WO2014038538A1 - ポリイミド及び耐熱性材料 - Google Patents
ポリイミド及び耐熱性材料 Download PDFInfo
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- WO2014038538A1 WO2014038538A1 PCT/JP2013/073658 JP2013073658W WO2014038538A1 WO 2014038538 A1 WO2014038538 A1 WO 2014038538A1 JP 2013073658 W JP2013073658 W JP 2013073658W WO 2014038538 A1 WO2014038538 A1 WO 2014038538A1
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- HEWYSGZPWQWEDB-UHFFFAOYSA-N Nc(cc1)ccc1-c1nc(ccc(-c2ccc3nc(-c(cc4)ccc4N)[o]c3c2)c2)c2[o]1 Chemical compound Nc(cc1)ccc1-c1nc(ccc(-c2ccc3nc(-c(cc4)ccc4N)[o]c3c2)c2)c2[o]1 HEWYSGZPWQWEDB-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- 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
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the present invention relates to a polyimide and a heat resistant material.
- the wholly aromatic polyimide has the highest heat resistance (solder heat resistance) among the existing resins, and is therefore applied to members for various uses mainly in the electronics field.
- the conventional polyimide film is strongly colored due to the charge transfer interaction derived from the molecular structure (for example, Non-Patent Document 1), and the advanced low thermal expansion characteristics required for various process compatibility are not always sufficient. Absent. Therefore, it is difficult to apply the current polyimide film as it is to an optical member such as a plastic substrate without improving the characteristics.
- Non-Patent Documents 2 to 4 disclose a method for making transparent.
- an alicyclic structural unit having poor heat resistance is introduced into the polyimide skeleton, a significant decrease in thermal stability is inevitable as compared with conventional wholly aromatic polyimides.
- introduction of an alicyclic structure also causes a decrease in the linearity of the polyimide main chain, colorless and transparent polyimides often do not exhibit low thermal expansion characteristics. As described above, it is not easy in material design to completely satisfy all the required characteristics as a plastic substrate.
- plastic substrate material specialized for some of the above required characteristics.
- a plastic substrate used in top emission organic light emitting diode (OLED) displays is a plastic substrate used in top emission organic light emitting diode (OLED) displays.
- plastic substrates for OLED displays of the top emission type have an extremely high VOC suppression capability (the property that VOC is not generated from the substrate material itself; the same shall apply hereinafter) and an extremely low linear thermal expansion coefficient (hereinafter referred to as CTE). ) And excellent film forming ability (film toughness).
- the structure of the material resin is determined based on the aliphatic hydrocarbon group, thioether group, sulfone group, amine group, carbonate group, urea group, urethane group, amide group, ester group, alkylene group, isopropyl group. It is desirable to completely eliminate substituents and linking groups that are inferior in heat resistance such as a redene group and a cyclohexylene group.
- the main chain structure is extremely rigid and linear from the viewpoint of the development of high low thermal expansion characteristics.
- an ideal molecular structure includes polyparaphenylene having a paraphenylene group represented by the following formula (X1) as a repeating unit.
- polyparaphenylene has no solubility in organic solvents, and if it is obtained by polymerization, precipitation occurs before the molecular weight increases, so the polymerization reaction itself is extremely difficult. is there.
- a polyimide having a repeating unit structure represented by the following formula (X2) having a rigid and linear main chain structure is insoluble in general organic solvents, but has the following formula (X3). It is formed into a film by a solution casting method at the stage of an amide solvent-soluble precursor (polyamic acid) having a repeating unit structure represented by It can be easily obtained as a polyimide film, and it has been reported that the film exhibits extremely low CTE (for example, Non-Patent Document 6).
- the excellent amide solvent solubility of the polyamic acid is due to the strong solvating ability of the COOH group which is a substituent in the above formula (X3) (for example, Non-Patent Document 6).
- Non-Patent Document 5 a polymer having a repeating unit structure represented by the above formula (X2) has almost no entanglement between polymer chains, so that the film is often significantly weakened and completely loses its film forming ability. There is a serious problem (for example, Non-Patent Document 5).
- polybenzoxazole having super heat resistance comparable to polyimide can also be a candidate for the above-mentioned top emission type plastic substrate material for OLED display.
- polybenzoxazole having a repeating unit structure represented by the following formula (X4) is an ideal molecular structure to be applied to the above-mentioned use, that is, has no substituents or linking groups, is rigid and linear It has a main chain structure.
- polybenzoxazole itself is completely insoluble in common organic solvents, so if the polybenzoxazole precursor is soluble in the solvent, a polybenzoxazole film can be produced via this. In principle it is possible.
- Non-Patent Document 7 When a molecular design is made so as to have a chain structure, a serious problem arises in that the solubility in an organic solvent becomes poor even at the stage of polyhydroxyamide, which is a precursor of polybenzoxazole (for example, Non-Patent Document 7).
- the present invention has been made in view of the above circumstances, and has a low linear thermal expansion coefficient, a high glass transition temperature, a high heat resistance, and a high film toughness.
- An object of the present invention is to provide a polyimide that can contribute to weight reduction and fragility improvement of an element by application.
- the inventors of the present invention are derived from a diamine compound containing a benzoxazole group and an aromatic tetracarboxylic dianhydride, and the substitution is inferior in heat resistance in the molecule.
