CN109957109B - Polyamide acid solution, transparent polyimide resin film using same, and transparent substrate - Google Patents
Polyamide acid solution, transparent polyimide resin film using same, and transparent substrate Download PDFInfo
- Publication number
- CN109957109B CN109957109B CN201811573922.6A CN201811573922A CN109957109B CN 109957109 B CN109957109 B CN 109957109B CN 201811573922 A CN201811573922 A CN 201811573922A CN 109957109 B CN109957109 B CN 109957109B
- Authority
- CN
- China
- Prior art keywords
- chemical formula
- group
- acid solution
- polyamic acid
- polyimide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Liquid Crystal (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention provides a polyamic acid solution, a transparent polyimide resin film using the same, and a transparent substrate, wherein the polyamic acid solution comprises: (a) a diamine mixture comprising a diamine represented by chemical formula 1 and a diamine represented by chemical formula 2; (b) a dianhydride mixture comprising a dianhydride represented by chemical formula 3 and a dianhydride represented by chemical formula 4; (c) an alkaline catalyst having a boiling point in the range of 140 to 200 ℃; and (d) an organic solvent. The transparent polyimide resin film and the transparent substrate produced by imidizing the polyamic acid solution have excellent optical properties and mechanical properties, and can be applied to a flexible display. Chemical formula 1
Chemical formula 2
Chemical formula 3
Chemical formula 4
Description
Technical Field
The present invention relates to a polyamic acid solution that can be applied to a flexible display, and a transparent polyimide resin film and a transparent substrate manufactured using the polyamic acid solution.
Background
Polyimide (PI) resins are insoluble and infusible resins having the highest heat resistance and excellent in electrical, chemical, thermal and mechanical properties, and thus are widely used for heat-resistant materials for the tips such as automobile materials, aircraft and spacecraft materials, and the like; such as insulating coating agents, insulating films, semiconductors, LCD electrode protective films, and the like.
As a method for synthesizing such a polyimide resin, there is generally a method of producing a Polyamic acid (polyamide acid) solution by polymerizing dianhydride and diamine in an organic solvent, and then curing the Polyamic acid solution by heat treatment to form a film, or a method of chemically imidizing (imidization), and then impregnating, washing, drying, and redissolving the film to form a film.
First, a method of manufacturing a polyimide resin film by curing a polyamic acid solution through a heat treatment includes a process of heating at a high temperature of 250 to 400 ℃ for several hours. In this process, the resin is colored, and thus there is a problem that the transmittance and yellowness in the visible light region are reduced, and it is difficult to use as an optical material requiring transparency. On the other hand, when heating is performed at a low temperature, not only the time required for producing the polyimide resin film is increased, but also the polyamic acid has a low molecular weight, which causes a problem that the strength of the produced polyimide resin film is lowered.
Next, a Method for chemically imidizing a polyamic acid solution to produce a polyimide resin film includes a process of adding xylene or toluene or the like to the polyamic acid solution to perform imidization by the Dean Stark Method, or a process of adding a catalyst such as pyridine or the like and a dehydrating agent such as acetic anhydride or the like to the polyamic acid solution to perform imidization at a low temperature. However, the above-mentioned chemical imidization method requires separate use of dean Stark apparatus or a plurality of processes such as dipping, washing, drying, and redissolving after imidization, and thus has a problem that the process is complicated and a large amount of contaminated wastewater is generated.
Therefore, development of a polyamic acid solution capable of producing a transparent polyimide resin film exhibiting high transparency and excellent thermal and mechanical properties through a relatively simple process has been demanded.
Disclosure of Invention
Problems to be solved
The present invention is directed to producing a transparent polyamic acid solution and a transparent polyimide film, each of which has a low YI (Yellow Index), a high transmittance, and mechanical properties that can be controlled, by selecting a dianhydride monomer and a diamine monomer having specific structures, adjusting the contents thereof to specific ranges, and curing the monomers at a certain temperature using a catalyst having a specific boiling point range.
