CN114920931A - Polyimide precursor composition, polyimide film, and method for producing same - Google Patents
Polyimide precursor composition, polyimide film, and method for producing same Download PDFInfo
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- CN114920931A CN114920931A CN202210594770.8A CN202210594770A CN114920931A CN 114920931 A CN114920931 A CN 114920931A CN 202210594770 A CN202210594770 A CN 202210594770A CN 114920931 A CN114920931 A CN 114920931A
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
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Abstract
The present invention relates to a polyimide precursor composition, a polyimide film and a method for preparing the same. The polyimide precursor composition is characterized by being prepared by adding tetracarboxylic acid into a reaction system of tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic acid can be converted into the tetracarboxylic dianhydride when being heated, the molar ratio of the tetracarboxylic dianhydride to the diamine is 0.900-1.100, the molar ratio of the tetracarboxylic acid to the diamine is 0.001-0.500, and the ratio of the molar mass of the tetracarboxylic dianhydride and the tetracarboxylic acid to the molar mass of the diamine is 0.900-1.100. According to the present invention, a polyimide precursor composition capable of producing a polyimide film excellent in heat resistance, thermal decomposition resistance and mechanical properties, and a polyimide film obtained from the precursor can be provided.
Description
Technical Field
The invention relates to the field of polyimide materials, in particular to a polyimide precursor composition, a polyimide film and a preparation method thereof.
Background
Polyimide is a generic term for polymers comprising imide rings (-CO-N-CO-) in the main chain. Polyimide is one of organic polymer materials with excellent comprehensive performance, has the heat-resistant temperature of more than 400 ℃, high insulativity, very small dielectric constant and dielectric loss and good chemical property.
Polyimide exhibits excellent application possibilities in many fields in view of its excellent thermal stability, chemical stability, mechanical properties and specific electrical properties. In recent years, with the progress of size reduction, weight reduction, and high performance of electronic devices such as organic EL, there has been a demand for polyimide materials having more excellent heat resistance and dimensional stability than conventional polyimide materials.
As a method for solving the above-mentioned problems, patent document 1 discloses a polyimide which is excellent in transparency and is formed by using tetracarboxylic dianhydride having an alicyclic structure and various diamines, and a precursor thereof, but the glass transition temperature of the polyimide obtained is at most 337 ℃. Patent document 2 discloses a method for producing a transparent polyimide having excellent mechanical properties by adding an imidazole compound.
Non-patent document 1 discloses that a diamine having an imidazole structure is mono-5-amino-2- (p-aminophenyl) benzimidazole, and is introduced into a molecular system of BPDA and PPD, thereby producing a polyimide fiber having excellent mechanical properties by a spinning technique.
However, the polyimide materials disclosed above do not satisfy the current requirements for heat resistance and dimensional stability of polyimides. Further, when a high-viscosity polyamic acid solution having a high polymerization degree is applied, it is necessary to prepare the solution itself to have a viscosity capable of application, but the polyamic acid solution prepared by the above method has a poor processability because the viscosity is difficult to control.
Documents of the prior art
Patent document
Patent document 1: JP2008-231327A
Patent document 2: CN109535423A
Non-patent literature
Non-patent document 1: ZhengSensen, GuoTao, DongJie, WangShihua, ZhangQinghua. preparation, structure and properties of high-strength high-modulus polyminicide containment b enzimizamidomethyl [ J ]. JournalofTextilereresearch, 2021,42(02):7-11+20.
Disclosure of Invention
In order to solve at least one of the above-mentioned problems, a first aspect of the present invention provides a polyimide precursor composition obtained by adding a tetracarboxylic acid to a reaction system of a tetracarboxylic dianhydride and a diamine, wherein the tetracarboxylic acid is converted into the tetracarboxylic dianhydride when heated, the molar ratio of the tetracarboxylic dianhydride to the diamine is 0.900 to 1.100, the molar ratio of the tetracarboxylic acid to the diamine is 0.001 to 0.500, and the molar ratio of the molar mass of the tetracarboxylic dianhydride and the tetracarboxylic acid to the molar mass of the diamine is 0.900 to 1.100;
preferably, the molar ratio of the tetracarboxylic dianhydride to the diamine is 0.900-0.990;
preferably, the solid content concentration of the polyamic acid solution is 5 to 50 wt%, more preferably, 10 to 25 wt%;
preferably, the molar ratio of the tetracarboxylic acid to the diamine is 0.005 to 0.100;
preferably, the ratio of the molar mass of the tetracarboxylic dianhydride and the tetracarboxylic acid to the molar mass of the diamine is 0.940 to 1.004.
