CN111542562B - Method for preparing polyamic acid, polyamic acid prepared by same, polyimide resin and polyimide film - Google Patents

Method for preparing polyamic acid, polyamic acid prepared by same, polyimide resin and polyimide film Download PDF

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CN111542562B
CN111542562B CN201880084832.2A CN201880084832A CN111542562B CN 111542562 B CN111542562 B CN 111542562B CN 201880084832 A CN201880084832 A CN 201880084832A CN 111542562 B CN111542562 B CN 111542562B
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polyamic acid
bis
pmda
bpda
block structure
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CN111542562A (en
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崔斗力
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Kolon Industries Inc
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Kolon Industries Inc
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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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film

Abstract

The present invention relates to a method for preparing polyamic acid, and polyamic acid, polyimide resin, and polyimide film prepared therefrom, and more particularly, to developing a polyimide composition from which a polyimide film having an improved linear thermal expansion coefficient is manufactured by changing to a batch injection method when one type of diamine is injected.

Description

Preparation method of polyamic acid, polyamic acid prepared by preparation method, polyimide resin and polyimide film
Technical Field
The present disclosure relates to a method of preparing polyamic acid, and polyamic acid, polyimide resin, and polyimide film prepared thereby.
Background
Generally, a Polyimide (PI) film is a film formed of a polyimide resin, which is a highly heat-resistant resin prepared by solution-polymerizing an aromatic dianhydride with an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, and imidizing the polyamic acid derivative by ring-closing dehydration at high temperature.
Such polyimide films are used in a wide range of fields of electronic materials such as semiconductor insulating films, TFT-LCD electrode protective films, and flexible printed circuit boards, due to excellent mechanical properties, heat resistance, and electrical insulating properties.
However, the polyimide resin has a brown/yellow color due to its high density of aromatic rings, and has low transmittance and a yellow-based color in a visible light region, thereby decreasing light transmittance and increasing birefringence, making it unsuitable for use as an optical member.
U.S. Pat. Nos. 4595548, 4603061, 4645824, 4895972, 5218083, 5093453, 5218077, 5367046, 5338826, 5986036 and 6232428, and Korean patent laid-open publication No.2003-0009437 report methods for preparing polyimides having novel structures by using a polyimide having a structure such as-O-, -SO-and SO forth 2 -or CH 2 The linker of-is linked to a monomer having a bent structure in meta position but not in para position, or has a structure such as-CF 3 The aromatic dianhydride and aromatic diamine monomers of (1) to have improved transmittance and color transparency without significant deterioration of thermal properties. However, such polyimide is not suitable as a material for display devices such as OLED, TFT-LCD and flexible display in terms of mechanical properties, heat resistance and birefringence.
Disclosure of Invention
Technical problem
Accordingly, it is an object of the present disclosure to provide a method for preparing polyamic acid capable of improving a linear thermal expansion coefficient while maintaining optical properties by using the same raw materials and the amounts thereof as conventional compositions, changing the feeding method; providing polyamic acid, polyimide resin, and polyimide film prepared by the preparation method; and providing an image display device including the polyimide film.
Technical scheme
In order to solve the above technical problems, according to an aspect of the present disclosure, there is provided a method for preparing polyamic acid, including: supplying a diamine comprising 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFDB) (2,2' -bis (trifluoromethylphenyl) benzidine) and a dianhydride comprising pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and supplying a diamine comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride comprising at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA).
The molar ratio of PMDA to at least one selected from 6FDA and BPDA is 90 to 25.
The molar ratio of PMDA to 6FDA is 90 to 70.
Molar ratio of PMDA to BPDA from 90 to 25.
Molar ratio of PMDA, 6FDA to BPDA is 90 to 50.
The production method further comprises further supplying at least one selected from 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) as a diamine.
The at least one selected from the group consisting of 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) is added in an amount of 1 to 20 mol% based on the total moles of diamine.
In another aspect of the present disclosure, there is provided a polyamic acid including: a first block structure having repeat units from 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and repeat units from pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and a second block structure having repeating units from 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and repeating units from at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA).
