213A1 WO2012033213A1 PCT/JP2011/070672 JP2011070672W WO2012033213A1 WO 2012033213 A1 WO2012033213 A1 WO 2012033213A1 JP 2011070672 W JP2011070672 W JP 2011070672W WO 2012033213 A1 WO2012033213 A1 WO 2012033213A1
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- 0 O=C1OC(*c(cc23)ccc2C(C=C[C@](C2)*=C(c4c5)O6)=C2C32c5ccc4C6=O)c3cc2ccc13 Chemical compound O=C1OC(*c(cc23)ccc2C(C=C[C@](C2)*=C(c4c5)O6)=C2C32c5ccc4C6=O)c3cc2ccc13 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
- 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
-
- 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
-
- 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
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- 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 polyimide and a polyimide film. More specifically, the present invention relates to a polyimide and a polyimide film using an aromatic diamine or aromatic tetracarboxylic dianhydride having a group derived from fluorene or a fluorene derivative as a raw material.
- Polyimide has not only excellent heat resistance, but also chemical resistance, radiation resistance, electrical insulation, and excellent mechanical properties. Therefore, it is currently widely used in various electronic devices such as flexible printed circuit boards, tape automation bonding base materials, protective films for semiconductor elements, and interlayer insulating films for integrated circuits.
- polyimide is a very useful material in terms of simplicity of manufacturing method, high film purity, and ease of property improvement.
- functional polyimide material design suitable for various applications has been made. Yes.
- polyimide is synthesized by polymerizing equimolar amounts of aromatic tetracarboxylic dianhydride such as pyromellitic anhydride and aromatic diamine such as diaminodiphenyl ether in an aprotic polar organic solvent such as dimethylacetamide.
- aromatic tetracarboxylic dianhydride such as pyromellitic anhydride
- aromatic diamine such as diaminodiphenyl ether
- aprotic polar organic solvent such as dimethylacetamide.
- Polyamide acid polyamic acid
- this polyamic acid is heated at 250 to 350 ° C. to advance a dehydration / cyclization (imidization) reaction.
- the polyimide molding process is used in a polyamic acid solution.
- a desired film, molded product, or coating film is obtained by drying the solution, and then heated and imidized.
- thermal stress generated in the process of cooling the polyimide / copper substrate laminate from the imidization temperature to room temperature often causes serious problems such as curling, film peeling and cracking.
- multilayer wiring boards have come to be used. However, even if film peeling or cracking does not occur, residual stress in the multilayer board significantly increases device reliability. Reduce.
- polyimide As a measure for reducing thermal stress, it is effective to reduce the expansion of polyimide.
- Most polyimides have a linear coefficient of thermal expansion in the range of 30 to 100 ppm / ° C., which is much higher than the linear coefficient of thermal expansion of 17 ppm / ° C. for metal substrates such as copper.
- a polyimide produced from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine is most well known as a practical low thermal expansion polyimide.
- This polyimide film made of polyimide is known to exhibit a very low linear thermal expansion coefficient of 5 to 10 ppm / ° C., depending on the film thickness and production conditions.
- polyimides exhibiting a low coefficient of thermal expansion have a rigid and linear main chain structure, as described above, and most of them have poor water vapor permeability and are liable to foam depending on film forming conditions. .
- Patent Document 1 there is an example in which water vapor permeability is improved by mixing other polyimide chains, but the improvement by mixing has a problem in the stable production of the polyimide film.
- an object of the present invention is to provide a polyimide and a polyimide film having a linear thermal expansion coefficient close to that of copper and having a high elastic modulus and good water vapor permeability without impairing heat resistance.
- the present invention includes the following (1) to (5).
- Component (I) an aromatic diamine represented by the following formula (1);
- the component (I) is 0.1 to 10.0 mol% and the component (II) is 99.9 to 90% with respect to the total amount of the component (I) and the component (II).
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, a nitrogen-containing atom group, or a linear or branched alkyl group having 1 to 12 carbon atoms.
- Component (III) an aromatic tetracarboxylic dianhydride represented by the following formula (2); Component (II): obtained by reacting 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine and 4,4′-diaminodiphenyl ether, The component (III) is 0.1 to 2.5 mol% and the component (II) is 99.9 to 97 with respect to the total amount of the component (III) and the component (II). .5 mol% polyimide:
- R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a nitrogen-containing atom group, a linear or branched alkyl group having 1 to 12 carbon atoms, or 2 carbon atoms. -12 linear or branched alkenyl group, linear or branched alkoxy group having 1 to 12 carbon atoms, hydroxy group, nitrile group, nitro group, carboxy group, carbamoyl group and 6 to 12 carbon atoms Selected from the group consisting of aromatic groups.
- Water vapor permeability is 10 to 100 g / m 2 / day, average linear thermal expansion coefficient at 50 to 200 ° C. is 10 to 25 ppm / ° C., no clear glass transition temperature, and tensile modulus Polyimide film as described in said (3) or (4) whose is 5.0 GPa or more.
- a specific aromatic diamine or a specific aromatic tetracarboxylic dianhydride having a group derived from fluorene or a fluorene derivative It is obtained by reacting 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine and 4,4′-diaminodiphenyl ether in a specific molar ratio.
- the polyimide film produced by imidizing the polyimide precursor has a linear thermal expansion coefficient close to that of copper, and it is known that the polyimide film has a high elastic modulus and good water vapor permeability without impairing heat resistance. Thus, the present invention has been completed.
- component (I) aromatic diamine represented by the following formula (1); component (II): 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic acid” It is obtained by reacting dianhydride, p-phenylenediamine and 4,4′-diaminodiphenyl ether, and the component (I) is 0 with respect to the total amount of the component (I) and the component (II).