According to the polyimide precursor composition, the tetracarboxylic acid serving as a viscosity modifier is added into a reaction system of the tetracarboxylic dianhydride and the diamine, so that the prepared polyimide precursor composition solution has proper viscosity and the processability is improved; further, a polyimide material having excellent thermal stability and mechanical properties can be obtained by adding a tetracarboxylic acid dianhydride and a tetracarboxylic acid to a diamine in a specific ratio to prepare a polyimide precursor composition having excellent processability and then performing a curing process.
In the above polyimide precursor composition, the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, 3,4, 4-benzophenone tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 4,4' -oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride, 4, 4-bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, sulfonylphthalic anhydride, cyclobutane-1, preferably, the tetracarboxylic acid dianhydride is 3,3',4,4' -biphenyltetracarboxylic acid dianhydride and/or trimellitic acid dianhydride.
In the polyimide precursor composition, the diamine is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenyl ether, p-methylenedianiline, m-methylenedianiline, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis (trifluoromethyl) benzidine, 2 ' -bis [4 (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (3-aminophenyl) hexafluoropropane, 2 ' -bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 2-bis [4- (4-aminophenoxy) -phenyl ] propane, p-phenylenediamine, m-methylenedianiline, 1, 3-bis (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (4-aminophenoxy) phenyl ] sulfone, 1, 3-cyclohexanediamine, 4-cyclohexanediamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4-aminophenyl) propane, 2-diphenylamine, and mixtures thereof, 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4 '-bis (3-aminophenoxy) diphenylsulfone, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene, and preferably, the diamine is one or more selected from the group consisting of p-phenylenediamine, m-phenylenediamine, and 4,4' -diaminodiphenyl ether.
In the polyimide precursor composition, the tetracarboxylic acid is one or more selected from the group consisting of 3,3',4,4' -biphenyltetracarboxylic acid, 2,3, 3', 4' -biphenyltetracarboxylic acid, 4,4'- (4, 4' -isopropenyldiphenoxy) bis (phthalic acid), 4,4'- (hexafluoroisopropylidine) dibenzoic acid, 4,4' -hydroxydibenzoic acid, and 3,3',4,4' -benzophenonetetracarboxylic acid, and preferably the tetracarboxylic acid is 3,3',4,4' -biphenyltetracarboxylic acid and/or 2,3, 3', 4' -biphenyltetracarboxylic acid.
A second aspect of the present invention provides a method for producing a polyimide precursor composition, characterized by comprising the steps of: completely dissolving diamine in an organic solvent to obtain a diamine solution, and slowly adding tetracarboxylic dianhydride while stirring the diamine solution to obtain a reaction solution; continuously stirring the reaction solution at the temperature of 20-80 ℃; adding a tetracarboxylic acid to the reaction solution, and completely dissolving the tetracarboxylic acid, thereby obtaining the polyimide precursor composition.
According to the method for producing a polyimide precursor composition of the present invention, by adding tetracarboxylic acid as a viscosity modifier to a reaction system of tetracarboxylic dianhydride and diamine, the resulting polyimide precursor composition solution can have an appropriate viscosity, and the processability can be improved, and by controlling the reaction temperature, the progress of imidization can be controlled, and the stability of the resulting polyimide precursor composition can be improved.
In the above-mentioned method for producing a polyimide precursor composition, the tetracarboxylic acid can be converted into a tetracarboxylic dianhydride when heated, and preferably, the tetracarboxylic acid can be converted into a tetracarboxylic dianhydride at 200 ℃ or higher.
A third aspect of the present invention provides a polyimide film having a thickness of 1 μm or more, preferably 2 μm or more, more preferably 5 μm or more, and 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, further preferably 15 μm or less; a 1% thermal decomposition temperature of 530 ℃ or higher, preferably 540 ℃ or higher, and more preferably 550 ℃ or higher; a coefficient of thermal expansion of 20 ppm/DEG C or less, preferably 15 ppm/DEG C or less, more preferably 12 ppm/DEG C or less at 50 to 450 ℃; the glass transition temperature is 430 ℃ or higher, preferably 440 ℃ or higher, and more preferably 450 ℃ or higher.
According to the polyimide film of the present invention, since it has an appropriate thickness, a low thermal expansion coefficient, a high thermal decomposition temperature, and a high glass transition temperature, it can be applied to electronic devices such as organic EL devices which are small and lightweight, and it has excellent heat resistance and dimensional temperature characteristics, and can withstand high temperatures or even higher temperatures in an annealing process of TFT.