The molar ratio of PMDA in the first block structure to at least one selected from 6FDA and BPDA in the second block structure is 90 to 25.
The molar ratio of PMDA in the first block structure to 6FDA in the second block structure is 90 to 70.
The molar ratio of PMDA in the first block structure to BPDA in the second block structure is from 90 to 25.
The molar ratio of PMDA in the first block structure, 6FDA in the second block structure and BPDA in the second block structure is from 90 to 50.
The second block structure has repeating units from TFDB and repeating units from at least one selected from 6FDA and BPDA, and further comprises repeating units from at least one selected from 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA).
The at least one selected from FDA and FFDA is contained in an amount of 1 to 20 mol% based on the total mol of the diamine.
In another aspect of the present disclosure, a polyimide resin prepared from the polyamic acid is provided.
In another aspect of the present disclosure, a polyimide film prepared from the polyimide resin is provided.
The polyimide film has a coefficient of thermal expansion of 30 ppm/DEG C or less at 50 to 350 ℃, a transmittance at 550nm of 85% or more as measured by a UV spectrometer, and a yellowness of 10 or less.
In another aspect of the present disclosure, there is provided an image display device including the polyimide film.
Advantageous effects
The present disclosure provides a method of preparing polyamic acid having an improved coefficient of linear thermal expansion while maintaining yellowness and transmittance after being formed into a film (a film or membrane), and a polyamic acid, a polyimide resin, and a polyimide film prepared by the same.
Detailed description of the preferred embodiments
In one aspect, the present disclosure relates to a method of preparing a polyamic acid, comprising: supplying a diamine comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride comprising pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and supplying a diamine comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride comprising at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA).
The present disclosure can obtain the effect of improving the linear thermal expansion coefficient while maintaining excellent optical properties by supplying, for example, one type of diamine at least once under specific conditions, for example, first and second supplies.
Hereinafter, the present disclosure will be described in more detail.
The preparation method of polyamic acid according to one embodiment preferably includes: supplying a diamine comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride comprising pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and a second supply of a diamine comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride comprising at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA).
The molar ratio of PMDA to at least one selected from 6FDA and BPDA is 90 to 25, preferably 90 to 30.
When the molar ratio of PMDA to at least one selected from 6FDA and BPDA does not fall within the range defined above, there is a problem that the yellowness is 10 or more and the thermal expansion coefficient is 30 ppm/deg.c or more.
Throughout the specification, feeding a diamine containing 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride containing pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)) may be referred to as "first feeding", and feeding a diamine containing 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride containing at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA) may be referred to as "second feeding". However, this is not a limitation on the feeding order, but merely serves to distinguish the feeding steps from each other.
At this time, the supply of at least two selected from at least one of 6FDA and BPDA in the second supply process means the total mole of dianhydride added at the time of the second supply relative to PMDA at the time of the first supply.
Further, when 6FDA is selected from at least one of 6FDA and BPDA and supplied at the time of the second feeding, the molar ratio of PMDA at the time of the first feeding to 6FDA at the time of the second feeding is 90 to 70, preferably 90 to 75.
When the molar ratio of PMDA at the first feed to 6FDA at the second feed does not fall within the above-defined range, more specifically, when the ratio of PMDA is higher than the range, there may be a problem that the linear thermal expansion coefficient is very low but the yellowness is very high, and when the ratio of 6FDA is higher than the range, there may be an advantage that the yellowness is very low but there may also be a problem that the linear thermal expansion coefficient is increased.
Further, when the BPDA is selected from at least one selected from 6FDA and BPDA at the time of the second feed and supplied, the molar ratio of PMDA at the time of the first feed to BPDA at the time of the second feed is 90 to 25, 10 to 75, preferably 85 to 30.
When the molar ratio of PMDA at the first feed to BPDA at the second feed does not fall within the range defined above, more specifically, when the ratio of PMDA is higher than the range, there may be a problem that the linear thermal expansion coefficient is very low but the yellowness is very high, whereas when the ratio of BPDA is higher than the range, there may be an advantage that the yellowness is very low as compared with PMDA but there may also be a problem that the linear thermal expansion coefficient is increased.