It is another object of the present invention to provide a polyamic acid composition and a transparent polyimide film that can be applied to a Plastic (Plastic) transparent substrate for Flexible (Flexible) displays, a TFT substrate, a Flexible printed circuit substrate, a Flexible (Flexible) OLED flat illumination substrate, a substrate material for electronic paper, and the like, for LCDs and OLEDs.
Means for solving the problems
In order to achieve the above object, the present invention provides a polyamic acid solution comprising (a) a diamine mixture containing a diamine represented by the following chemical formula 1 and a diamine represented by the following chemical formula 2; (b) a dianhydride mixture containing a dianhydride represented by the following chemical formula 3 and a dianhydride represented by the following chemical formula 4; (c) an alkaline catalyst having a boiling point in the range of 140 to 200 ℃; and (d) an organic solvent.
[ chemical formula 1]
(in the above-mentioned chemical formula 1,
a is selected from the group consisting of a single bond, -C (═ O) -, -C (═ O) NH-, and C6～C20Is a group consisting of arylene groups of (a),
X1and X2Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
wherein, when A is a single bond, X1And X2At least one of them being halogen or C substituted with halogen atom1～C6The alkyl group of (a) is,
c above6～C20The arylene group of (A) may be halogen or C substituted with a halogen atom1～C6Alkyl is substituted, and m is an integer of 0 to 2. )
[ chemical formula 2]
(in the above-mentioned chemical formula 2,
b is selected from C1-C6 alkylene, which is substituted by a single bond, C1-C6 alkylene, or one or more hydrogens by halogen atoms, -O-B-O-, -S (═ O)2-, -C (═ O) NH and C6～C20Is a group consisting of arylene groups of (a),
X3and X4Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
c above6～C20Arylene of (A) may be substituted by halogen, C1～C6Alkyl or C substituted by halogen atoms1～C6Alkyl substituted)
[ chemical formula 3]
(in the above-mentioned chemical formula 3,
c is selected from C with 4 valence6～C20Aromatic ring radical and 4-valent C4～C40A group consisting of an aliphatic ring group,
c having the above-mentioned valence of 46～C20Each aromatic ring radical independently may be substituted by C1～C6The substitution of the alkyl group is carried out,
the above-mentioned C may be plural rings, in which case, plural rings may be the same as or different from each other, and plural rings may be substituted by one or more groups selected from the group consisting of-C (═ O) -, -C (═ O) NH-, -C (═ O) -O-and-S (═ O)2-one or more linking groups of the group consisting of
[ chemical formula 4]
(in the above-mentioned chemical formula 4,
d is selected from C1～C6Alkylene, C having one or more hydrogens replaced by halogen atoms1～C6Alkylene, -O-, -S-, -C (═ O) -and-S (═ O)2-a group of components selected from the group consisting of,
X5and X6Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
n is an integer of 1 to 3).
Effects of the invention
In the present invention, a transparent polyamic acid solution and a polyimide resin film having excellent optical properties, mechanical properties, thermal properties, and the like can be provided by selecting a diamine monomer and a dianhydride monomer having specific structures, adjusting the contents thereof to specific ranges, and using a catalyst having a specific boiling point range.
In addition, in the present invention, by applying the composition for transparent polyimide having excellent optical properties, mechanical properties, thermal properties, and the like to a substrate, it is possible to provide a transparent substrate for flexible display exhibiting excellent physical properties and product reliability.
Detailed Description
The present invention will be described in detail below. However, these are provided as examples, and the present invention is not limited thereto, and is defined only by the scope of the claims to be described later.
< polyamic acid solution >
The polyamic acid solution of the present invention is used for manufacturing a polyimide resin film having improved mechanical properties and thermal properties while maintaining high transparency and excellent optical properties, and comprises (a) a diamine mixture containing a diamine represented by the following chemical formula 1 and a diamine represented by the following chemical formula 2; (b) a dianhydride mixture containing a dianhydride represented by the following chemical formula 3 and a dianhydride represented by the following chemical formula 4; (c) an alkaline catalyst having a boiling point in the range of 140 to 200 ℃; and (d) an organic solvent.