- the polyimide represented by the following formula (1) that does not have a group or a linking group is particularly required for top emission type plastic substrate materials for OLED displays, that is, extremely high VOC suppression ability, advanced low thermal expansion characteristics And it discovered that it showed the outstanding film formation ability, and came to complete this invention. That is, the present invention 1.
- X 1 represents a tetravalent aromatic group having 6 to 14 carbon atoms which may be substituted with an aromatic group having 6 to 20 carbon atoms.
- X 1 is at least one tetravalent group selected from the group consisting of formulas (2) to (4).
- 3. It is obtained by dehydrating and cyclizing a polyimide precursor having a repeating unit represented by the formula (5) having an intrinsic viscosity of 0.3 dL / g or more. Or 2.
- X 1 represents the same meaning as described above.
- Heat-resistant thin film made of heat-resistant materials 6). 4. The thickness is 1 to 100 ⁇ m.
- Heat resistant thin film 7. It has a linear thermal expansion coefficient of not more than 7.15 ppm / K, a glass transition temperature of not less than 370 ° C., and a 5% weight loss temperature of not less than 570 ° C. and a breaking elongation of not less than 20% in a nitrogen atmosphere, 5). Or 6.
- Heat resistant thin film 8.5. ⁇ 7.
- a method for producing a heat-resistant thin film characterized in that any one of the above varnishes is applied onto a substrate and heated at 350 ° C. or higher. 13.
- the polyimide of the present invention has not only a very low coefficient of linear thermal expansion necessary to achieve a very high thermal stability and a high degree of dimensional stability, but also a very high glass transition temperature and excellent film toughness. . Therefore, the polyimide of the present invention is suitable for substrate materials for electronic devices such as photoelectric conversion elements, light emitting elements, image display devices, etc., particularly plastic substrate materials for OLED displays, which have recently been required for these characteristics. It can contribute to weight reduction and vulnerability improvement.
- Example 2 is an FT-IR spectrum of the polyimide precursor thin film described in Example 1.
- 3 is an FT-IR spectrum of the polyimide thin film described in Example 1.
- the polyimide of this invention has a repeating unit represented by Formula (1).
- X 1 represents a tetravalent aromatic group having 6 to 14 carbon atoms which may be substituted with an aromatic group having 6 to 20 carbon atoms.
- a tetravalent aromatic group having 6 to 14 carbon atoms include benzene-1,2,4,5-tetrayl group, benzene-1,2,3,4-tetrayl group, naphthalene- 1,2,3,4-tetrayl group, naphthalene-1,2,5,6-tetrayl group, naphthalene-1,2,6,7-tetrayl group, naphthalene-1,2,7,8-tetrayl group, Naphthalene-2,3,5,6-tetrayl group, naphthalene-2,3,6,7-tetrayl group, naphthalene-1,4,5,8-tetrayl group, biphenyl-2,2 ′, 3,3 ′ -Tetrayl group, biphenyl-2,2
- X 1 in the repeating unit may be the same or different.
- X 1 represents benzene-1,2,4,5-tetrayl group, naphthalene-1,2,3,4-tetrayl group, naphthalene-1,2,5,6-tetrayl group, naphthalene-1 , 2,6,7-tetrayl group, naphthalene-1,2,7,8-tetrayl group, naphthalene-2,3,5,6-tetrayl group, biphenyl-2,2 ′, 3,3′-tetrayl group Biphenyl-2,3,3 ′, 4′-tetrayl group and biphenyl-3,3 ′, 4,4′-tetrayl group are preferable, and any one of the following formulas (2) to (4) It is more preferable.
- any hydrogen atom on the aromatic ring of a tetravalent aromatic group having 6 to 14 carbon atoms in the repeating structure may be substituted with an aromatic group having 6 to 20 carbon atoms.
- the aromatic group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl. Group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
- the polyimide of this invention can be manufactured from the polyimide precursor which has a repeating unit represented by following formula (5).
- the method for producing the polyimide precursor having the repeating unit represented by the above formula (5) is not particularly limited, and a known method can be applied. More specifically, for example, it can be obtained by the following method.
- a diamine represented by the following formula (8) (corresponding to the diamine represented by the formula (6) obtained by the method described later) is dissolved in a solvent, and the tetra represented by the following formula (7) is dissolved therein.
- Carboxylic dianhydride is gradually added and stirred at 0 to 100 ° C., preferably 20 to 60 ° C. for 0.5 to 100 hours, preferably 1 to 72 hours, using a mechanical stirrer.
- the substance amount (mol) ratio between the diamine represented by the formula (8) and the acid dianhydride represented by the formula (7) was 0.8 to 1 with respect to the diamine 1.
- the concentration of the monomer (diamine and dianhydride) in the reaction solvent is 5 to 50% by mass, preferably 10 to 40% by mass.
- the concentration of the monomer (diamine and dianhydride) in the reaction solvent is 5 to 50% by mass, preferably 10 to 40% by mass.
- the polymerization degree of a polyimide precursor increases too much and it becomes difficult to stir a polymerization solution, it can also be suitably diluted with the same solvent as the solvent used for reaction.
- the intrinsic viscosity of the polyimide precursor is preferably 0.3 dL / g or more, preferably 0.3 to 5.0 dL / More preferably, it is within the range of g.