In one embodiment of the present disclosure, when at least two selected from at least one of 6FDA and BPDA are fed in the second feeding process, the molar ratio of PMDA at the first feeding, 6FDA at the second feeding, and BPDA at the second feeding is more preferably from 90 to 50.
When the molar ratio of PMDA at the time of the first feed to 6FDA and BPDA at the time of the second feed does not fall within the range defined above, there is a problem that the yellowness is 10 or more and the thermal expansion coefficient is 30 ppm/deg.c or more.
In the present disclosure, it is more preferable to first supply a dianhydride containing PMDA and then supply a dianhydride containing at least one selected from 6FDA and BPDA than to first supply a dianhydride containing at least one selected from 6FDA and BPDA and then supply a dianhydride containing PMDA, because the thermal expansion coefficient and yellowness can be improved.
That is, in one embodiment of the present disclosure, it is more preferable to first supply a diamine containing 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride containing pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)), and then supply a diamine containing 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride containing at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA), because physical properties of the present disclosure can be further improved.
In addition, at the second feeding, at least one selected from 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) may be fed as the diamine. When at least one selected from the FDA and FFDA is further supplied, an effect of improving the glass transition temperature can be obtained.
The content of at least one selected from FDA and FFDA is 1 to 20 mol%, preferably 1 to 10 mol%, based on the total mol of the diamine. When the content of at least one selected from the FDA and FFDA does not fall within the above range, more specifically, when the content is less than 1 mol%, there may be almost no effect of improving the glass transition temperature due to the low content, and when the content exceeds 20 mol%, there may be problems of an increase in yellowness and deterioration of the thermal expansion coefficient.
In one embodiment of the present disclosure, the preparation method may further include: after the second feeding, a diamine containing 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride containing at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA) are supplied in a third feeding.
The diamine and dianhydride supplied in the third supply process may be appropriately adjusted and added within the range of the molar ratio of the diamine and dianhydride supplied in the first supply and second supply processes.
In addition to TFDB, FDA and FFDA, the diamine used in one embodiment of the present disclosure may further include at least one selected from 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (pda), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mda), 1,3-bis (3-aminophenoxy) benzene (133 APB), 1,3-bis (4-aminophenoxy) benzene (134 APB), 2,2' -bis [4 (4-aminophenoxy) phenyl ] hexafluoropropane (4 af), 2,2'-bis (3-aminophenyl) hexafluoropropane (33-6F), 2,2' -bis (4-aminophenyl) hexafluoropropane (44-6F), bis (4-aminophenyl) sulfone) (4 DDS), bis (3-aminophenyl sulfone) (3 DDS), 1,3-cyclohexanediamine (13 d), 3735-cyclohexyldiamine (p), bis [ 3-aminophenyl) hexafluoropropane (5283-3-dff) and bis (3-aminophenyl) hexafluoropropane (5283) but not hmdft 3-tds) (5232-3-tdp), 5-bis (3-aminophenyl) and fft 3-bis (3-aminop) p, 35).
Also, the dianhydrides used in the present disclosure may include, in addition to PMDA, 6FDA and BPDA, a dianhydride selected from the group consisting of 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA), 4,4-Oxydiphthalic Dianhydride (ODPA), bis (3,4-dicarboxyphenyl) dimethyl-silane dianhydride (SiDA), 4,4-bis (3432 zxft SDA 3432-dicarboxyphenoxy) diphenyl sulfide dianhydride (BDD), sulfonyl diphthalic anhydride (SO 2) 2 At least one of DPA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), and 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) (6 HBDA), but is not limited thereto.
In one embodiment of the present disclosure, the diamine and dianhydride components described above are used in the polymerization reaction.
The conditions of the reaction are not particularly limited, but the reaction temperature is preferably 0 ℃ to 80 ℃ and the reaction time is preferably 2 hours to 48 hours. Further, the reaction is more preferably carried out under an inert gas atmosphere such as argon or nitrogen.