(a) Diamine mixtures
The polyamic acid solution of the present invention contains, as diamine components, a diamine represented by the following chemical formula 1 and a diamine represented by the following chemical formula 2.
[ chemical formula 1]
In the chemical formula 1 described above,
a is selected from the group consisting of a single bond, -C (═ O) -, -C (═ O) NH-, and C6～C20Is a group consisting of arylene groups of (a),
X1and X2Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
wherein, when A is a single bond, X1And X2At least one of them being halogen or C substituted with halogen atom1～C6The alkyl group of (a) is,
c above6～C20The arylene group of (A) may be halogen or C substituted with a halogen atom1～C6The substitution of the alkyl group is carried out,
m is an integer of 0 to 2.
[ chemical formula 2]
(in the above-mentioned chemical formula 2,
b is selected from a single bond, C1～C6Alkylene, C having one or more hydrogens replaced by halogen atoms1～C6Alkylene, -O-B-O-, -S (═ O)2-, C (═ O) NH-and C6～C20Is a group consisting of arylene groups of (a),
X3and X4Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
c above6～C20Arylene of (A) may be substituted by halogen, C1～C6Alkyl or C substituted by halogen atoms1～C6Alkyl substitution.
According to a preferred embodiment of the present invention, X is1And X4May be a conventional Electron Withdrawing Group (EWG) known in the art, each independently preferably fluorine (F) or CF3。
Further, the above A may be a general C known in the art6～C20Specific examples of the arylene group in (b) include phenylene, biphenylene, and terphenylene. In particular, a is preferably selected from the group of substituents represented by the following chemical formula.
In the above substituents, the site connecting to the above chemical formula 1 is meant. Furthermore, R1～R3Are the same or different from each other and are each independently selected from the group consisting of hydrogen, F and CF3Group (d) of (a).
By introducing at least one fluorine (F) or CF in the above chemical formula 13And an Electron Withdrawing Group (EWG) to control the formation of a Charge Transfer Complex (CTC) between and within molecular chains, thereby improving the transparency of the polyimide resin.
In the present invention, the diamine represented by the above chemical formula 1 may be selected from structures derived from 2,2 '-bis (trifluoromethyl) biphenyl-4, 4' -diamine (TFDB), 4-amino-N- (4-aminophenyl) aniline, bis (4-aminophenyl) ketone, and the like, but is not limited thereto. Among them, the diamine having a structure containing a fluorinated biphenyl group can adjust reactivity with a dianhydride and realize a high glass transition temperature and low thermal expansion to improve thermal characteristics. For example, in the case of using TFDB, it is possible to increase the transmittance and glass transition temperature of the polyimide resin and to reduce the thermal expansion coefficient.
The content of the diamine represented by the above chemical formula 1 is not particularly limited, and may be 50 to 99.9 mol%, preferably 70 to 99 mol%, based on 100 mol% of the diamine mixture. In the case where the diamine represented by chemical formula 1 is included in the above range, the optical characteristics can be more improved due to the charge transfer effect between the substituents within the monomer.
In the present invention, the diamine represented by the above chemical formula 2 may be derived from 2,2' -dimethylbiphenyl-4, 4' -diamine, 4' -oxydianiline (4,4' -ODA), 3, 4-oxydianiline (3,4' -ODA), 3,3' -oxydianiline (3,3' -ODA), 4' -oxybis (3- (trifluoromethyl) aniline) (FODA), 4' - (1, 4-phenylenebis (oxy)) bis (3- (trifluoromethyl) aniline) (FAPB), 4' - (perfluoropropane-2, 2' -diyl) diphenylamine, 4' - (2,2' - (1, 4-phenylene) bis (1,1,1,3,3, 3-hexafluoropropane-2, 2-diyl) diphenylamine, 4' -sulfonyldiphenylamine (4,4' -DDS), 4' - (4,4' - (perfluoropropane-2, 2-diyl) bis (4, 1-phenylene)) bis (oxy) diphenylamine, 4' - (4,4' -sulfonylbis (4, 1-phenylene) bis (oxy)) diphenylamine, 4' - (1, 4-phenylenebis (oxy)) diphenylamine, 4' - (4,4' - (propane-2, 2-diyl) bis (4, 1-phenylene)) bis (oxy) diphenylamine, cyclohexane-1, 4-diamine, 4' -methylenedicyclohexylamine, 4' -methylenebis (2-methylcyclohexylamine) and the like, but is not limited thereto. The diamine represented by chemical formula 2 may include phenyl, biphenyl, Sulfone (SO)2) Silane groups, and the like. In this case, when m-Tolidine (m-Tolidine), 4'-ODA, FODA, FAPB, DABA, 4' -DDS, or 4,4'- (perfluoropropane-2, 2' -diyl) diphenylamine is used, the optical properties can be further improved without lowering the thermal properties of the polyimide resin.