- the polyimide targeted by the present invention is an aromatic tetracarboxylic acid that does not contain any substituents other than phenyl groups or linking groups other than ether groups when polymerizing polyimide from the viewpoint of developing extremely high thermal stability.
- a dianhydride is used.
- the use of an alicyclic tetracarboxylic acid is not preferred because even if it is in a small amount, the thermal stability may be remarkably impaired.
- aromatic tetracarboxylic dianhydride is not particularly limited as long as it satisfies the above conditions, but pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride , Naphthalene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride , Naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene-2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride Anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, biphenyl-2,2 ′, 3,3′-tetracarboxy
- a tetracarboxylic acid having a rigid and linear structure from the viewpoint of low thermal expansion characteristics, availability and cost.
- Dianhydrides, ie, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride It is preferable to use it as a dianhydride component.
- the content of these tetracarboxylic dianhydrides is 50 to 100 mol%, preferably 70 to 100 mol%, based on the total amount of tetracarboxylic dianhydrides used.
- a substituent other than a phenyl group or a linking group other than an ether group may be partially used.
- the use of alicyclic diamines is not preferred because even if the amount is small, the thermal stability may be significantly impaired.
- Such an aromatic diamine is not particularly limited as long as it is within the above-mentioned conditions, but p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′- Diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 2,2′-diaminodiphenyl ether, benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4- Examples include aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, p-terphenylenediamine, and the like. These may be used alone or in combination of two or more. The amount of these copolymerized diamine components used is 0 to 30 mol
- Solvents used in polymerizing the polyimide precursor of the present invention include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 3-methoxy-N, N -Aprotic such as dimethylpropanamide, 3-n-butoxy-N, N-dimethylpropanamide, 3-sec-butoxy-N, N-dimethylpropanamide, 3-t-butoxy-N, N-dimethylpropanamide
- an organic solvent there is no problem as long as the raw material monomer and the polyimide precursor to be produced are dissolved, and the structure is not particularly limited.
- amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, Cyclic ester solvents such as ⁇ -methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, etc.
- Phenol solvents acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like can be used. Furthermore, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene
- a general solvent such as chlorobenzene may be partially used.
- the polyimide precursor polymerization solution of the present invention may be used as it is to produce the heat-resistant thin film of the present invention.
- the polyimide precursor is dropped, filtered and dried in a large amount of poor solvent such as water or methanol. What was obtained and dissolved again in a solvent (such as the solvent used in the production of the polyimide precursor described above) may be used to produce the heat-resistant thin film of the present invention.
- the polyimide precursor polymerization solution and the polyimide precursor dissolved again in a solvent are both varnishes containing the polyimide precursor and are the subject of the present invention.
- the heat-resistant thin film of the present invention can be produced by subjecting the polyimide precursor obtained by the above method to a heat dehydration cyclization reaction (imidation reaction).
- the heat resistant thin film of the present invention is produced as follows.
- the varnish containing the polyimide precursor of the present invention is cast on a substrate of glass, copper, aluminum, stainless steel, silicon or the like and dried in an oven at 40 to 180 ° C., preferably 50 to 150 ° C.
- the obtained heat-resistant thin film (polyimide film) of the present invention is obtained by heating the obtained polyimide precursor film on a substrate in a vacuum, in an inert gas such as nitrogen, or in the air. At this time, the heating temperature is 200 ° C. or higher from the viewpoint of completing the imidization reaction, preferably 250 ° C. or higher, and 450 ° C. or lower, preferably 430 ° C. or lower from the viewpoint of suppressing thermal decomposition of the produced polyimide film.
- the imidization is preferably performed in a vacuum or in an inert gas, but may be performed in air if the imidization temperature is not too high.
- the imidization reaction can be performed by immersing the polyimide precursor film in a solution containing a dehydrating cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine instead of the heat treatment.
- a dehydrating cyclization reagent such as acetic anhydride
- a tertiary amine such as pyridine or triethylamine instead of the heat treatment.
- these dehydration cyclization reagents are charged and stirred at room temperature in advance in a varnish containing a polyimide precursor, and cast and dried on the substrate to obtain a partially imidized polyimide precursor film.
- a polyimide film can be obtained by further heat-treating it as described above.
- an adhesiveless flexible printed circuit board can be manufactured by etching the metal layer into a desired circuit shape using an etching solution such as an aqueous ferric chloride solution.
- the thickness of the heat-resistant thin film of the present invention is not particularly limited, and the thickness may be appropriately determined according to the purpose of use.
- the heat-resistant thin film itself is converted into a photoelectric conversion such as organic solar electricity or silicon solar cell.
- a light emitting element such as an element or an organic EL element, or as a substrate for circuit electronics
- about 1 to 100 ⁇ m is preferable.
- the heat-resistant thin film of the present invention described above can be easily manufactured from the polyimide precursor having the excellent film forming ability of the present invention, and has extremely high VOC suppression ability and advanced low thermal expansion characteristics. It can be suitably used as a heat-resistant thin film on a substrate such as an organic EL element, a liquid crystal display element or organic solar electricity.
- the polyimide precursor and polyimide of this invention are obtained from the tetracarboxylic dianhydride and BO containing diamine which are the monomers as mentioned above.
- the BO group-containing diamine used in the present invention is represented by the following formula (8).
- the BO group-containing diamine represented by the above formula (8) is synthesized using bis (o-aminophenol) represented by the following formula (9) as a starting material.