The organic solvent used for the solution polymerization of the monomers is not particularly limited as long as it is a solvent capable of dissolving the polyamic acid. At least one polar solvent selected from known reaction solvents such as m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, diethylformamide (DEF), diethylacetamide (DEA), propylene Glycol Monomethyl Ether (PGME), propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl lactate, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-methylpropionamide is used. In addition, a low boiling point solvent such as Tetrahydrofuran (THF) or chloroform, or a low absorption solvent such as γ -butyrolactone may be used. The solvent is not limited to the type of the above solvent, and the above solvents may be used alone or in a combination of two or more depending on the purpose.
The content of the organic solvent is not particularly limited, but the content of the organic solvent is preferably 50 to 95% by weight, more preferably 70 to 90% by weight, relative to the entire polyamic acid solution, to obtain a suitable molecular weight and viscosity of the polyamic acid solution.
In another aspect, the present disclosure relates to a polyamic acid comprising: a first block structure having repeat units from 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and repeat units from pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and a second block structure having repeating units from 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and repeating units from at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA).
The polyamic acid is preferably prepared by the preparation method described above.
The polyamic acid prepared by the above-described preparation method includes a first block structure and a second block structure each including a specific content of one type of diamine obtained by supplying one type of diamine in a batch manner, thereby providing an effect of improving a linear thermal expansion coefficient while avoiding deterioration of yellowness and transmittance, as compared with a polyamic acid prepared by a conventional method including supplying one type of diamine at a time.
The molar ratio of PMDA in the first block structure to at least one selected from 6FDA and BPDA in the second block structure is 90 to 25.
When the molar ratio of PMDA in the first block structure to at least one selected from the group consisting of 6FDA and BPDA in the second block structure does not fall within the range defined above, there may be a problem that the yellowness is 10 or more or the thermal expansion coefficient is 30ppm/° c or more.
In addition, the molar ratio of PMDA in the first block structure to 6FDA in the second block structure is 90 to 70, preferably 90 to 75.
When the molar ratio of PMDA in the first block structure to 6FDA in the second block structure does not fall within the range defined above, more specifically, when the ratio of PMDA is higher than the range, there may be a problem that the linear thermal expansion coefficient is very low but the yellowness is very high, whereas when the ratio of 6FDA is higher than the range, there may be an advantage that the yellowness is very low but there may also be a problem that the linear thermal expansion coefficient increases.
In addition, the molar ratio of PMDA in the first block structure to BPDA in the second block structure is from 90 to 25, preferably from 85 to 30.
When the molar ratio of PMDA in the first block structure to BPDA in the second block structure does not fall within the range defined above, more specifically, when the proportion of PMDA is higher than the range, there may be a problem that the linear thermal expansion coefficient is very low but the yellowness is very high, whereas when the proportion of BPDA is higher than the range, there may be an advantage that the yellowness is very low as compared with PMDA but there may be a problem that the linear thermal expansion coefficient increases.
In one embodiment of the present disclosure, the molar ratio of PMDA in the first block structure, 6FDA in the second block structure and BPDA in the second block structure is preferably from 90 to 50.
When the molar ratio of PMDA in the first block structure to 6FDA and BPDA in the second block structure does not fall within the range defined above, there is a problem that the yellowness is 10 or more and the thermal expansion coefficient is 30 ppm/deg.c or more.
In addition, the second block structure having a repeating unit derived from TFDB and a repeating unit derived from at least one selected from 6FDA and BPDA may further include a repeating unit derived from at least one selected from 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA). When the block structure further contains at least one selected from FDA and FFDA, the effect of improving the glass transition temperature can be obtained.
The content of the at least one selected from FDA and FFDA is preferably 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, based on the total mol of diamine. When the content of at least one selected from FDA and FFDA does not fall within the above range, more specifically, when the content is less than 1 mol%, there may be little effect of improving the glass transition temperature due to the low content, and when the content exceeds 20 mol%, there may be a problem of deterioration of yellowness and thermal expansion coefficient.