In the polyimide film, the polyimide film has a strain at break of 15% or more, a stress at break of 0.30GPa, and an initial modulus of 6.0GPa or more.
The polyimide film according to the present invention has excellent mechanical properties, can have high durability, and has a wide range of applications.
The fourth aspect of the present invention provides a method for producing a polyimide film, wherein the polyimide precursor composition is produced by a curing process.
In the above polyimide film manufacturing method, the curing process includes the following steps: heating the polyimide precursor composition at a heating rate of 2 to 10 ℃/min from room temperature in a nitrogen atmosphere, holding the heated polyimide precursor composition at 100 ℃ for 10 minutes, and heating the heated polyimide precursor composition to 500 ℃ at 2 ℃/min. Then keeping the temperature at 500 ℃ for 10 minutes, and then cooling to room temperature.
According to the preparation method of the polyimide film, the secondary reaction and the dehydration reaction of residual tetracarboxylic acid in the curing process are effectively controlled in a step heating mode, a more stable film layer can be obtained, and the secondary reaction can enable the structure and the performance of the film to be more stable.
The present invention can provide a polyimide material having excellent thermal stability and mechanical properties by a curing process by adding a tetracarboxylic dianhydride and a tetracarboxylic acid to a diamine in a specific ratio to prepare a polyamic acid solution having excellent processability.
According to the present invention, a polyimide precursor composition capable of producing a polyimide film excellent in heat resistance, thermal decomposition resistance and mechanical properties, and a polyimide film obtained from the precursor can be provided. Further, according to the present invention, the workability of the polyamic acid solution itself can be improved by adding tetracarboxylic acid as a viscosity modifier.
The polyimide precursor composition can realize better film forming effect without adding other additives such as extra curing agent and the like, and can obtain better film performance.
Detailed Description
Polyamide acid solution and polyimide film
The polyamic acid used in the present invention is produced by polymerizing a diamine and a tetracarboxylic dianhydride in a solvent. Then, tetracarboxylic acid was added as an additive and dissolved to obtain a polyamic acid solution, and the polyamic acid solution was cured to obtain a polyimide film.
< diamine >
According to the polyamic acid solution and the method for producing a polyimide of the present invention, the diamine is preferably selected from the group consisting of p-phenylenediamine (PPD), m-phenylenediamine (MPD), and 4,4 '-diaminodiphenyl ether (4, 4' -ODA), but is not limited thereto. Also, p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), 1, 3-bis (3-aminophenoxy) benzene (133APB), 1, 3-bis (4-aminophenoxy) benzene (134APB), bis (trifluoromethyl) benzidine (TFDB), 2 ' -bis [4 (4-aminophenoxy) phenyl ] hexafluoropropane (4BDAF), 2 ' -bis (3-aminophenyl) hexafluoropropane (33-6F), 2 ' -bis (4-aminophenyl) hexafluoropropane (44-6F), bis (4-aminophenyl) sulfone (4DDS), bis (3-aminophenyl) sulfone (3DDS), 1, 3-cyclohexanediamine (13CHD), 1, 4-cyclohexanediamine (14CHD), 2-bis [4- (4-aminophenoxy) -phenyl ] propane (6HMDA) 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (DBOH), 4' -bis (3-aminophenoxy) diphenylsulfone (DBSDA), 9-bis (4-aminophenyl) fluorene (BAFL), 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA).
< tetracarboxylic dianhydride >
According to the polyamic acid solution and the method for preparing a polyimide of the present invention, preferably, the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) and/or pyromellitic dianhydride (PMDA), but is not limited thereto. It may also be selected from 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), 3,4, 4-benzophenonetetracarboxylic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), 4,4' -Oxydiphthalic Dianhydride (ODPA), bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride (SiDA), 4, 4-bis (3, 4-dicarboxyphenoxy) diphenylsulfide dianhydride (BDSDA), sulfonylphthalic anhydride (SO2DPA), cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA), 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride), 4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride) (6 HBDA).
< solvent >
According to the polyamic acid solution and the method for producing polyimide of the present invention, the solvent may be one or a mixed solvent of two or more of N-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, Diethylformamide (DEF), Diethylacetamide (DEA), Propylene Glycol Monomethyl Ether (PGME), m-methylphenol, and the like. Further, as the solvent, a low boiling point solution such as Tetrahydrofuran (THF) or chloroform, or a low absorption solvent such as γ -butyrolactone can be used. More preferably, the solvent is DMAc or NMP, or a mixed solvent of the two.