- polyimide (1) 0.1 to 10.0 mol% and the component (II) is 99.9 to 90.0 mol%
- component (II) is 99.9 to 90.0 mol%
- component (III) aromatic tetracarboxylic dianhydride represented by the following formula (2), and component (II): 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic acid 2 Anhydrides, p-phenylenediamine and 4,4'-diamino Obtained by reacting with phenyl ether, the component (III) is 0.1 to 2.5 mol% with respect to the total amount of the component (III) and the component (II), and the A polyimide film in which component (II) is 99.9 to 97.5 mol% (hereinafter sometimes referred to as “polyimide (2)”), and polyimide (1) or polyimide (2). .
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a nitrogen-containing atom group, or 1 carbon atom.
- the nitrogen-containing atom group is not particularly limited as long as it is a monovalent group containing a nitrogen atom, but preferably has a free valence on the nitrogen atom.
- an amino group —NH 2
- Monomethylamino group —NHCH 3
- dimethylamino group —N (CH 3 ) 2
- the linear or branched alkyl group having 1 to 12 carbon atoms is not particularly limited as long as the general formula is a group represented by C n H 2n + 1- (n: a natural number of 1 to 12). Examples thereof include a methyl group, an ethyl group, a 1-propyl group (n-propyl group), a 2-propyl group (isopropyl group) and the like (hereinafter the same).
- the linear or branched alkenyl group having 2 to 12 carbon atoms is not particularly limited as long as the general formula is a group represented by C n H 2n-1- (n: a natural number of 2 to 12).
- the valence may be on an unsaturated carbon atom or a saturated carbon atom. Specific examples include a vinyl group and an allyl group (the same applies hereinafter).
- the linear or branched alkoxy group having 1 to 12 carbon atoms is not particularly limited as long as the general formula is represented by C n H 2n + 1 O- (n: a natural number of 1 to 12). Examples include methoxy group and ethoxy group (the same applies hereinafter).
- the said component (I) consists of aromatic diamine represented by the said Formula (1).
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, a nitrogen-containing atom group, a linear or branched alkyl group having 1 to 12 carbon atoms, or the number of carbon atoms.
- R 1 , R 2 , R 3 and R 4 are simultaneously a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or 2 to It is preferably a linear or branched alkenyl group having 12 or a linear or branched alkoxy group having 1 to 12 carbon atoms, and R 1 , R 2 , R 3 and R 4 are simultaneously a hydrogen atom or methyl
- R 1 , R 2 , R 3 and R 4 are more preferably a hydrogen atom at the same time.
- the component (II) is composed of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine and 4,4′-diaminodiphenyl ether.
- M BPTC 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
- M PMDA pyromellitic dianhydride
- the molar ratio of the number of moles of p-phenylenediamine (M PPDA ) to the number of moles of 4,4′-diaminodiphenyl ether (M DAPE ) is not particularly limited, but M PPDA : M DAPE is It is preferably 1: 0.5 to 1: 2, more preferably 1: 0.7 to 1: 1.4, and even more preferably 1: 0.9 to 1: 1.1. More preferably, it is 1: 1.
- tetracarboxylic dianhydride contained in the component (II)
- the tetracarboxylic dianhydrides listed in 1 may be used alone or in admixture of two or more:
- diamine contained in the said component (II) replaces with a part of p-phenylenediamine or 4,4'- diamino diphenyl ether, and the diamine hung up below is used individually by 1 type or in mixture of 2 or more types. And may be used:
- Aliphatic diamines such as benzene aromatic diamino compounds, heteroaromatic diamino compounds, non-benzene aromatic diamino compounds; etc.
- the aliphatic diamine is preferably a compound in which two hydrogen groups of a chain hydrocarbon compound having 2 to 15 carbon atoms are each substituted with an amino group.
- the benzene aromatic diamino compound is preferably a compound having one benzene nucleus or 2 to 10 condensed or non-condensed benzene nuclei, and examples thereof include the following:
- Phenylenediamine such as m-phenylenediamine; phenylenediamine derivative in which an alkyl group such as methyl group or ethyl group is bonded to phenylenediamine such as 2-methyl-1,4-diaminobenzene;
- Two aminophenyl groups and one phenylene such as 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4-bis (p-aminophenoxy) benzene
- 1,3-bis (m-aminophenoxy) benzene 1,3-bis (p-aminophenoxy) benzene
- 1,4-bis (p-aminophenoxy) benzene A diaminotriphenyl compound in which any group is bonded via another linking group (the linking group mentioned in the section of diaminodiphenyl compound);
- Diaminonaphthalenes such as 1,5-diaminonaphthalene and 2,6-diaminonaphthalene; aminophenylaminoindanes such as 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindane;
- Diaminotetraphenyls such as 4,4′-bis (p-aminophenoxy) biphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and 4,4′-bis (3-aminophenoxy) benzophenone A compound; and
- the component (III) is composed of an aromatic tetracarboxylic dianhydride represented by the above formula (2).
- R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a nitrogen-containing atom group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a straight chain having 2 to 12 carbon atoms.
- R 5 and R 6 are simultaneously selected from the group consisting of a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, or is preferably a straight-chain or branched alkoxy group having a carbon number of 1 ⁇ 12, R 5 and R 6 simultaneously, more preferably a hydrogen atom or a methyl group, R 5 and R 6 are simultaneously water A still more preferred atoms.
- Component (I) is 0.1 to 10.0 mol% and Component (II) is 99.9 to 90.0 mol% with respect to the total amount of component (I) and component (II) It is. Within this range, the water vapor permeability is in a necessary and sufficient range, and film forming properties are also ensured.