The content of the diamine represented by the above chemical formula 2 is not particularly limited, and may be 0.01 to 50 mol%, and preferably 0.1 to 30 mol%, based on 100 mol% of the diamine mixture. When the diamine represented by chemical formula 2 is included in the above range, the optical properties (transmittance and yellowness) can be further improved.
In view of high transparency and low yellowness of the polyimide resin, the diamine (a) of the present invention preferably uses TFDB as the diamine represented by the above chemical formula 1 and m-Tolidine, 4'-ODA, FODA, FAPB, DABA, 4' -DDS, or 4,4'- (perfluoropropane-2, 2' -diyl) diphenylamine as the diamine represented by the above chemical formula 2.
(b) Dianhydride mixture
The polyamic acid solution of the present invention contains a dianhydride represented by the following chemical formula 3 and a dianhydride represented by the following chemical formula 4 as dianhydride components.
[ chemical formula 3]
In the chemical formula 3 above, the first and second,
c is selected from C with 4 valence6～C20Aromatic ring radical and 4-valent C4～C40A group consisting of an aliphatic ring group,
c having the above-mentioned valence of 46～C20The aromatic ring groups may each independently be substituted by halogen or C1～C6Alkyl or C substituted by halogen atoms1～C6The substitution of the alkyl group is carried out,
the above-mentioned C may be plural rings, in which case, plural rings may be the same as or different from each other, and plural rings may be substituted by one or more groups selected from the group consisting of-C (═ O) -, -C (═ O) NH-, -C (═ O) -O-and-S (═ O)2-one or more linking groups (L) from the group consisting.
[ chemical formula 4]
In the chemical formula 4 above, the first and second,
d is selected from C1～C6Alkylene, C having one or more hydrogens replaced by halogen atoms1～C6Alkylene, -O-, -S-, -C (═ O)) -and-S (═ O)2-a group of components selected from the group consisting of,
X5and X6Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
n is an integer of 1 to 3.
According to a preferred embodiment of the present invention, C is a general 4-valent hydrocarbon ring group known in the art, and C is mentioned as an example of the hydrocarbon ring group6～C20Aromatic ring radical or C4～C40Aliphatic ring groups, and the like. The above C is preferably a 4-valent 6-membered aromatic ring group or a 4-valent 6-membered aliphatic ring group. At this time, when C is a 6-membered aromatic ring group having a valence of 4, the dianhydride of chemical formula 3 may be an aromatic dianhydride containing a diamine structure, and when C is a 6-membered aliphatic ring group having a valence of 4, the dianhydride of chemical formula 3 may be a non-aromatic dianhydride containing a diamine structure.
The above-mentioned C may be a plurality of rings. In this case, the rings may be the same or different from each other, and the rings may be selected from the group consisting of-C (═ O) -, -C (═ O) NH-, -C (═ O) -O-, and-S (═ O)2-one or more linking groups from the group consisting of.
For example, when the above-mentioned C is a 4-valent 6-membered aromatic ring group, it may be one or more of the usual C known in the art6～C40The arylene group, the sulfone group, or a form in which the arylene group and the sulfone group are linked. Specific examples thereof include phenylene, biphenylene, terphenylene, and sulfonyl diphenylene. In particular, C is preferably selected from the group of substituents represented by the following chemical formula.