A method for preparing a polyimide resin by imidizing the above polyamic acid is not particularly limited, and a conventionally known method may be followed. The method of imidizing the polyamic acid may be thermal imidization, chemical imidization, or a combination of thermal imidization and chemical imidization. Thermal imidization is preferred. More preferably, the solution obtained by chemical imidization is precipitated, purified, dried, and then dissolved in a solvent before use. The type of the solvent is the same as described above. Chemical imidization is a method of applying a dehydrating agent represented by an acid anhydride such as acetic anhydride and an imidization catalyst represented by a tertiary amine such as isoquinoline, β -picoline or pyridine to a polyamic acid solution. Thermal imidization may be used in combination with chemical imidization, and heating conditions may be changed depending on the type of polyamic acid solution, the thickness of a film, and the like.
In another aspect, the present disclosure relates to a polyimide film prepared from the polyimide resin.
The polyimide film can also be obtained by the following method: imidizing the obtained polyamic acid solution, adding the imidized solution to a second solvent, precipitating, filtering, and drying the obtained solution to obtain a polyimide resin solid, and forming a film using a polyimide solution obtained by dissolving the obtained polyimide resin solid in the first solvent.
That is, the above polyamic acid is chemically imidized to prepare a polyimide resin, the polyimide resin is precipitated, dried, and dissolved in a solvent to prepare a polyimide solution, the polyimide solution is coated on a support, and the coated solution is formed into a film on the support by dry air and heat treatment.
The first solvent may be the same solvent as that used for polymerization of the polyamic acid solution, and the second solvent may have a lower polarity than the first solvent, so as to obtain a solid polyimide resin, and specific examples thereof may include at least one selected from the group consisting of water, alcohols, ethers, and ketones. In this case, the content of the second solvent is not particularly limited, but is preferably 5 to 20 times the weight of the polyamic acid solution.
The temperature at which the film is formed is preferably 250 ℃ to 500 ℃, and the support used herein may be a glass plate, an aluminum foil, a circulating stainless steel belt or a stainless steel drum, or the like.
The process time required for film formation depends on the temperature, the type of support, the amount of polyamic acid solution applied, and the mixing conditions of the catalyst, and is not limited to a predetermined time. Preferably, film formation is carried out for 5 minutes to 30 minutes.
The heat treatment temperature is 100 ℃ to 500 ℃ and the treatment time is 1 minute to 30 minutes. After completion of drying and imidization by heat treatment, the film was peeled off from the support.
The thickness of the resulting polyimide film is not particularly limited, but is preferably in the range of 10 μm to 250 μm, more preferably in the range of 10 μm to 100 μm.
In addition, the term "polyimide" as used herein includes any polyimide-based polymer, such as polyimide-amide.
The polyimide film produced in the present disclosure preferably has a coefficient of thermal expansion of 30 ppm/deg.C or less at 50 deg.C to 350 deg.C.
The polyimide film produced in the present disclosure has a transmittance of 85% or more, preferably 90% or more at 550nm, wherein the transmittance is measured by a UV spectrometer based on a thickness of 10 to 100 μm.
Further, the polyimide film has a yellowness of 10 or less, preferably 5 or less, based on a film thickness of 10 to 100 μm.
Hereinafter, the present disclosure will be described in more detail with reference to examples. These examples are provided only for a better understanding of the present disclosure and should not be construed as limiting the scope of the present disclosure.