- p-HAB is dissolved in a well-dehydrated amide solvent in a three-necked flask, and pyridine is added thereto as a deoxidizing agent, which is then sealed with a septum cap to obtain liquid A.
- 2-nitrobenzoic acid chloride of 2-fold molar amount of p-HAB is dissolved in the same solvent as the liquid A in an eggplant type flask, and sealed with a septum cap to obtain a liquid B.
- liquid A is cooled in an ice bath, liquid B is gradually added to liquid A with a syringe while stirring with a rotor, and stirring is continued for several hours after completion of the addition to synthesize a diamide.
- the dinitro compound represented by the above formula (10) is dissolved in an amide solvent in a three-necked flask, an appropriate amount of Pd / C is added as a catalyst, and 1 to 24 at room temperature to 150 ° C. in a hydrogen atmosphere. Perform a time reduction reaction. The progress of the reaction can be followed by thin layer chromatography. After completion of the reaction, Pd / C is separated by filtration, and then the filtrate is slowly dropped into a large amount of water to precipitate the product. The precipitate is collected by filtration, washed repeatedly with water and then vacuum dried at 100 ° C. for 12 hours. If necessary, it can be highly purified by recrystallization from an appropriate solvent. In this way, a BO group-containing diamine represented by the following formula (6) that can be used for polymerization of the polyimide precursor of the present invention is obtained.
- ⁇ Infrared absorption spectrum> Using a Fourier transform infrared spectrophotometer (FT-IR5300 manufactured by JASCO Corporation), the infrared absorption spectrum of the BO group-containing diamine was measured by the KBr plate method. Moreover, the infrared absorption spectrum of the polyimide precursor film and the polyimide film (about 5 micrometers thickness) was measured with the transmission method.
- FT-IR5300 Fourier transform infrared spectrophotometer
- ⁇ Differential scanning calorimetry melting point and melting curve
- the melting point and melting curve of the BO group-containing diamine were measured using a differential scanning calorimeter (DSC3100) manufactured by Bruker Ax in a nitrogen atmosphere at a heating rate of 2 ° C./min. The higher the melting point and the sharper the melting peak, the higher the purity.
- T g Glass of polyimide film (thickness: 20 ⁇ m) was measured from the peak temperature of the loss energy curve at a frequency of 0.1 Hz and a heating rate of 5 ° C./min by dynamic viscoelasticity measurement using a thermomechanical analyzer (TMA4000) manufactured by Bruker Ax. The transition temperature was determined.
- TMA4000 thermomechanical analyzer manufactured by Bruker Ax
- a range of 100 to 200 ° C. from the elongation of the test piece at a load of 0.5 g / film thickness of 1 ⁇ m and a temperature increase rate of 5 ° C./min was determined by thermomechanical analysis.
- CTE of a polyimide film (20 ⁇ m thickness) was determined as an average value at. ⁇ 5% weight loss temperature (T d 5 )> Using a thermogravimetric analyzer (TG-DTA2000) manufactured by Bruker Ax, the initial weight of the polyimide film (20 ⁇ m thickness) is 5% in the temperature rising process at a temperature rising rate of 10 ° C./min in nitrogen or air. The temperature at the time of decrease was measured. Higher values indicate higher thermal stability.
- the dinitro compound represented by the above formula (10) (6.13 g, 11.9 mmol) was dissolved in NMP (250 mL), and Pd / C (0.63 g) was added as a catalyst.
- the reduction reaction was performed in a hydrogen atmosphere at 100 ° C. for 15 hours. The progress of the reaction was followed by thin layer chromatography. After completion of the reaction, Pd / C was separated by filtration, and then the filtrate was slowly added dropwise to water to precipitate the product. The precipitate was collected by filtration, washed repeatedly with water and then vacuum dried at 100 ° C. for 12 hours to obtain a brown powder with a crude product yield of 82%.
- Example 1 A well-dried sealed reaction vessel with a stirrer is charged with 5 mmol of the BO group-containing diamine represented by the above formula (6), dissolved in NMP sufficiently dehydrated with Molecular Sieves 4A at about 50 ° C., and then allowed to cool to room temperature. Then, 5 mmol of 2,3,6,7′-naphthalenetetracarboxylic dianhydride (manufactured by JFE Chemical Co., Ltd., hereinafter referred to as NTDA) powder was added to this solution (total solute concentration: 13% by mass).
- NTDA 2,3,6,7′-naphthalenetetracarboxylic dianhydride
- FIG. 1 shows an infrared absorption spectrum of the thin film of the polyimide precursor obtained.
- FIG. 2 shows an infrared absorption spectrum of a polyimide film prepared separately under the same conditions.
- the obtained polyimide film showed no solubility in any organic solvent.
- a glass transition point was observed at 408 ° C.
- the linear thermal expansion coefficient showed a very low value of 8.4 ppm / K. This is due to the fact that the main chain structure of the polyimide of the present invention is extremely rigid and highly linear, and that the main chain of the polyimide is remarkably oriented in the direction parallel to the film surface in the thermal imidization process. It is done.
- the 5% weight loss temperature was 603 ° C. in nitrogen and 592 ° C. in air, and it was found that the obtained polyimide had extremely high thermal stability.