- the ratio of the component (I) to the total amount of the component (I) and the component (II) is more preferably 2.0 to 8.0 mol%, further preferably 4.5 to 6.5 mol% (here In the calculation of mol%, the first decimal place is rounded off to the first decimal place).
- the total number of moles of aromatic diamine (M FL ) contained in component (I) and the total number of moles of diamine (M DA ) contained in component (II) (M FL + M DA ), and contained in component (II)
- the ratio of the total number of moles of tetracarboxylic acid anhydride (M TC ) is preferably (M FL + M DA ): M TC is 1: 0.90 to 1: 1.10, and 1: 0 It is more preferably from 95 to 1: 1.05, and even more preferably from 1: 0.99.
- the ratio of (a + b + c + d) :( e + f) in the formula (3) is 99.9 to 90.0 mol%: 0.1 to 10.0 mol%.
- the ratio of (e + f) is more preferably 2.0 to 8.0 mol%, and further preferably 4.5 to 6.5 mol% (where the decimal point is rounded off to the second decimal place for calculation of mol%). Seek up to first place).
- Component (III) is 0.1 to 2.5 mol% and component (II) is 99.9 to 97.5 mol% based on the total amount of component (III) and component (II) It is. Within this range, the water vapor permeability is in a necessary and sufficient range, and film forming properties are also ensured.
- the amount of component (III) with respect to the total amount of component (III) and component (II) is more preferably 1.0 to 2.5 mol% (here, the second decimal place is rounded off in the calculation of mol%). To the first decimal place).
- the total number of moles of diamine contained in component (II) (M DA ′), the number of moles of aromatic tetracarboxylic acid anhydride contained in component (I) (M FL ′), and the tetra number contained in component (II)
- the ratio of the total number of moles of carboxylic anhydride (M TC ′) to the total (M FL ′ + M TC ′) is such that M DA ′: (M FL ′ + M TC ′) is 1: 0.90 to 1: It is preferably 1.10, more preferably 1: 0.95 to 1: 1.05, and even more preferably 1: 0.99.
- the ratio of (a + b + c + d) :( g + h) in formula (4) is 99.9 to 97.5 mol%: 0.1 to 2.5 mol%. Within this range, the water vapor permeability is in a necessary and sufficient range, and film forming properties are also ensured.
- the ratio of (g + h) is more preferably 1.0 to 1.5 mol%. (Here, in calculating mol%, the first decimal place is rounded off to the first decimal place).
- the tensile elastic modulus of the polyimide film of the present invention is a value measured by a measuring method according to ASTM D882, and is preferably 5.0 GPa or more. Within this range, the tensile strength is sufficient. The higher the tensile elastic modulus, the better, more preferably 5.8 GPa or more, still more preferably 6.0 GPa or more, even more preferably 6.3 GPa or more, and even more preferably 6.5 GPa or more.
- the linear thermal expansion coefficient of the polyimide film of the present invention is 50 ° C. to 200 ° C. from the elongation of the test piece at a load of 0.5 g and a heating rate of 5.0 ° C./min using TMA (Thermal Mechanical Analysis) -60 manufactured by Shimadzu
- a value obtained as an average value in the range is preferably in the range of 10 to 25 ppm / ° C. Within this range, since it is close to the linear thermal expansion coefficient of copper of 17 ppm / ° C., it is possible to reduce thermal stress when used as a polyimide / copper substrate laminate.
- the glass transition temperature of the polyimide film of the present invention is measured from the change point of specific heat by heating with a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min.
- the polyimide film of the present invention preferably has no clear glass transition temperature.
- the water vapor permeability of the polyimide film of the present invention is measured at a measurement temperature of 40 ° C., a measurement area of 50 cm 2 , a relative humidity of 90%, a high humidity side of 100%, and a low humidity side according to a measurement method based on JIS K 7129: 2008 It is preferably 10 to 100 g / m 2 / day, measured as 10% and a measurement lower limit of 0.2 g / m 2 / day. Within this range, water vapor permeability is necessary and sufficient, and foaming is less likely to occur, which is advantageous for stable production.
- the water vapor permeability is more preferably 25 to 100 g / m 2 / day or more, further preferably 40 to 100 g / m 2 / day or more, and further preferably 50 to 100 g / m 2 / day or more.
- a chemistry for dehydration and cyclization (imidization) using a catalyst As a means for producing the polyimide of the present invention, in order to ensure a low linear thermal expansion coefficient and a high elastic modulus, as a means for enhancing the in-plane orientation, a chemistry for dehydration and cyclization (imidization) using a catalyst. It is preferable to use an imidization method. For example, a tetracarboxylic dianhydride component and a diamine component are polymerized in an organic solvent at 5 to 40 ° C. for 3 to 10 hours, and then a dehydrating agent and a dehydrating catalyst are mixed at a temperature of 0 ° C.
- a method is used in which a film is formed and heat-treated at a temperature of usually 200 ° C. to 400 ° C., preferably 250 ° C. to 350 ° C. for 0.5 to 15 hours, preferably 1 to 5 hours under an inert gas atmosphere or reduced pressure. .
- Solvents used here include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, phenolic solvents such as cresols, and glycols such as diglyme. A solvent is mentioned. These solvents can be used alone or in combination of two or more. There is no particular limitation on the amount of solvent used, but the content of polyimide to be produced is preferably 5 to 40% by mass.
- Examples of the dehydrating agent and catalyst for chemically dehydrating and cyclizing include a combination of acetic anhydride and picoline, a combination of trifluoroacetic anhydride and picoline, and the like.