< molar ratio of diamine to tetracarboxylic acid component >
In the method for producing a polyimide according to the present invention, the tetracarboxylic dianhydride and the diamine are used in substantially equimolar amounts (preferably, the molar ratio of [ tetracarboxylic dianhydride ]/[ diamine ] is 0.900 to 1.100). More preferably, the molar ratio of [ tetracarboxylic dianhydride ]/[ diamine ] is 0.900 to 0.990. The amount of the solvent is defined by the solid content concentration of the polyamic acid solution produced, preferably, the solid content concentration of the polyamic acid solution is 5 to 50% by weight, more preferably, 10 to 25% by weight.
When the diamine is in excess relative to the tetracarboxylic dianhydride, the tetracarboxylic acid may be added in an amount substantially corresponding to the excess mole number of the diamine component, if necessary. The molar ratio of [ tetracarboxylic acid ]/[ diamine ] is 0.001 to 0.500, preferably 0.005 to 0.100. As a result, the molar numbers of the diamine, the tetracarboxylic dianhydride, and the tetracarboxylic acid are substantially close to equimolar amounts during heating. The molar ratio of (tetracarboxylic dianhydride ] + [ tetracarboxylic acid ])/[ diamine ] is 0.900 to 1.100, preferably 0.940 to 1.004.
< tetracarboxylic acid >
The tetracarboxylic acid used in the present invention is preferably one which does not substantially increase the viscosity of the polyamic acid varnish (i.e., does not substantially participate in the growth of the molecular chain). However, the tetracarboxylic acid can be converted into a tetracarboxylic dianhydride upon heating, and then reacted with a diamine to produce the polyamic acid of the present invention. In one embodiment, the temperature at which s-BPTA is converted to tetracarboxylic dianhydride is 200 ℃. According to the polyamic acid solution and the method for producing a polyimide of the present invention, the tetracarboxylic acid is preferably 3,3',4,4' -biphenyltetracarboxylic acid (BPTA), but is not limited thereto. The tetracarboxylic acid may be one or a combination of two or more of 2,3, 3', 4' -biphenyltetracarboxylic acid (a-BPTA), 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic acid) (BPABP), 4,4'- (hexafluoroisopropylidine) phthalic acid (6FDP), 4,4' -hydroxybenzenedicarboxylic acid (ODP), and 3,3',4,4' -benzophenonetetracarboxylic acid (BTTA).
< polyamic acid solution and method for producing polyimide film >
As described above, the method for producing polyamic acid according to the present invention is a method for producing a polyamic acid solution by adding tetracarboxylic acid that can be converted into tetracarboxylic dianhydride to a reaction system of diamine and tetracarboxylic dianhydride.
More specifically, the preparation process of polyamic acid includes the steps of: completely dissolving diamine in an organic solvent, slowly adding tetracarboxylic dianhydride while stirring the solution, and then continuously stirring for 1-72 hours at the temperature of 20-80 ℃. Finally, the tetracarboxylic acid is added to the reaction solution and sufficiently dissolved, depending on the amounts of the diamine and the tetracarboxylic dianhydride added first. However, the preparation method is not limited thereto. Note that if the reaction is carried out at 80 ℃ or higher, the molecular weight of the polyamic acid as a product changes depending on the temperature at the time of polymerization, and imidization progresses due to the high temperature, so that the polyimide precursor composition may be unstable, and the molecular weight of the polyamic acid may easily increase. Therefore, the order of addition of the diamine and the tetracarboxylic dianhydride in the above-mentioned production method is preferable. The reason for this is that, although the solubility of the tetracarboxylic dianhydride in the solvent is very limited, since the diamine and the resulting polyamic acid solution have good solubility, the diamine having high solubility in the solvent is added first, and then the tetracarboxylic dianhydride having low solubility is added, and the diamine and the tetracarboxylic dianhydride react with each other to produce the polyamic acid having high solubility, thereby improving the dissolution efficiency of the tetracarboxylic dianhydride. Accordingly, the amount of precipitation (precipitation is a tetracarboxylic dianhydride that is not completely dissolved in the solvent) is also reduced, and the above-described procedure is preferred.