- Example 2 Except for using the same molar amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as BPDA) instead of NTDA as the tetracarboxylic dianhydride component, A polyimide precursor was polymerized according to the method described in Example 1, and film formation, thermal imidization, and film physical properties were evaluated. Table 1 shows the physical properties. Similar to the polyimide described in Example 1, excellent characteristics were exhibited. In the table, ND represents that no glass transition was detected in the dynamic viscoelasticity measurement from room temperature to 500 ° C.
- BPDA 4,4′-biphenyltetracarboxylic dianhydride
- Example 3 A polyimide precursor according to the method described in Example 1 except that the same molar amount of pyromellitic dianhydride (Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as PMDA) was used instead of NTDA as the tetracarboxylic dianhydride component.
- PMDA pyromellitic dianhydride
- NTDA tetracarboxylic dianhydride component
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Abstract
Description
しかしながら、従来のポリイミドフィルムは、分子構造由来の電荷移動相互作用により強く着色しており(例えば非特許文献1)、また、各種プロセス適合性のために求められる高度な低熱膨張特性は必ずしも十分ではない。
そのため、現行のポリイミドフィルムを何ら特性改善することなくそのままプラスチック基板等の光学部材に適用することは困難である。
しかしながら、この場合、ポリイミド骨格中に耐熱性に劣る脂環構造単位が導入されるため、従来の全芳香族ポリイミドに比べると、熱安定性の大幅な低下は避けられない。また、脂環構造導入はポリイミド主鎖の直線性の低下も招くため、無色透明ポリイミドはしばしば低熱膨張特性を示さない。
このように、プラスチック基板として全ての要求特性を完璧に満たすことは材料設計上容易なことではない。
そのため、OLED用プラスチック基板材料としては、できるだけ高温域までVOCの発生を抑制するための極めて高い熱安定性、高度な熱寸法安定性(即ち、低熱膨張特性)、ガラス並みの無色透明性及び優れた膜形成能(膜靱性)を併せ持つ、従来にない材料が求められているが、これら全ての要求特性をターゲットとする樹脂材料開発のハードルは極めて高い。
そのため、トップ・エミッション方式のOLEDディスプレー用プラスチック基板では、極めて高いVOC抑制能(基板材料自身からVOCが発生しない性質のことである。以下同じ。)、極めて低い線熱膨張係数(以下CTEと称する)及び優れた膜形成能(膜靱性)が求められる。
しかし、ポリパラフェニレンは有機溶媒への溶解性を全く有しておらず、これを重合して得ようとすると分子量が増加する前に沈殿が生じてしまうため、その重合反応そのものが極めて困難である。
例えば、下記式(X4)で表される繰り返し単位構造を有するポリベンゾオキサゾールは、上記用途に適用するのに理想的な分子構造、即ち、置換基や連結基を一切有さず、剛直で直線状の主鎖構造を有している。
この点に加え、VOC抑制能と低熱膨張特性の発現を目指して、上記式(X4)に例示したように、ポリベンゾオキサゾールから連結基を完全に排除した上で、剛直で直線性の高い主鎖構造となるように分子設計すると、ポリベンゾオキサゾールの前駆体であるポリヒドロキシアミドの段階でさえも有機溶媒への溶解性が乏しくなるという重大な問題が生じる(例えば非特許文献7)。
即ち、本発明は、
1.式(1)で表される繰り返し単位を有するポリイミド、
2.前記X1が、式(2)~(4)からなる群より選ばれる少なくとも1種の4価の基である1.のポリイミド、
4.1.~3.のいずれかのポリイミドからなる耐熱性材料、
5.4.の耐熱性材料からなる耐熱性薄膜、
6.厚さが1~100μmである5.の耐熱性薄膜、
7.15ppm/K以下の線熱膨張係数、370℃以上のガラス転移温度、及び、窒素雰囲気中、570℃以上の5%重量減少温度及び20%以上の破断伸びを有することを特徴とする、5.又は6.の耐熱性薄膜、
8.5.~7.のいずれかの耐熱性薄膜からなる、光電変換素子、発光素子又は電子回路用の基板、
9.式(5)で表される繰り返し単位を有するポリイミド前駆体を含むワニス、
10.前記X1が、式(2)~(4)からなる群より選ばれる少なくとも1種の4価の基である9.のワニス、