- ⁇ Measuring method> The linear thermal expansion coefficient, mechanical toughness, glass transition temperature, and water vapor permeability of the polyimide films of Examples and Comparative Examples were measured by the following methods.
- Tensile elastic modulus Tensile elastic modulus was measured using Shimadzu Autograph AGS-J500N, using a strip-shaped test piece of 90 mm in length and 10 mm in width, according to ASTM D882, distance between chucks of 50 mm, pulling speed of 50.8 mm / Min, measured at 23 ° C.
- the measurement conditions were a measurement temperature of 40 ° C., a measurement area of 50 cm 2 , a relative humidity of 90%, a high humidity side of 100%, a low humidity side of 10%, and a measurement lower limit of 0.2 g / m 2 / day.
- Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introducing tube, 17.4 g (0.05 mol) of 9,9-bis (4-aminophenyl) fluorene (BAFL) and 48.6 g of p-phenylenediamine (0 .45 mol) and 100 g (0.50 mol) of 4,4′-diaminodiphenyl ether were charged, and 1932 g of N, N-dimethylacetamide (DMAc) was added and completely dissolved.
- BAFL 9,9-bis (4-aminophenyl) fluorene
- DMAc N, N-dimethylacetamide
- Example 2 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 34.8 g (0.10 mol) of 9,9-bis (4-aminophenyl) fluorene (BAFL) and 43.2 g of p-phenylenediamine (0 .40 mol) and 4,4′-diaminodiphenyl ether (100 g, 0.50 mol) were charged, and 1986 g of N, N-dimethylacetamide (DMAc) was added to completely dissolve the mixture.
- BAFL 9,9-bis (4-aminophenyl) fluorene
- p-phenylenediamine (0 .40 mol
- 4,4′-diaminodiphenyl ether 100 g, 0.50 mol
- Example 3 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 37.6 g (0.10 mol) of 9,9-bis (4-amino-3-methylphenyl) fluorene (BTFL), p-phenylenediamine 43 .2 g (0.40 mol) and 4,4′-diaminodiphenyl ether 100 g (0.50 mol) were charged, and N, N-dimethylacetamide (DMAc) 1988 g was added and completely dissolved.
- BTFL 9,9-bis (4-amino-3-methylphenyl) fluorene
- p-phenylenediamine 43 .2 g (0.40 mol
- 4,4′-diaminodiphenyl ether 100 g (0.50 mol
- Example 4 A reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube was charged with 54.0 g (0.50 mol) of p-phenylenediamine and 100 g (0.50 mol) of 4,4′-diaminodiphenyl ether, and N, N -1983 g of dimethylacetamide (DMAc) was added and completely dissolved.
- DMAc dimethylacetamide
- Example 5 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 38.4 g (0.10 mol) of 9,9-bis (4-amino-3-fluorophenyl) fluorene (BFAF), p-phenylenediamine 43 .3 g (0.40 mol) and 4,4′-diaminodiphenyl ether 100 g (0.50 mol) were charged, and N, N-dimethylacetamide (DMAc) 1995 g was added and completely dissolved.
- BFAF 9,9-bis (4-amino-3-fluorophenyl) fluorene
- p-phenylenediamine 43 .3 g (0.40 mol) and 4,4′-diaminodiphenyl ether 100 g (0.50 mol) were charged, and N, N-dimethylacetamide (DMAc) 1995 g was added and completely dissolved.
- DMAc N,
- Example 6 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 50.1 g (0.10 mol) of 9,9-bis (4-amino-3-phenylphenyl) fluorene (BPAF), p-phenylenediamine 43 .3 g (0.40 mol) and 4,4′-diaminodiphenyl ether 100 g (0.50 mol) were charged, and 2050 g of N, N-dimethylacetamide (DMAc) was added and completely dissolved.
- BPAF 9,9-bis (4-amino-3-phenylphenyl) fluorene
- p-phenylenediamine 43 .3 g (0.40 mol) and 4,4′-diaminodiphenyl ether 100 g (0.50 mol) were charged, and 2050 g of N, N-dimethylacetamide (DMAc) was added and completely dissolved.
- Example 7 A reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube was charged with 54.0 g (0.50 mol) of p-phenylenediamine and 100 g (0.50 mol) of 4,4′-diaminophenyl ether. 1950 g of N-dimethylacetamide (DMAc) was added and completely dissolved.
- DMAc N-dimethylacetamide
- Acetic anhydride and ⁇ -picoline were added to this precursor, a film was formed on a smooth glass plate, dried and imidized by heating, and a polyimide film with a thickness of 30 ⁇ m was obtained.
- a polyimide film with a thickness of 30 ⁇ m was obtained.
- the tensile elasticity modulus, the linear thermal expansion coefficient, the glass transition temperature, and water vapor transmission rate were measured with the above-mentioned measuring method. The measurement results are shown in the column of Comparative Example 2 in Table 1.
- Example 1 0.05 mol of 9,9-bis (4-aminophenyl) fluorene was used as component (I), p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3, A total of 1.942 moles of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are used.
- Component (I) was 2.5 mol% and component (II) was 97.5 mol% based on the sum of component (I) and component (II).
- Table 1 all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Example 2 As component (I), 9,9-bis (4-aminophenyl) fluorene was 0.10 mol, and as component (II), p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3, A total of 1.892 moles of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are used. Component (I) was 5.0 mol% and component (II) was 95.0 mol% based on the sum of component (I) and component (II). As is clear from Table 1, all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Example 3 ⁇ Description of Example 3>
- 0.10 mol of 9,9-bis (4-amino-3-phenylphenyl) fluorene was used as component (I)
- p-phenylenediamine, 4,4′-diamino was used as component (II).