< example 1>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 273.882g of N-methyl-2-pyrrolidone (NMP) was added while passing nitrogen through the reactor, 28.821g of TFDB was dissolved therein, and 19.631g of PMDA was added thereto, followed by stirring for 3 hours. Then, 3.202g of TFDB was dissolved therein, and 4.443g of 6FDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then cured by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< example 2>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 284.922g of N-methyl-2-pyrrolidone (NMP) was added while passing nitrogen through the reactor, 25.618g of TFDB was dissolved therein, and 17.450g of PMDA was added thereto, followed by stirring for 3 hours. Then, 6.405g of TFDB was dissolved therein, and 8.885g of 6FDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< example 3>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 295.963g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through the reactor, 22.416g of TFDB was dissolved therein, and 15.268g of PMDA was charged thereto, followed by stirring for 3 hours. Then, 9.607g of TFDB was dissolved therein, and 13.328g of 6FDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< example 4>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 281.419g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through the reactor, 16.012g of TFDB was dissolved therein, and 10.906g of PMDA was charged thereto, followed by stirring for 3 hours. Then, 16.012g of TFDB was dissolved therein, and 14.711g of BPDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then cured by isothermal treatment at a temperature of 350 ℃ for 10 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< example 5>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 283.076g of N, N-dimethylacetamide (DMAc) was added while passing nitrogen through the reactor, 13.450g of TFDB was dissolved therein, and 9.161g of PMDA was added thereto, followed by stirring for 3 hours. Then, 23.825g of TFDB and 1.384g of FFDA were dissolved therein, and 22.949g of BPDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 20% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then cured by isothermal treatment at a temperature of 350 ℃ for 10 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< example 6>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 288.638g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through the reactor, 22.416g of TFDB was dissolved therein, and 15.268g of PMDA was charged thereto, followed by stirring for 3 hours. Then, 9.607g of TFDB was dissolved therein, and 8.885g of 6FDA was added thereto, after which the reaction was allowed to proceed for 3 hours. Finally, 2.942g of BPDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< example 7>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 288.638g of N-methyl-2-pyrrolidone (NMP) was added while passing nitrogen through the reactor, 22.416g of TFDB was dissolved therein, and 15.268g of PMDA was added thereto, followed by stirring for 3 hours. Then, 6.405g of TFDB was dissolved therein, and 8.885g of 6FDA was added thereto, after which the reaction was allowed to proceed for 3 hours. Finally, 3.202g of TFDB was dissolved therein and 2.942g of BPDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< comparative example 1>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 268.362g of N-methyl-2-pyrrolidone (NMP) was added while passing nitrogen through the reactor, 32.023g of TFDB was dissolved therein, and 20.721g of PMDA was added thereto, followed by stirring for 3 hours. Then, 2.221g of 6FDA was added thereto, and thereafter, the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< comparative example 2>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 295.963g of N-methyl-2-pyrrolidone (NMP) was added while passing nitrogen through the reactor, 32.023g of TFDB was dissolved therein, and 15.268g of PMDA was added thereto, followed by stirring for 3 hours. Then, 13.328g of 6FDA was added thereto, after which the reaction was allowed to proceed for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then cured by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< comparative example 3>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 295.963g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through the reactor, 32.023g of TFDB was dissolved therein, and 13.328g of 6FDA was added thereto, followed by stirring for 3 hours. Then, 15.268g of PMDA was added thereto, followed by stirring for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
< comparative example 4>
To a 500mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 301.483g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through the reactor, 32.023g of TFDB was dissolved therein, and 14.178g of PMDA was charged thereto, followed by stirring for 3 hours. Then, 15.549g of 6FDA was added thereto, followed by stirring for 15 hours. As a result, a polyamic acid solution having a solid content of 17% by weight was obtained. After the reaction was completed, the resulting solution was coated on a glass plate, treated with hot air at 80 ℃ for 20 minutes, and then solidified by isothermal treatment at a temperature of 370 ℃ for 30 minutes. Then, the resultant was slowly cooled and separated from the glass plate to obtain a polyimide film.
Physical properties of the polyimide films prepared in examples and comparative examples were evaluated by the following methods, and the results are shown in table 1 below.
(1) Measuring Transmission Rate (TT)
The three transmissions were measured at 550nm using a UV spectrometer (Cotica Minolta CM-3700 d), with the average shown in Table 1.
(2) Measuring yellowness (Y.I.)
Yellowness was measured using a UV spectrometer (Konita Minolta, CM-3700 d) according to ASTM E313 standard.
(3) Measurement of Coefficient of Thermal Expansion (CTE)
The linear thermal expansion coefficient at 50 ℃ to 350 ℃ was measured twice using TMA (TA Instrument, Q400) according to the TMA method. The dimensions of the sample were 4mm X24 mm, the load was 0.02N and the heating rate was 10 ℃/min. After the heat treatment, residual stress may remain on the formed film. The residual stress is thus completely removed by the first run, whereby the second value is provided as the actual measured value.