12.9.~11.のいずれかのワニスを基板上に塗布し、これを350℃以上で加熱することを特徴とする、耐熱性薄膜の製造方法、
13.式(5)で表される繰り返し単位を有するポリイミド前駆体、
14.固有粘度が、0.3dL/g以上である13.のポリイミド前駆体
を提供する。
本発明のポリイミドは、式(1)で表される繰り返し単位を有する。
このような炭素原子数6~14の4価の芳香族基の具体例としては、ベンゼン-1,2,4,5-テトライル基、ベンゼン-1,2,3,4-テトライル基、ナフタレン-1,2,3,4-テトライル基、ナフタレン-1,2,5,6-テトライル基、ナフタレン-1,2,6,7-テトライル基、ナフタレン-1,2,7,8-テトライル基、ナフタレン-2,3,5,6-テトライル基、ナフタレン-2,3,6,7-テトライル基、ナフタレン-1,4,5,8-テトライル基、ビフェニル-2,2’,3,3’-テトライル基、ビフェニル-2,3,3’,4’-テトライル基、ビフェニル-3,3’,4,4’-テトライル基、アントラセン-1,2,3,4-テトライル基、アントラセン-1,2,5,6-テトライル基、アントラセン-1,2,6,7-テトライル基、アントラセン-1,2,7,8-テトラキル基、アントラセン-2,3,6,7-テトライル基、フェナントラセン-1,2,3,4-テトライル基、フェナントラセン-1,2,5,6-テトライル基、フェナントラセン-1,2,6,7-テトライル基、フェナントラセン-1,2,7,8-テトライル基、フェナントラセン-1,2,9,10-テトライル基、フェナントラセン-2,3,5,6-テトライル基、フェナントラセン-2,3,6,7-テトライル基、フェナントラセン-2,3,9,10-テトライル基、フェナントラセン-3,4,5,6-テトライル基、フェナントラセン-3,4,9,10-テトライル基、フェニルエーテル-3,3’,4,4’-テトライル基、ハイドロキノン-ジフタリックアンハイドライド-テトライル基等が挙げられる。繰り返し単位中のX1は、同一であっても、異なっていてもよい。
これらの中でも、X1は、ベンゼン-1,2,4,5-テトライル基、ナフタレン-1,2,3,4-テトライル基、ナフタレン-1,2,5,6-テトライル基、ナフタレン-1,2,6,7-テトライル基、ナフタレン-1,2,7,8-テトライル基、ナフタレン-2,3,5,6-テトライル基、ビフェニル-2,2’,3,3’-テトライル基、ビフェニル-2,3,3’,4’-テトライル基、ビフェニル-3,3’,4,4’-テトライル基であることが好ましく、下記式(2)~(4)のいずれかであることがより好ましい。
このような炭素原子数6~20の芳香族基の具体例としては、フェニル基、1-ナフチル基、2-ナフチル基、1-アントリル基、2-アントリル基、9-アントリル基、1-フェナントリル基、2-フェナントリル基、3-フェナントリル基、4-フェナントリル基、9-フェナントリル基等が挙げられる。
本発明のポリイミドは、下記式(5)で表される繰り返し単位を有するポリイミド前駆体から製造することができる。
まず、下記式(8)で表されるジアミン(後述の方法により得られる式(6)で表されるジアミンに対応する)を溶媒に溶解し、これに下記式(7)で表されるテトラカルボン酸二無水物を徐々に添加し、メカニカルスターラーを用い、0~100℃、好ましくは20~60℃で0.5~100時間、好ましくは1~72時間撹拌する。
本発明の耐熱性薄膜の靭性の観点から、ポリイミド前駆体の重合度はできるだけ高いことが望ましく、それゆえ、反応溶媒中のモノマー濃度を5~50質量%、好ましくは10~40質量%としてポリイミド前駆体を調製することが望ましい。
例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン等のアミド溶媒、γ-ブチロラクトン、γ-バレロラクトン、δ-バレロラクトン、γ-カプロラクトン、ε-カプロラクトン、α-メチル-γ-ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、m-クレゾール、p-クレゾール、3-クロロフェノール、4-クロロフェノール等のフェノール系溶媒、アセトフェノン、1,3-ジメチル-2-イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが使用可能である。
更に、フェノール、o-クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールモノメチルエーテルアセテート、テトラヒドロフラン、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン等の一般的な溶媒も部分的に使用してもよい。
本発明の耐熱性薄膜は、上記の方法で得られたポリイミド前駆体を加熱脱水環化反応(イミド化反応)することで製造することができる。
本発明のポリイミド前駆体を含むワニスを、ガラス、銅、アルミニウム、ステンレス、シリコン等の基板上に流延し、オーブン中、40~180℃、好ましくは50~150℃で乾燥し、ポリイミド前駆体フィルムを作製する。
得られたポリイミド前駆体フィルムを基板上で真空中、窒素等の不活性ガス中、あるいは空気中、加熱することで本発明の耐熱性薄膜(ポリイミドフィルム)が得られる。
この際、加熱温度は、イミド化反応を完結するという観点から200℃以上、好ましくは250℃以上、生成したポリイミドフィルムの熱分解を抑制するという観点から450℃以下、好ましくは430℃以下である。