- a total of 1.892 mols of diphenyl ether, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are used.
- Component (I) was 5.0 mol% and component (II) was 95.0 mol% based on the sum of component (I) and component (II).
- Table 1 all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Example 4 includes 0.05 mol of 4,4 ′-(9-fluorenylidene) bisphthalic anhydride as component (III), p-phenylenediamine, 4,4′-diaminodiphenyl ether as component (II), A total of 1.942 moles of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are used.
- Component (III) was 2.5 mol% and component (II) was 97.5 mol% based on the sum of component (III) and component (II). As is clear from Table 1, all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Example 5 ⁇ Description of Example 5>
- 0.10 mol of 9,9-bis (4-amino-3-fluorophenyl) fluorene (BFAF) was used as component (I) and p-phenylenediamine was used as component (II).
- a total of 1.892 mol of '-diaminodiphenyl ether, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride is used.
- Component (I) was 5.0 mol% and component (II) was 95.0 mol% based on the sum of component (I) and component (II).
- Table 1 all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Example 6 9,9-bis (4-amino-3-phenylphenyl) fluorene (BPAF) was 0.10 mol, as component (II), p-phenylenediamine, 4,4 A total of 1.892 mol of '-diaminodiphenyl ether, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride is used.
- Component (I) was 5.0 mol% and component (II) was 95.0 mol% based on the sum of component (I) and component (II). As is clear from Table 1, all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Example 7 is 0.10 mol of 4,4 ′-(9-fluorenylidene) bisphthalic anhydride as component (III), p-phenylenediamine, 4,4′-diaminodiphenyl ether as component (II), A total of 1.892 moles of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are used.
- Component (III) was 5.0 mol% and component (II) was 95.0 mol% based on the sum of component (III) and component (II). As is clear from Table 1, all of the tensile modulus, linear thermal expansion coefficient, glass transition temperature, and water vapor permeability were good.
- Comparative Example 1 ⁇ Description of Comparative Example 1>
- no component corresponding to component (I) or component (III) is used, and polyimide is synthesized only from the component corresponding to component (II).
- the molar ratio of diamine to tetracarboxylic dianhydride was 1.00: 0.992. Although the tensile modulus, linear thermal expansion coefficient and glass transition temperature were good, the water vapor permeability was not sufficient.
- Comparative Example 2 ⁇ Description of Comparative Example 2> In Comparative Example 2, none of the components corresponding to Component (I), Component (II) and Component (III) was used, 1.0 mol of p-phenylenediamine as diamine, and 3 as tetracarboxylic dianhydride. , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used to synthesize polyimide. The molar ratio of diamine to tetracarboxylic dianhydride was 1.00: 0.992. The tensile modulus, linear thermal expansion coefficient and glass transition temperature were good, but the water vapor permeability was insufficient.
- the present invention it is possible to provide a polyimide film having a linear thermal expansion coefficient similar to copper and having a high elastic modulus and good water vapor permeability without impairing heat resistance. Therefore, it can greatly contribute to industry.
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Abstract
Description
(1)成分(I):下記式(1)で表される芳香族ジアミンと、
成分(II):3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルとを反応させて得られ、
当該成分(I)と当該成分(II)との合計量に対して、当該成分(I)が0.1~10.0モル%であり、かつ、当該成分(II)が99.9~90.0モル%であるポリイミド:
成分(II):3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルとを反応させて得られ、