The method for producing a polyimide film according to the present invention is a process for obtaining a polyimide film by curing a polyamic acid solution. Specifically, the process comprises the following steps: first, a polyamic acid solution is applied to a substrate, or electrostatic spinning or the like is performed, thereby preparing a coating film in a desired shape; then, the polyimide was cured by heating (gradient heating) in a nitrogen atmosphere. Preferably, the thermal curing is gradient heating, more preferably, the heating speed of the gradient heating is 2-10 ℃/min, the heating process is that the heating is carried out at 100 ℃ for 10 minutes, and the heating is carried out to 500 ℃ in a mode of 2 ℃/min. Then, the temperature is kept at 500 ℃ for 10 minutes, and then the temperature is reduced to room temperature. The polyimide can be obtained from the coating film of the polyamic acid solution by thermal method, i.e., dehydrative cyclization under high temperature conditions. The present invention is not particularly limited with respect to the specific curing process and additives used in the heating process.
According to the present invention, a polyamic acid solution having excellent processability can be prepared by adding a tetracarboxylic acid, and a polyimide material having excellent thermal stability and mechanical properties can be obtained by a curing process. The polyimide film obtained by the present invention is excellent in properties and therefore can be suitably used for substrates of organic EL, displays, touch panels, and solar cells.
In another aspect of the present invention, there is provided a polyimide film obtained by the above-mentioned production method. Compared with the prior art, the invention has the following beneficial effects: in the present invention, by adding tetracarboxylic acid as a viscosity modifier, the tetracarboxylic acid is converted into tetracarboxylic dianhydride to participate in the reaction during polymerization and cyclization of polyamic acid, which contributes to the growth of polymer molecular chains, thereby improving the mechanical properties (tensile strength, ductility, etc.) of the polyimide film produced.
< structural formula of tetracarboxylic dianhydride and diamine >
The abbreviations, full names and structural formulae of the preferred tetracarboxylic dianhydrides, diamines, tetracarboxylic acids and solvents are listed here:
s-BPDA:3, 3',4,4' -Biphenyltetracarboxylic dianhydride
And (3) PMDA: pyromellitic dianhydride
4,4' -ODA: 4,4' -diaminodiphenyl ether
TFDB: bis (trifluoromethyl) benzidine
PPD (p-phenylene diamine): p-phenylenediamine
s-BPTA:3, 3',4,4' -biphenyltetracarboxylic acid
NMP: n-methyl pyrrolidone
Physical Properties of polyimide film
The thickness of the polyimide film is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 5 μm or more, and is, for example, 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, and further preferably 15 μm or less, depending on the application.
The polyimide film of the present invention is excellent in mechanical properties, thermal properties and heat resistance. The term "heat resistance" as used herein refers to phase change (glass transition temperature is an index) and thermal decomposition (weight reduction is an index). Since the two phenomena are different, there is no direct relationship. The polyimide film of the present invention is excellent in both glass transition temperature and thermal decomposition resistance. The evaluation of the thermal decomposition resistance of the polyimide film can be set based on physical properties required in the production process of flexible organic el (oled) or the like.
For example, the thermal decomposition temperature (Td 1%) of the polyimide film can be evaluated. The thermal decomposition temperature (Td 1%) is 530 ℃ or higher, preferably 540 ℃ or higher, and more preferably 550 ℃ or higher.
The polyimide film of the present invention has an extremely low thermal expansion coefficient. In one embodiment of the present invention, the polyimide film has a Coefficient of Thermal Expansion (CTE) of from 50 ℃ to 450 ℃ of preferably 20 ppm/DEG C or less, more preferably 15 ppm/DEG C or less, and still more preferably 12 ppm/DEG C or less, as measured as a film having a thickness of 10 μm.
In one embodiment of the present invention, the glass transition temperature (Tg) of the polyimide film is 430 ℃ or higher, preferably 440 ℃ or higher, and more preferably 450 ℃ or higher.
In one embodiment of the present invention, the polyimide film has a strain at break of 15% or more, preferably 20% or more, when measured as a film having a thickness of 10 μm. In one embodiment of the present invention, the breaking stress of the polyimide film is 0.30GPa, preferably 0.35 GPa. Further, in one embodiment of the present invention, the initial modulus of the polyimide film is 5.5GPa, preferably 6.0 GPa.
In order to satisfy the application, a polyimide film satisfying the above properties is particularly preferable.
The present invention will be further described with reference to examples and comparative examples.
Examples
In each of the following examples, evaluation was performed by the following method.
Evaluation of polyimide film
[ light transmittance test ]
The light transmittance of a polyimide film having a thickness of about 10 μm in the range of 380-780nm was measured using an ultraviolet-visible spectrophotometer/Cary 60UV-vis (Agilent technologies).
[ initial modulus, fracture Strain and fracture stress test ]
A polyimide film having a film thickness of about 10 μm was cut into a long strip of 4mm × 60mm to obtain a test piece, and the initial modulus, strain at break and stress at break were measured at an inter-chuck distance of 40mm and a tensile rate of 10mm/min using a tensile tester/EZTestEZ-LX (manufactured by Shimadzu corporation).