また、イミド化は真空中あるいは不活性ガス中で行うことが望ましいが、イミド化温度が高すぎなければ空気中で行ってもよい。
また、これらの脱水環化試薬をあらかじめポリイミド前駆体を含むワニス中に室温で投入・撹拌し、それを上記基板上に流延・乾燥することで、部分的にイミド化したポリイミド前駆体フィルムを作製することもでき、これを更に上記のように熱処理することでポリイミドフィルムが得られる。
以上説明した本発明の耐熱性薄膜は、本発明の優れた膜形成能を有するポリイミドの前駆体から容易に製造することができ、極めて高いVOC抑制能と高度な低熱膨張特性を有することから、有機EL素子、液晶表示素子や有機太陽電気等の基板における耐熱性の薄膜として好適に用いることができる。
本発明のポリイミド前駆体及びポリイミドは、前述したようにそのモノマーであるテトラカルボン酸二無水物とBO含有ジアミンより得られる。
本発明で用いるBO基含有ジアミンは、下記式(8)で表される。
次に、ナス型フラスコ中、p-HABの2倍モル量の4-ニトロ安息香酸クロリドをA液と同様の溶媒に溶解し、セプタムキャップでシールしてB液とする。
そして、A液を氷浴中で冷却し、回転子で撹拌しながらシリンジにてB液をA液に少しずつ加え、添加終了後数時間撹拌を続け、ジアミド体を合成する。
生成した沈殿物を濾過により集めて水で繰り返し洗浄した後、100℃で12時間真空乾燥して下記式(10)で表されるジニトロ体を合成する
反応終了後、濾過によりPd/Cを分離した後、濾液を大量の水にゆっくりと滴下して生成物を析出させる。沈殿物を濾過により集めて水で繰り返し洗浄した後、100℃で12時間真空乾燥する。必要に応じて適当な溶媒から再結晶して高純度化することもできる。
このようにして、本発明のポリイミド前駆体の重合に用いることができる下記式(6)で表されるBO基含有ジアミンが得られる。
フーリエ変換赤外分光光度計(日本分光社製FT-IR5300)を用い、KBrプレート法にてBO基含有ジアミンの赤外線吸収スペクトルを測定した。また透過法にてポリイミド前駆体フィルム及びポリイミドフィルム(約5μm厚)の赤外線吸収スペクトルを測定した。
<1H-NMRスペクトル>
日本電子社製NMR分光光度計(ECP400)を用い、重水素化ジメチルスルホキシド中でBO基含有ジアミンの1H-NMRスペクトルを測定した。
<示差走査熱量分析(融点及び融解曲線)>
BO基含有ジアミンの融点及び融解曲線は、ブルカーエイエックス社製示差走査熱量分析装置(DSC3100)を用いて、窒素雰囲気中、昇温速度2℃/分で測定した。融点が高く融解ピークがシャープであるほど、高純度であることを示す。
<固有粘度>
0.5質量%のポリイミド前駆体溶液を、オストワルド粘度計を用いて30℃で測定した。
<ガラス転移温度(Tg)>
ブルカーエイエックス社製熱機械分析装置(TMA4000)を用いて動的粘弾性測定により、周波数0.1Hz、昇温速度5℃/分における損失エネルギー曲線のピーク温度からポリイミドフィルム(20μm厚)のガラス転移温度を求めた。
<線熱膨張係数:CTE>
ブルカーエイエックス社製熱機械分析装置(TMA4000)を用いて、熱機械分析により、荷重0.5g/膜厚1μm、昇温速度5℃/分における試験片の伸びより、100~200℃の範囲での平均値としてポリイミドフィルム(20μm厚)のCTEを求めた。
<5%重量減少温度(Td 5)>
ブルカーエイエックス社製熱重量分析装置(TG-DTA2000)を用いて、窒素中または空気中、昇温速度10℃/分での昇温過程において、ポリイミドフィルム(20μm厚)の初期重量が5%減少した時の温度を測定した。これらの値が高いほど、熱安定性が高いことを表す。
<弾性率、破断伸び、破断強度>
東洋ボールドウィン社製引張試験機(テンシロンUTM-2)を用いて、ポリイミド試験片(3mm×30mm×20μm厚)について引張試験(延伸速度:8mm/分)を実施し、応力―歪曲線の初期の勾配から弾性率を、フィルムが破断した時の伸び率から破断伸び(%)を求めた。破断伸びが高いほどフィルムの靭性が高いことを意味する。
<BO基含有ジアミンの合成>
3つ口フラスコ中、p-HAB(和歌山精化社製、2.61g、12mmol)をよく脱水させたN-メチル-2-ピロリドン(以下、NMPという。)(81mL)に溶解し、これに脱酸剤としてピリジン(2.9mL、36mmol)を添加し、セプタムキャップでシールしてA液とした。次に別のナス型フラスコ中、4-ニトロ安息香酸クロリド(4.49g、24mmol)をNMP(17mL)に溶解し、セプタムキャップでシールしてB液とした。A液を氷浴中で冷却し、回転子で撹拌しながらシリンジにてB液をA液に少しずつ加え、添加終了後3時間撹拌を続け、ジアミド体を合成した。
得られた生成物は、DMSO-d6やCDCl3に殆ど不溶であったため、1H-NMR測定は実施しなかったが、その赤外線吸収スペクトルは、1605cm-1にBO基C=N伸縮振動バンド、1518/1348cm-1にニトロ基伸縮振動バンドを示し、アミドC=O伸縮振動バンドやフェノール性O-H伸縮振動バンドは見られなかった。
これらの結果から、得られた生成物は、下記式(10)で表されるジニトロ体であると考えられる。
得られた生成物の赤外線吸収スペクトルは、3454/3380/3210cm-1にアミノ基N-H伸縮振動バンド、1621/1607cm-1にBO基C=N伸縮振動バンド、1499cm-1に1,4-フェニレン基伸縮振動バンドを示し、ニトロ基伸縮振動バンドやアミドC=O伸縮振動バンドは見られなかった。
この赤外線吸収スペクトルの結果と下記1H-NMRスペクトル及び元素分析の結果から、得られた生成物は、下記式(6)で表されるBO基含有ジアミンであることが確認された。