当該成分(III)と当該成分(II)との合計量に対して、当該成分(III)が0.1~2.5モル%であり、かつ、当該成分(II)が99.9~97.5モル%であるポリイミド:
本発明は、「成分(I):下記式(1)で表される芳香族ジアミンと、成分(II):3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルとを反応させて得られ、当該成分(I)と当該成分(II)との合計量に対して、当該成分(I)が0.1~10.0モル%であり、かつ、当該成分(II)が99.9~90.0モル%であるポリイミド」(以下、「ポリイミド(1)」という場合がある。)または「成分(III):下記式(2)で表される芳香族テトラカルボン酸二無水物と、成分(II):3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルとを反応させて得られ、当該成分(III)と当該成分(II)との合計量に対して、当該成分(III)が0.1~2.5モル%であり、かつ、当該成分(II)が99.9~97.5モル%であるポリイミド」(以下、「ポリイミド(2)」という場合がある。)、およびポリイミド(1)またはポリイミド(2)からなるポリイミドフィルムである。
上記成分(I)は、上記式(1)で表される芳香族ジアミンからなる。R1,R2,R3およびR4は上記のとおり、それぞれ独立に、水素原子、ハロゲン原子、含窒素原子基、炭素原子数1~12の直鎖状または分岐状アルキル基、炭素原子数2~12の直鎖状または分岐状アルケニル基、炭素原子数1~12の直鎖状または分岐状アルコキシ基、ヒドロキシ基、ニトリル基、ニトロ基、カルボキシ基、カルバモイル基および炭素原子数6~12の芳香族基からなる群から選ばれるが、R1,R2,R3およびR4が同時に、水素原子、炭素原子数1~12の直鎖状または分岐状アルキル基、炭素原子数2~12の直鎖状または分岐状アルケニル基または炭素原子数1~12の直鎖状または分岐状アルコキシ基であるのが好ましく、R1,R2,R3およびR4が同時に、水素原子またはメチル基であるのがより好ましく、R1,R2,R3およびR4が同時に、水素原子であるのがさらに好ましい。
上記成分(II)は、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルからなるものである。
上記成分(III)は、上記式(2)で表される芳香族テトラカルボン酸二無水物からなる。R5およびR6は、上記のとおり、それぞれ独立に、水素原子、ハロゲン原子、含窒素原子基、炭素原子数1~12の直鎖状または分岐状アルキル基、炭素原子数2~12の直鎖状または分岐状アルケニル基、炭素原子数1~12の直鎖状または分岐状アルコキシ基、ヒドロキシ基、ニトリル基、ニトロ基、カルボキシ基、カルバモイル基および炭素原子数6~12の芳香族基からなる群から選ばれるが、R5およびR6が同時に、水素原子、炭素原子数1~12の直鎖状または分岐状アルキル基、炭素原子数2~12の直鎖状または分岐状アルケニル基または炭素原子数1~12の直鎖状または分岐状アルコキシ基であるのが好ましく、R5およびR6が同時に、水素原子またはメチル基であるのがより好ましく、R5およびR6が同時に、水素原子であるのがさらに好ましい。
成分(I)と成分(II)との合計量に対して、成分(I)が0.1~10.0モル%であり、かつ、成分(II)が99.9~90.0モル%である。この範囲内であると、水蒸気透過度が必要十分な範囲となり、製膜性も確保される。成分(I)と成分(II)との合計量に対する成分(I)の割合は、2.0~8.0モル%がより好ましく、4.5~6.5モル%がさらに好ましい(ここで、モル%の計算上、小数点第2位を四捨五入して小数点第1位までを求める)。
成分(I)に含まれる芳香族ジアミンのモル数(MFL)および成分(II)に含まれるジアミンの合計モル数(MDA)の合計(MFL+MDA)と、成分(II)に含まれるテトラカルボン酸無水物の合計モル数(MTC)との比は、(MFL+MDA):MTCが、1:0.90~1:1.10であるのが好ましく、1:0.95~1:1.05であるのがより好ましく、1:0.99であるのがさらに好ましい。
即ち、高分子ユニットとして、式(3)中の(a+b+c+d):(e+f)の比が99.9~90.0モル%:0.1~10.0モル%である。この範囲内であると、水蒸気透過度が必要十分な範囲となり、製膜性も確保される。(e+f)の割合は2.0~8.0モル%がより好ましく、4.5~6.5モル%がさらに好ましい(ここで、モル%の計算上、小数点第2位を四捨五入して小数点第1位までを求める)。
成分(III)と成分(II)との合計量に対して、成分(III)が0.1~2.5モル%であり、かつ、成分(II)が99.9~97.5モル%である。この範囲内であると、水蒸気透過度が必要十分な範囲となり、製膜性も確保される。成分(III)と成分(II)との合計量に対する成分(III)の量は、1.0~2.5モル%がより好ましい(ここで、モル%の計算上、小数点第2位を四捨五入して小数点第1位までを求める)。
成分(II)に含まれるジアミンの合計モル数(MDA´)と、成分(I)に含まれる芳香族テトラカルボン酸無水物のモル数(MFL´)および成分(II)に含まれるテトラカルボン酸無水物の合計モル数(MTC´)の合計(MFL´+MTC´)との比は、MDA´:(MFL´+MTC´)が、1:0.90~1:1.10であるのが好ましく、1:0.95~1:1.05であるのがより好ましく、1:0.99であるのがさらに好ましい。
即ち、高分子ユニットとして、式(4)中の(a+b+c+d):(g+h)の比が99.9~97.5モル%:0.1~2.5モル%である。この範囲内であると、水蒸気透過度が必要十分な範囲となり、製膜性も確保される。(g+h)の割合は1.0~1.5モル%がより好ましい。(ここで、モル%の計算上、小数点第2位を四捨五入して小数点第1位までを求める)。
本発明のポリイミドフィルムの引張弾性率は、ASTM D882に準ずる測定方法によって測定した値で、5.0GPa以上であることが好ましい。この範囲であると、引張り強さが十分なものとなる。引張弾性率は大きいほどよく、5.8GPa以上がより好ましく、6.0GPa以上がさらに好ましく、6.3GPa以上がいっそう好ましく、6.5GPa以上がよりいっそう好ましい。
本発明のポリイミドフィルムの線熱膨張係数は、島津製TMA(Thermomechanical Analysis)−60を用い、荷重0.5g、昇温速度5.0℃/分における試験片の伸びより50℃~200℃の範囲での平均値として求めた値で、10~25ppm/℃の範囲内であることが好ましい。この範囲内であると、銅の線熱膨張係数である17ppm/℃に近いため、ポリイミド/銅基板積層体として用いたときにの熱応力の低減を図ることができる。
本発明のポリイミドフィルムのガラス転移温度は、示差走査熱量計(DSC)を用いて、窒素雰囲気中、昇温速度20℃/分の条件で加熱し、比熱の変化点より測定したものである。本発明のポリイミドフィルムには、明確なガラス転移温度がないことが好ましい。
本発明のポリイミドフィルムの水蒸気透過度は、JIS K 7129:2008(A法)に準拠した測定方法により、測定温度40℃、測定面積50cm2、相対湿度90%、高湿側100%、低湿側10%、測定下限値0.2g/m2/dayとして測定した値で、10~100g/m2/dayであることが好ましい。この範囲内であると、水蒸気透過度が必要十分であり、発泡を起こしにくくなるため、安定製造のために有利である。
水蒸気透過度は25~100g/m2/day以上がより好ましく、40~100g/m2/day以上がさらに好ましく、50~100g/m2/day以上がいっそう好ましい。
本発明のポリイミドを製造する手段としては、低い線熱膨張係数並びに高弾性率を確保する為に、面内配向性を高める手段として、触媒を用いて脱水・環化(イミド化)をする化学イミド化法を用いるのが好ましい。例えば、有機溶媒中でテトラカルボン酸二無水物成分とジアミン成分を5~40℃で3~10時間で重合し、その後、0℃以下の温度で脱水剤と脱水触媒を混合して、ガラス板上に製膜し、不活性ガス雰囲気または減圧下に通常200℃~400℃、好ましくは250℃~350℃の温度で0.5~15時間、好ましくは1~5時間熱処理をする方法を用いる。
実施例および比較例のポリイミドフィルムの線熱膨張係数、機械的靱性、ガラス転移温度および水蒸気透過度は、下記の方法により測定した。
(1)引張弾性率
引張弾性率は、島津製オートグラフAGS−J500Nを用い縦90mm×横10mmの短冊状試験片を使用して、ASTM D882に準じ、チャック間距離50mm、引張り速度50.8mm/min、23℃で測定した。
(2)線熱膨張係数