[ Coefficient of Thermal Expansion (CTE) and glass transition temperature (Tg) test ]
A polyimide film having a film thickness of about 10 μm was cut into a strip of 5mm × 20mm to prepare a test piece, and the test piece was heated to 500 ℃ at a distance between chucks of 15mm, a stress of 1MPa, and a heating rate of 10 ℃/min using a thermomechanical analyzer/TMA 8311 (manufactured by Physics Co., Ltd.). From the TMA curve (thermomechanical analysis curve) obtained, the thermal expansion coefficient was determined at 50 to 450 ℃. The glass transition temperature (Tg) was obtained from the inflection point.
[ 1% thermal decomposition temperature (Td 1%) test ]
A polyimide film having a film thickness of about 10 μm was used as a test piece, and the temperature was raised at a temperature rise rate of 10 ℃ per minute from room temperature to 800 ℃ in a nitrogen atmosphere using a thermogravimetric differential thermal analyzer/DTG-60 AH (Shimadzu corporation). From the obtained weight curve, the thermal decomposition temperature (Td 1%) was determined with the weight of the measurement starting temperature as 100%.
Raw material
The abbreviations for the raw materials used in the following examples are as follows:
[ diamine component ]
PPD (p-phenylenediamine)
[ Tetracarboxylic acid component ]
3,3',4,4' -Biphenyltetracarboxylic acid of s-BPTA
Above 200 ℃, it can be converted to BPDA: biphenyltetracarboxylic acid dianhydride
[ tetracarboxylic dianhydride ]
3,3',4,4' -Biphenyltetracarboxylic dianhydride of s-BPDA
[ solvent ]
NMP N-methyl-2-pyrrolidone
Example 1
[ preparation of polyimide precursor composition ]
NMP was charged into a 30L reaction vessel purged with nitrogen, 28,000g of total monomer mass (18 mass%) was charged, and the starting materials were charged in the order of sBPTA113g (0.342 mol), PPD1838g (16.996 mol) and s-BPDA4700g (15.974 mol). At room temperature, stirring evening, whereby a homogeneous and viscous polyamic acid solution was obtained. The polyamic acid solution at this time had a solid content concentration of 17.7[ wt% ], and a viscosity of 5100[ cps ].
[ production of polyimide film ]
OA-11 (Japanese electric glass, 320 mm. times.420 mm. times.5 mmt) was used as the glass substrate. The polyimide precursor composition was coated on a glass substrate by a bar coater, heated at 60 ℃ and placed in a vacuum oven to evaporate NMP in the polyamic acid solution, thereby drying under reduced pressure of-0.1 MPa for about 10 min. Then, the polyimide film/substrate laminate was obtained by heating the glass substrate from room temperature to 500 ℃ under a nitrogen atmosphere and performing thermal imidization. The laminate was immersed in pure water to peel the polyimide film from the glass substrate, and after drying, the properties of the polyimide film were evaluated.
Example 2
A polyamic acid solution was obtained in the same manner as in example 1, except that the amounts (molar ratio) of biphenyl tetracarboxylic acid, biphenyl tetracarboxylic dianhydride, and diamine in example 1 were changed as shown in table 1. The polyamic acid solution at this time had a solid content of 17.8[ wt% ], and a viscosity of 5300[ cps ]. Then, a polyimide film was produced in the same manner as in example 1, and the physical properties of the film were evaluated.
Example 2
A polyamic acid solution was obtained in the same manner as in example 1, except that the amounts (molar ratios) of biphenyltetracarboxylic acid, biphenyltetracarboxylic dianhydride, and diamine in example 1 were changed as shown in table 1. The solid concentration and viscosity of the polyamic acid solution at this time were 17.8[ wt% ], 5300[ cps ], respectively.
Example 3
A polyamic acid solution was obtained in the same manner as in example 1, except that the amounts (molar ratio) of biphenyl tetracarboxylic acid, biphenyl tetracarboxylic dianhydride, and diamine in example 1 were changed as shown in table 1. The solid concentration and viscosity of the polyamic acid solution at this time were 18.0[ wt% ], 8300[ cps ], respectively.
Example 4
A polyamic acid solution was obtained in the same manner as in example 1, except that the amounts (molar ratios) of biphenyltetracarboxylic acid, biphenyltetracarboxylic dianhydride, and diamine in example 1 were changed as shown in table 1. The solid content concentration and viscosity of the polyamic acid solution at this time were 20.73[ wt% ], 3100[ cps ], respectively.