1H-NMRスペクトル(400MHz,DMSO-d6,δ,ppm):8.06(s,2H),7.90-7.88(d,4H),7.75-7.71(m,4H),6.72-6.70(d,4H),6.04(s,4H)
元素分析:推定値C;74.63%,H;4.34%,N;13.39%,分析値C;74.41%,H;4.47%,N;13.26%
[実施例1]
よく乾燥した撹拌機付密閉反応容器中に上記式(6)で表されるBO基含有ジアミン5mmolを入れ、モレキュラーシーブス4Aで十分に脱水したNMPに約50℃で溶解した後、室温まで放冷し、この溶液に2,3,6,7’-ナフタレンテトラカルボン酸二無水物(JFEケミカル社製、以下NTDAと称する)粉末5mmolを加えた(全溶質濃度:13質量%)。その後、室温で72時間撹拌して、均一で粘稠なポリイミド前駆体を含む溶液(ポリイミド前駆体溶液)を得た。
NMP中、30℃、0.5質量%の濃度でオストワルド粘度計にて測定したポリイミド前駆体の固有粘度は1.15dL/gであった。
上記ポリイミド前駆体溶液をガラス基板に塗布し、熱風乾燥機中80℃で3時間乾燥してポリイミド前駆体フィルムを作製した。
図1に得られたポリイミド前駆体の薄膜の赤外線吸収スペクトルを示す。2600cm-1付近にブロードな吸収帯(水素結合性COOH基O-H伸縮振動バンド)、1711cm-1に水素結合性COOH基C=O伸縮振動バンド、1678cm-1(ショルダー)/1530cm-1にアミド基C=O伸縮振動バンド、1501cm-1に1,4-フェニレン基伸縮振動バンドが観測され、一方、モノマー由来のアミノ基N-H伸縮振動バンドやテトラカルボン酸二無水物の酸無水物基C=O伸縮振動バンドが見られないことから、目的とするポリイミド前駆体の生成が確認された。
図2に同一条件で別途作製されたポリイミドフィルムの赤外線吸収スペクトルを示す。3046cm-1に芳香族C-H伸縮振動バンド、1777/1721cm-1にイミド基C=O伸縮振動バンド、1618cm-1にBO基C=N伸縮振動バンド、1501cm-1に1,4-フェニレン基伸縮振動バンド、1356cm-1にイミド基N-C(芳香族)伸縮振動バンドが観測され、一方、COOH基やアミド基に由来する吸収帯が見られないことから、イミド化反応は完結しており、目的とするポリイミドの生成が確認された。
テトラカルボン酸二無水物成分としてNTDAの代わりに3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(和光純薬社製、以下BPDAと称する)を同モル量用いた以外は、実施例1に記載した方法に従ってポリイミド前駆体を重合し、製膜、熱イミド化、膜物性評価を行った。表1に物性を示す。実施例1に記載のポリイミドと同様、優れた特性を示した。
なお、表中、NDは室温~500℃までの動的粘弾性測定においてガラス転移が未検出であったことを表す。
テトラカルボン酸二無水物成分としてNTDAの代わりにピロメリット酸二無水物(三菱瓦斯化学社製、以下PMDAと称する)を同モル量用いた以外は、実施例1に記載した方法に従ってポリイミド前駆体を重合し、製膜、熱イミド化、膜物性評価を行った。表1に物性を示す。実施例1に記載のポリイミドと同様、優れた特性を示した。
テトラカルボン酸二無水物成分としてPMDA、ジアミン成分としてp-フェニレンジアミンを同モル量用い、実施例1に記載した方法に準じて重合、製膜、熱イミド化してポリイミドフィルムを作製した。このポリイミドフィルムは極めて低いCTE(2.8ppm/K)を示したが、非常に脆弱であり破断伸びは0%であった。また、このフィルムは折り曲げることで容易に破断した。これは、このポリイミド系の棒状主鎖構造に由来するもので、ポリマー鎖間の絡み合いが殆どないためである。
テトラカルボン酸二無水物成分としてPMDAを同モル量、ジアミン成分として4,4’-オキシジアニリンを同モル量それぞれ用い、実施例1に記載した方法に準じて重合、製膜、熱イミド化、膜物性評価を行った。このポリイミドフィルムは極めて高いガラス転移温度(408℃)を示し、破断伸び85%と優れた靱性を有していたが、CTEは42.8ppm/Kであり、低熱膨張特性を示さなかった。
Claims (14)
- 請求項1乃至3のいずれか1項に記載のポリイミドからなる耐熱性材料。
- 請求項4に記載の耐熱性材料からなる耐熱性薄膜。
- 厚さが1乃至100μmである、請求項5に記載の耐熱性薄膜。
- 15ppm/K以下の線熱膨張係数、370℃以上のガラス転移温度、及び、窒素雰囲気中、570℃以上の5%重量減少温度及び20%以上の破断伸びを有することを特徴とする、請求項5又は6に記載の耐熱性薄膜。
- 請求項5乃至7のいずれか1項に記載の耐熱性薄膜からなる、光電変換素子、発光素子又は電子回路用の基板。
- 前記ポリイミド前駆体が、0.3dL/g以上の固有粘度を有する、請求項9又は10に記載のワニス。
- 請求項9乃至11のいずれか1項に記載のワニスを基板上に塗布し、これを350℃以上で加熱することを特徴とする、耐熱性薄膜の製造方法。
- 固有粘度が0.3dL/g以上である、請求項13に記載のポリイミド前駆体。
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KR102147319B1 (ko) | 2019-09-30 | 2020-08-24 | 에스케이이노베이션 주식회사 | 폴리이미드계 필름 및 이를 포함하는 플렉서블 디스플레이 패널 |
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