In the above substituents, R represents a site linked to the above chemical formula 34～R6The same or different from each other, each independently may be hydrogen or C1～C6Preferably each independently may be hydrogen orA methyl group.
The dianhydride represented by chemical formula 3 is not decomposed by heat or light because an arylene group and/or a sulfone group having a rigid structure are introduced between dianhydrides, and thus is more stable against external impact, and can effectively improve optical properties, thermal properties, mechanical properties, and the like of a polyimide resin produced using the dianhydride. In addition, the compound represented by chemical formula 3 has an amide group (-C (═ O) -NH-), introduced between dianhydrides, and thus reacts with an oxygen atom in another dianhydride monomer to form a hydrogen bond, thereby generating a constant binding force in the main chain of the polymer, thereby effectively improving the mechanical properties and heat resistance of the polyimide resin.
Further, when the C is a 6-membered aliphatic cyclic group having a valence of 4, since pi electrons are not present in the compound structure by controlling the formation of a Charge Transfer Complex (CTC), it plays a great role in realizing high transmittance and low yellowness of the polyimide resin.
The dianhydride represented by the above chemical formula 3 may be selected from structures derived from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (CHDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride (CPBA), bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2.2.2] -7-octene-2, 3,5, 6-tetracarboxylic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride (S-BPDA), 2,3,3',4' -biphenyltetracarboxylic dianhydride (a-BPDA), pyromellitic dianhydride (PMDA), N '- (4,4' -sulfonylbis (4, 1-phenylene)) bis (1, 3-dioxo-octahydroisobenzofuran-5-carboxamide), and the like, but is not limited thereto.
The content of the dianhydride represented by chemical formula 3 is not particularly limited, and may be 10 to 95 mol%, preferably 50 to 90 mol%, based on 100 mol% of the dianhydride mixture. In the case where the dianhydride represented by chemical formula 3 is included in the above range, the thermal expansion coefficient of the polyimide resin can be further reduced while maintaining high transmittance and low yellowness of the polyimide resin.
Further, according to a preferred embodiment of the present invention, X is5And X6May be a conventional electron withdrawing group (elec) known in the arttron with a fluorine (F) or CF) independently of one another3。
The dianhydride represented by the above chemical formula 4 may be selected from structures derived from 5,5' - (perfluoropropane-2, 2-diyl) diisobenzofuran-1, 3-dione (6-FDA), 5' -oxydisisobenzofuran-1, 3-dione (ODPA), 5' -sulfonyldiisobenzofuran-1, 3-dione (DSDA), benzophenone-3, 3',4,4' -tetracarboxylic dianhydride (BTDA), and the like, but is not limited thereto. In this case, when 6FDA is used, the transparency of the polyimide resin can be improved by controlling the formation of Charge Transfer Complexes (CTCs) between and within molecular chains.
The content of the dianhydride represented by chemical formula 4 is not particularly limited, and may be 5 to 90 mol%, and preferably 10 to 50 mol%, based on 100 mol% of the dianhydride.
As described above, in one example of the present invention, in the case where the diamine represented by chemical formula 1 and the diamine represented by chemical formula 2 are used as the diamine component, and the dianhydride represented by chemical formula 3 and the dianhydride represented by chemical formula 4 are used as the dianhydride component, the (a) diamine mixture and the (b) dianhydride mixture may be mixed in a weight ratio of (a) to (b) 1:0.1 to 10 in order to improve the yellowness and mechanical properties of the polyimide resin.
(c) Basic catalyst
The basic catalyst is a basic catalyst having a boiling point of 140 to 200 ℃, and may be, for example, 4-methoxypyridine, 4-ethylpyridine, 2-methylpiperazine, 2, 6-dimethylpiperazine, 4-tert-butylpyridine, 2-propylpyridine, 4-propylpyridine, 2,3, 5-trimethylpyridine, 2, 5-dimethylpyridine, 2, 6-dimethylpyridine, 2, 3-dimethylpyridine, 4-diazabicyclo [2.2.2] octane, 3-ethylpyridine, 3-methylpyridine, 2, 3-dimethylpyrazine, 2, 5-dimethylpyrazine, or the like, and these may be used alone or in a mixture of two or more.