[ Table 1]
Figure GDA0003994441760000141
Figure GDA0003994441760000151
When examples and comparative examples are compared with each other, it can be seen from table 1 that examples 1 to 7, in which TFDB was supplied in a batch manner, satisfied excellent yellowness, transmittance, and linear thermal expansion coefficient. On the other hand, comparative example 1 has significantly deteriorated transmittance, while comparative examples 2 to 4 have significantly deteriorated linear thermal expansion coefficients.
These results show that examples 1 to 7 overcome the trade-off relationship between yellowness and linear thermal expansion coefficient by feeding TFDB in a batch manner.
In addition, when the first dianhydride is PMDA and the second dianhydride is 6FDA, the content of PMDA is preferably higher than 65 mol% to provide a linear thermal expansion coefficient of 30 ppm/deg.c or less, and not higher than 90 mol% to prevent deterioration of yellowness. Further, the same effects as described above can be obtained even when the second dianhydride is BPDA. Even when FFDA is further applied, the linear thermal expansion coefficient can be improved by supplying TFDB in a batch manner. As can be seen from example 3, when the dianhydride supplied first is PMDA, the effect of improving the linear thermal expansion coefficient is greater than when the dianhydride supplied first is 6 FDA. Further, it can be seen from examples 7 and 8 that when the third dianhydride is applied, the linear thermal expansion coefficient is further improved as the addition of TFDB increases in a batch manner.

Claims (18)

1. A method of preparing a polyamic acid comprising:
supplying a diamine comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and a dianhydride comprising pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and, then
Diamines comprising 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and dianhydrides comprising at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA) were supplied.
2. The production method according to claim 1, wherein a molar ratio of PMDA to at least one selected from 6FDA and BPDA is 90 to 25.
3. The method of claim 1, wherein the molar ratio of PMDA to 6FDA is 90 to 70.
4. The production method according to claim 1, wherein the molar ratio of PMDA to BPDA is from 90 to 25.
5. The method of claim 1, wherein the molar ratio of PMDA, 6FDA to BPDA is from 90 to 50.
6. The production method according to claim 1, further comprising further supplying at least one selected from 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) as the diamine.
7. The production method according to claim 6, wherein the at least one selected from the group consisting of 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) is added in an amount of 1 to 20 mol% based on the total moles of diamines.
8. A polyamic acid prepared by the process of claim 1, comprising:
a first block structure having repeat units from 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and repeat units from pyromellitic dianhydride (1,2,4,5-pyromellitic dianhydride (PMDA)); and
a second block structure having repeat units from 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) and repeat units from at least one selected from 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA) and 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA).
9. The polyamic acid of claim 8, wherein the molar ratio of PMDA in the first block structure to at least one selected from the group consisting of 6FDA and BPDA in the second block structure is from 90 to 25.
10. The polyamic acid of claim 8, wherein the molar ratio of PMDA in the first block structure to 6FDA in the second block structure is from 90 to 70.
11. The polyamic acid of claim 8, wherein the molar ratio of PMDA in the first block structure to BPDA in the second block structure is from 90 to 25.
12. The polyamic acid of claim 8, wherein the molar ratio of PMDA in the first block structure, 6FDA in the second block structure and BPDA in the second block structure is from 90 to 50.
13. The polyamic acid of claim 8, wherein the second block structure has repeating units from TFDB and repeating units from at least one selected from 6FDA and BPDA, further comprising repeating units from at least one selected from 9,9-bis (4-aminophenyl) Fluorene (FDA) and 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA).
14. The polyamic acid according to claim 13, wherein the at least one selected from FDA and FFDA is contained in an amount of 1 to 20 mol% based on the total mol of the diamine.
15. A polyimide resin prepared from the polyamic acid according to claim 8.
16. A polyimide film prepared from the polyimide resin according to claim 15.
17. The polyimide film according to claim 16, wherein the polyimide film has a coefficient of thermal expansion of 30ppm/° c or less at 50 ℃ to 350 ℃, a transmittance of 85% or more at 550nm as measured by a UV spectrometer, and a yellowness of 10 or less.
18. An image display device comprising the polyimide film according to claim 16.
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