Example 5
A polyamic acid solution was obtained in the same manner as in example 1, except that the amounts (molar ratio) of biphenyl tetracarboxylic acid, biphenyl tetracarboxylic dianhydride, and diamine in example 1 were changed as shown in table 1. The solid concentration and viscosity of the polyamic acid solution at this time were 18.0[ wt% ], 5100[ cps ], respectively.
Comparative example 1
The amounts of biphenyl tetracarboxylic dianhydride and diamine were changed as shown in table 1 without adding biphenyl tetracarboxylic acid, to obtain a polyamic acid solution. The polyamic acid solution at this time had a solid content concentration of 14.8[ wt% ]and a viscosity of 4700[ cps ]. Then, a polyimide film was produced in the same manner as in example 1, and the physical properties of the film were evaluated.
Comparative example 2
The molar ratio of [ tetracarboxylic dianhydride (mol) ] + [ tetracarboxylic dianhydride (mol) ]/[ diamine (mol) ] was changed to an amount of 1.005 or more as shown in table 1, to obtain a polyamic acid solution. The solid content concentration and viscosity of the polyamic acid solution at this time were 15.2[ wt% ], 5600[ cps ] in comparative example 2. Then, a polyimide film was produced in the same manner as in example 1, and the physical properties of the film were evaluated.
[ Table 1]
Table 1 shows the composition ratios of examples and comparative examples and the evaluation results of various physical properties in a comprehensive manner. It was confirmed that the examples in table 1 satisfy the composition ratios described in claim 1, and all of the preferable physical property values described above. Specifically, the thermal decomposition temperature (Td 1%) of 1% is 550 ℃ or higher, and the CTE (50-450 ℃) of the coefficient of thermal expansion is 12ppm DEG C -1 The glass transition temperature (Tg) is 450 ℃ or higher, and the breaking stress of mechanical properties is 0.40[ GPa ]]Above, breaking strain 20 [%]Above and initial modulus of 6.0[ GPa ]]。
On the other hand, it was confirmed that the physical property values required in the present invention were not attained by comparative examples 1 and 2 which did not satisfy the above component ratio ([ tetracarboxylic dianhydride ] + [ tetracarboxylic acid ])/[ diamine ] of 0.995 or more.
As a result, in example 2, by setting the monomer composition ratio to be in the vicinity of BPDA/PDA of 0.954, BPTA/PDA of 0.030, or (BPDA + BPTA)/PDA of 0.984, a polyimide film having various mechanical property values in an optimum balance can be obtained.
It should be understood that the above-described embodiments are merely examples for clarity of description and are not intended to limit the scope of the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This list is neither intended to be exhaustive nor exhaustive. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (11)
1. A polyimide precursor composition, comprising: tetracarboxylic acid dianhydride, diamine, and tetracarboxylic acid, wherein,
the molar ratio of the tetracarboxylic dianhydride to the diamine is 0.900 to 1.100,
the molar ratio of the tetracarboxylic acid to the diamine is 0.001 to 0.500,
the ratio of the molar mass of the tetracarboxylic dianhydride to the molar mass of the tetracarboxylic diamine is 0.900 to 1.100.
2. The polyimide precursor composition according to claim 1, wherein the composition is free of a curing agent.
3. The polyimide precursor composition according to claim 1, wherein,
the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, 3,4, 4-benzophenonetetracarboxylic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, 4,4' -oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride, 4, 4-bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, sulfonylphthalic anhydride, cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride) and 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride),
preferably, the tetracarboxylic dianhydride is 3,3',4,4' -biphenyltetracarboxylic dianhydride and/or pyromellitic dianhydride.
4. The polyimide precursor composition according to claim 1, wherein,
the diamine is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4 '-diaminodiphenyl ether, p-methylenediphenylamine, m-methylenediphenylamine, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis (trifluoromethyl) benzidine, 2' -bis [4 (4-aminophenoxy) phenyl ] hexafluoropropane, 2 '-bis (3-aminophenyl) hexafluoropropane, 2' -bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 2-bis [4- (4-aminophenoxy) -phenyl ] propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, More than one of 4,4' -bis (3-aminophenoxy) diphenyl sulfone, 9-bis (4-aminophenyl) fluorene and 9, 9-bis (3-fluoro-4-aminophenyl) fluorene,
preferably, the diamine is one or more selected from the group consisting of p-phenylenediamine, m-phenylenediamine, and 4,4' -diaminodiphenyl ether.