If the boiling point of the basic catalyst group is lower than 140 ℃, it is difficult to form a film. On the other hand, if the boiling point exceeds 200 ℃, it is difficult to remove the catalyst at the curing temperature of the present invention, and if the curing temperature is increased for removing the catalyst, the optical characteristics are impaired.
(d) Organic solvent
The solvent used for synthesizing the polyamic acid solution is not particularly limited as long as it is a solvent known in the art. The organic solvent may be a polar solvent such as m-cresol, N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate, dimethyl phthalate (DMP), or the like; low boiling point solutions such as Tetrahydrofuran (THF) and chloroform; and low water-absorbing solvents such as γ -butyrolactone, which may be used singly or in combination.
In the polyamic acid solution of the present invention described above, the content of the diamine mixture, the dianhydride mixture, the catalyst and the organic solvent is not particularly limited, and (a) the diamine mixture may be 1 to 20% by weight, (b) the dianhydride mixture may be 1 to 20% by weight, (c) the catalyst may be used in an amount generally known in the art, for example, about 0.01 to 20% by weight, specifically about 0.01 to 15% by weight, more specifically about 0.1 to 10% by weight, and (d) the organic solvent may be the rest, based on 100% by weight of the whole polyamic acid solution. In this case, when the content of each component in the polyamic acid solution is less than the above range, the viscosity of the polyamic acid solution may become too low, and when the content is more than the above range, the viscosity of the polyamic acid solution may become too high. Accordingly, if the contents of the components in the polyamic acid solution of the present invention are adjusted in the above ranges, the polyamic acid solution may have a viscosity ranging from about 1,000 to 500,000cps, preferably from about 10,000 to 200,000 cps. In addition, when the viscosity of the polyamic acid solution is in the above range, the thickness of the polyamic acid solution can be easily adjusted when the polyamic acid solution is applied, and the surface of the applied coating film can be uniformly formed.
On the other hand, the polyamic acid solution of the present invention may contain additives such as a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, and the like in a small amount as necessary within a range not significantly impairing the object and effect of the present invention.
If the polyamic acid solution of the present invention as described above is subjected to solution polymerization, a polyamic acid can be obtained. Specifically, the diamine represented by chemical formula 1 and the diamine represented by chemical formula 2 may be put in an organic solvent to be dissolved, and then the dianhydride represented by chemical formula 3 and the dianhydride represented by chemical formula 4 may be added thereto to perform a solution polymerization reaction, thereby producing the polyamic acid. In this case, the reaction conditions are not particularly limited, and the reaction can be carried out at-20 to 80 ℃ for 1 to 12 hours (preferably 1 to 3 hours).
< transparent polyimide resin film >
The present invention provides a transparent polyimide resin film produced by imidizing the polyamic acid solution.
In this case, the polyimide resin may be in the form of a random copolymer (random copolymer) or a block copolymer (block copolymer).
The transparent polyimide resin film of the present invention is produced using the above polyamic acid solution, and therefore has improved mechanical properties (elastic modulus, strength) as well as optical properties (transparency and yellowness), and excellent thermal properties (thermal expansion coefficient and glass transition temperature) can be expected. Specifically, the transparent polyimide resin film of the present invention has a light transmittance of 88% or more at a wavelength of 550nm, a Yellowness (YI) at a wavelength of 550nm of 5.0 or less, a Haze (Haze) of 1.0 or less, an elastic Modulus (Modulus) of 3 to 6GPa, and a mechanical Strength (Strength) of 120 to 200 MPa.
In addition, the transparent polyimide resin film of the present invention contains an imide group (imide), and therefore is excellent in heat resistance, chemical resistance, abrasion resistance, and mechanical properties.
The method for producing such a transparent polyimide resin film is not particularly limited, and for example, the transparent polyamic acid composition can be applied (cast) onto a glass substrate, a metal substrate, or a heat-resistant polymer substrate, and then imidized (imidization) is carried out for 1 to 12 hours while gradually raising the temperature in the range of 80 to 300 ℃.