島津製TMA(Thermomechanical Analysis)−60を用い、荷重0.5g、昇温速度5.0℃/分における試験片の伸びより50℃~200℃の範囲での平均値として線熱膨張係数を求めた。
(3)ガラス転移温度
ガラス転移温度(Tg)は、示差走査熱量計(DSC)を用いて、窒素雰囲気中、昇温速度20℃/分の条件で加熱し、比熱の変化点より測定した。明確なガラス転移温度がなかったものを「検出なし」とした。
(4)水蒸気透過度
Lyssy製L80シリーズ水蒸気透過度計を用いJIS K 7129:2008(A法)に準ずる手法により測定した。測定条件は、測定温度40℃、測定面積50cm2、相対湿度90%、高湿側100%、低湿側10%、測定下限値0.2g/m2/dayとした。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、9,9−ビス(4−アミノフェニル)フルオレン(BAFL)17.4g(0.05モル)、p−フェニレンジアミン48.6g(0.45モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1932gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物161.7g(0.55モル)を投入し、室温下で重合させ、さらに、ピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例1の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、9,9−ビス(4−アミノフェニル)フルオレン(BAFL)34.8g(0.10モル)、p−フェニレンジアミン43.2g(0.40モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1986gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物161.7g(0.55モル)を投入し、室温下で重合させ、さらに、ピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例2の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、9,9−ビス(4−アミノ−3−メチルフェニル)フルオレン(BTFL)37.6g(0.10モル)、p−フェニレンジアミン43.2g(0.40モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1988gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物161.7g(0.55モル)を投入し、室温下で重合させ、さらにピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、ことで、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例3の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、p−フェニレンジアミン54.0g(0.50モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1983gを投入して完全に溶解した。
その後、4,4’−(9−フルオレニリデン)ビス無水フタル酸23g(0.05モル)および3,3’,4,4’−ビフェニルテトラカルボン酸二無水物147.0g(0.50モル)を投入し、室温下で重合させ、さらにピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例4の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、9,9−ビス(4−アミノ−3−フルオロフェニル)フルオレン(BFAF)38.4g(0.10モル)、p−フェニレンジアミン43.3g(0.40モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1995gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物161.75g(0.55モル)を投入し、室温下で重合させ、さらにピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例5の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、9,9−ビス(4−アミノ−3−フェニルフェニル)フルオレン(BPAF)50.1g(0.10モル)、p−フェニレンジアミン43.3g(0.40モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)2050gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物161.75g(0.55モル)を投入し、室温下で重合させ、さらにピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例6の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、p−フェニレンジアミン54.0g(0.50モル)および4,4’−ジアミノフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1950gを投入して完全に溶解した。
その後、4,4’−(9−フルオレニリデン)ビス無水フタル酸46g(0.10モル)および3,3’,4,4’−ビフェニルテトラカルボン酸二無水物132.1g(0.45モル)を投入し、室温下で重合させ、さらにピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の実施例7の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、p−フェニレンジアミン54g(0.50モル)および4,4’−ジアミノジフェニルエーテル100g(0.50モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1877gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物161.7g(0.55モル)を投入し、室温下で重合させ、さらにピロメリット酸二無水物(PMDA)96.36g(0.442モル)を加えて粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の比較例1の欄に示す。
攪拌機、還流冷却器、窒素導入管を備えた反応容器に、p−フェニレンジアミン108g(1.0モル)を仕込み、N,N−ジメチルアセトアミド(DMAc)1821gを投入して完全に溶解した。
その後、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物291.6(0.992モル)を投入し、室温下で重合させ、粘度約1500ポイズのポリイミド前駆体を調製した。
この前駆体に無水酢酸およびβ−ピコリンを加え、平滑なガラス板に製膜し、加熱により乾燥、イミド化する事で、膜厚30μmのポリイミドフィルムを得た。
得られたポリイミドフィルムについて、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度を、上記した測定方法によって、測定した。測定結果は表1の比較例2の欄に示す。
実施例1は、成分(I)として、9,9−ビス(4−アミノフェニル)フルオレンを0.05モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.942モル、使用するものである。
成分(I)と成分(II)との合計に対して、成分(I)は2.5モル%、成分(II)は97.5モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
実施例2は、成分(I)として、9,9−ビス(4−アミノフェニル)フルオレンを0.10モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.892モル、使用するものである。
成分(I)と成分(II)との合計に対して、成分(I)は5.0モル%、成分(II)は95.0モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
実施例3は、成分(I)として、9,9−ビス(4−アミノ−3−フェニルフェニル)フルオレンを0.10モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.892モル、使用するものである。