5. The polyimide precursor composition according to claim 1, wherein,
the tetracarboxylic acid is selected from at least one of the group consisting of 3,3',4,4' -biphenyltetracarboxylic acid, 2,3, 3', 4' -biphenyltetracarboxylic acid, 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic acid), 4,4'- (hexafluoroisopropylidene) phthalic acid, 4,4' -hydroxybenzene dicarboxylic acid, and 3,3',4,4' -benzophenonetetracarboxylic acid,
preferably, the tetracarboxylic acid is 3,3',4,4' -biphenyltetracarboxylic acid and/or 2,3, 3', 4' -biphenyltetracarboxylic acid.
6. A method for preparing a polyimide precursor composition, comprising the steps of:
completely dissolving diamine in an organic solvent to obtain a diamine solution, and slowly adding tetracarboxylic dianhydride while stirring the diamine solution to obtain a reaction solution;
continuously stirring the reaction solution at the temperature of 20-80 ℃;
adding a tetracarboxylic acid to the reaction solution, and completely dissolving the tetracarboxylic acid, thereby obtaining the polyimide precursor composition.
7. The method for preparing a polyimide precursor composition according to claim 5, wherein,
the tetracarboxylic acid can be converted into a tetracarboxylic dianhydride upon heating,
preferably, the tetracarboxylic acid is capable of being converted to a tetracarboxylic dianhydride at 200 ℃ or higher.
8. A polyimide film obtained from the polyimide precursor composition according to claim 1 to 5,
the thickness of the polyimide film is 1 [ mu ] m or more and 30 [ mu ] m or less, the 1% thermal decomposition temperature is 530 ℃ or more, the thermal expansion coefficient from 50 ℃ to 450 ℃ is 20 ppm/DEG C or less, and the glass transition temperature is 430 ℃ or more.
9. The polyimide film according to claim 8,
the polyimide film has a strain at break of 15% or more, a stress at break of 0.30GPa, and an initial modulus of 6.0GPa or more.
10. A method for producing a polyimide film, which comprises curing the polyimide precursor composition according to claims 1 to 5.
11. The method for producing a polyimide film according to claim 10,
the curing process comprises the following steps:
heating the polyimide precursor composition at a heating rate of 2-10 ℃/min from room temperature in a nitrogen atmosphere, holding the heated polyimide precursor composition at 100 ℃ for 10 minutes, heating the heated polyimide precursor composition to 500 ℃ at 2 ℃/min, holding the heated polyimide precursor composition at 500 ℃ for 10 minutes, and cooling the heated polyimide precursor composition to room temperature.
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|---|---|---|---|---|
| JPS62263228A (en) * | 1986-05-08 | 1987-11-16 | Ube Ind Ltd | Polyimide tubular body |
| JP2000001545A (en) * | 1998-06-18 | 2000-01-07 | Unitika Ltd | Production of polyimide powder |
| WO2019004677A1 (en) * | 2017-06-30 | 2019-01-03 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition, preparation method therefor, and polyimide substrate manufactured therefrom |
| CN111087619A (en) * | 2019-12-31 | 2020-05-01 | 阜阳欣奕华材料科技有限公司 | Polyamide acid solution, polyimide film and application thereof |
| WO2020091432A1 (en) * | 2018-10-31 | 2020-05-07 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition for enhancing adhesiveness of polyimide film and polyimide film manufactured therefrom |
| CN113667120A (en) * | 2021-07-13 | 2021-11-19 | 中化学科学技术研究有限公司 | Polyimide and preparation method thereof |
-
2022
- 2022-05-27 CN CN202210594770.8A patent/CN114920931A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62263228A (en) * | 1986-05-08 | 1987-11-16 | Ube Ind Ltd | Polyimide tubular body |
| JP2000001545A (en) * | 1998-06-18 | 2000-01-07 | Unitika Ltd | Production of polyimide powder |
| WO2019004677A1 (en) * | 2017-06-30 | 2019-01-03 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition, preparation method therefor, and polyimide substrate manufactured therefrom |
| WO2020091432A1 (en) * | 2018-10-31 | 2020-05-07 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition for enhancing adhesiveness of polyimide film and polyimide film manufactured therefrom |
| CN111087619A (en) * | 2019-12-31 | 2020-05-01 | 阜阳欣奕华材料科技有限公司 | Polyamide acid solution, polyimide film and application thereof |
| CN113667120A (en) * | 2021-07-13 | 2021-11-19 | 中化学科学技术研究有限公司 | Polyimide and preparation method thereof |
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