成分(I)と成分(II)との合計に対して、成分(I)は5.0モル%、成分(II)は95.0モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
実施例4は、成分(III)として、4,4’−(9−フルオレニリデン)ビス無水フタル酸を0.05モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.942モル、使用するものである。
成分(III)と成分(II)との合計に対して、成分(III)は2.5モル%、成分(II)は97.5モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
実施例5は、成分(I)として、9,9−ビス(4−アミノ−3−フルオロフェニル)フルオレン(BFAF)を0.10モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.892モル、使用するものである。
成分(I)と成分(II)との合計に対して、成分(I)は5.0モル%、成分(II)は95.0モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
実施例6は、成分(I)として、9,9−ビス(4−アミノ−3−フェニルフェニル)フルオレン(BPAF)を0.10モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.892モル、使用するものである。
成分(I)と成分(II)との合計に対して、成分(I)は5.0モル%、成分(II)は95.0モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
実施例7は、成分(III)として、4,4’−(9−フルオレニリデン)ビス無水フタル酸を0.10モル、成分(II)として、p−フェニレンジアミン、4,4’−ジアミノジフェニルエーテル、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物およびピロメリット酸二無水物を合計1.892モル、使用するものである。
成分(III)と成分(II)との合計に対して、成分(III)は5.0モル%、成分(II)は95.0モル%であった。
表1から明らかなように、引張弾性率、線熱膨張係数、ガラス転移温度および水蒸気透過度のいずれも良好であった。
比較例1は、成分(I)または成分(III)に相当する成分を使用せず、成分(II)に相当する成分のみによってポリイミドが合成されるものである。
ジアミンとテトラカルボン酸二無水物とのモル比は、1.00:0.992であった。
引張弾性率、線熱膨張率およびガラス転移温度は良好であったが、水蒸気透過度が十分ではなかった。
比較例2は、成分(I)、成分(II)および成分(III)に相当する成分のいずれも使用せず、ジアミンとしてp−フェニレンジアミンを1.0モル、テトラカルボン酸二無水物として3,3’,4,4’−ビフェニルテトラカルボン酸二無水物を0.992モル使用して、ポリイミドが合成されるものである。
ジアミンとテトラカルボン酸二無水物とのモル比は、1.00:0.992であった。
引張弾性率、線熱膨張率およびガラス転移温度は良好であったが、水蒸気透過度が不十分であった。
Claims (5)
- 成分(I):下記式(1)で表される芳香族ジアミンと、
成分(II):3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルとを反応させて得られ、
該成分(I)と該成分(II)との合計量に対して、該成分(I)が0.1~10.0モル%であり、かつ、該成分(II)が99.9~90.0モル%であるポリイミド:
- 成分(III):下記式(2)で表される芳香族テトラカルボン酸二無水物と、
成分(II):3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、p−フェニレンジアミンおよび4,4’−ジアミノジフェニルエーテルとを反応させて得られ、
該成分(III)と該成分(II)との合計量に対して、該成分(III)が0.1~2.5モル%であり、かつ、該成分(II)が99.9~97.5モル%であるポリイミド:
- 請求項1に記載のポリイミドからなるポリイミドフィルム。
- 請求項2に記載のポリイミドからなるポリイミドフィルム。
- 水蒸気透過度が10~100g/m2/dayであり、50~200℃の平均線熱膨張係数が10~25ppm/℃であり、明確なガラス転移温度がなく、かつ、引張弾性率が5.0GPa以上である、請求項3または4に記載のポリイミドフィルム。
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KR102551047B1 (ko) * | 2019-02-01 | 2023-07-04 | 주식회사 엘지화학 | 폴리이미드 필름, 이를 이용한 플렉서블 기판 및 플렉서블 기판을 포함하는 플렉서블 디스플레이 |
CN116348296A (zh) * | 2020-10-22 | 2023-06-27 | 株式会社钟化 | 聚酰胺酸、聚酰胺酸溶液、聚酰亚胺、聚酰亚胺膜、层叠体、电子器件、及聚酰亚胺膜的制造方法 |
WO2022202769A1 (ja) * | 2021-03-23 | 2022-09-29 | 株式会社カネカ | ポリアミド酸、ポリアミド酸溶液、ポリイミド、ポリイミド基板および積層体ならびにそれらの製造方法 |
EP4219606A4 (en) * | 2021-12-08 | 2024-05-29 | Lg Chem, Ltd. | POLYIMIDE RESIN FILM, SUBSTRATE FOR DISPLAY DEVICE THEREOF, AND OPTICAL DEVICE |
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- 2011-09-05 US US13/821,118 patent/US20130211040A1/en not_active Abandoned
- 2011-09-05 KR KR1020137007803A patent/KR20130050373A/ko not_active Application Discontinuation
- 2011-09-05 WO PCT/JP2011/070672 patent/WO2012033213A1/ja active Application Filing
- 2011-09-07 TW TW103124712A patent/TWI582135B/zh active
- 2011-09-07 TW TW100132191A patent/TWI448487B/zh active
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WO2019069723A1 (ja) * | 2017-10-04 | 2019-04-11 | 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 |
JPWO2019069723A1 (ja) * | 2017-10-04 | 2020-09-10 | 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 |
JP7215428B2 (ja) | 2017-10-04 | 2023-01-31 | 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 |
Also Published As
Publication number | Publication date |
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TW201217435A (en) | 2012-05-01 |
US20130211040A1 (en) | 2013-08-15 |
TWI582135B (zh) | 2017-05-11 |
KR20130050373A (ko) | 2013-05-15 |
TW201500410A (zh) | 2015-01-01 |
JP2012077285A (ja) | 2012-04-19 |
JP5727885B2 (ja) | 2015-06-03 |
TWI448487B (zh) | 2014-08-11 |
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