The coating method may be any conventional method known in the art, and examples thereof include Spin coating (Spin coating), Dip coating (Dip coating), Solvent casting (Solvent casting), Slot die coating (Slot die coating), and spray coating (spray coating).
The thickness of the transparent polyimide resin film is not particularly limited, and the polyamic acid composition may be applied 1 or more times to be adjusted to several hundred nm to several tens μm.
The transparent polyimide resin film described above can be used in various fields, and is particularly useful for a display for an organic EL element (OLED), a display for a liquid crystal element, a TFT substrate, a Flexible printed circuit substrate, a Flexible (Flexible) OLED flat lighting substrate, a substrate for a Flexible display such as a substrate material for electronic paper, and a protective film, which require high transparency and heat resistance.
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.
[ example 1]
1-1. production of polyamic acid solution
After a 1500ml three-necked round-bottomed flask was charged with 640.016g of N, N-dimethylacetamide (DMAc), the temperature of the flask was raised to 50 ℃. Then, 85.0g of 2,2 '-bis (trifluoromethyl) biphenyl-4, 4' -diamine (TFDB) was added to the flask, and 1.743g of 2,2 '-dimethylbiphenyl-4, 4' -diamine (m-Tol) was added after 60 minutes. This was stirred for 1 hour to completely dissolve TFDB and m-Tol. Thereafter, 45.615g of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA) and 18.235g of 5,5' - (perfluoropropane-2, 2-diyl) diisobenzofuran-1, 3-dione (6FDA) were added to the flask in this order and dissolved therein. At this time, the solid content was 15%, and then the reaction was carried out by stirring for 5.5 hours. After confirming the completion of the reaction between the monomers by the increase in viscosity, 37g of 4-t-butylpyridine was slowly added and stirred for 4.5 hours. Thereafter, it was naturally cooled to obtain a polyamic acid solution (solution viscosity at 25 ℃ C.: 85000 CPs).
1-2. production of transparent polyimide resin film
The polyamic acid solution produced in 1-1 of example 1 was applied to a glass plate for LCD using a Bar Coater (Bar Coater), and then dried while gradually raising the temperature in stages in a convection oven under nitrogen atmosphere such that the temperature was 30 minutes at 80 ℃, 30 minutes at 150 ℃,1 hour at 200 ℃ and 1 hour at 280 ℃ to perform imidization (imidization). As a result, a transparent polyimide resin film (imidization rate: 85% or more) having a film thickness of 52 μm was produced. Thereafter, the film was separated from the glass plate, thereby obtaining a transparent polyimide resin film.
[ example 2]
2-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 85000CPs) was produced in the same manner as in 1-1 of example 1.
2-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1 except that the imidization reaction was performed by drying in a convection oven under nitrogen atmosphere while gradually raising the temperature in a negative stepwise manner at 80 ℃ for 30 minutes, 150 ℃ for 30 minutes, 200 ℃ for 1 hour, and 320 ℃ for 1 hour.
[ example 3]
3-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 85000CPs) was produced in the same manner as in 1-1 of example 1.
1-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 350 ℃ for 1 hour.
[ example 4]
4-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 79000CPs) was prepared in the same manner as in 1-1 of example 1, except that 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
4-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 5]
5-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 82000CPs) was prepared in the same manner as in 1-1 of example 1, except that 4-ethylpyridine was used in place of 4-t-butylpyridine.
5-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 6]
6-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 81000CPs) was prepared in the same manner as in 1-1 of example 1, except that 2-methylpiperazine was used instead of 4-t-butylpyridine.
6-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 7]
7-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 122000CPs) was prepared in the same manner as in 1-1 of example 1, except that TFDB:4,4' -ODA: CBDA:6FDA was used in a molar ratio of 9:1:9: 1.
7-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 8]
8-1. Polyamic acid solutionProduction of liquids
A polyamic acid solution (solution viscosity at 25 ℃ C.: 118000CPs) was prepared in the same manner as in 7-1 of example 7, except that 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
8-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 9]
9-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 119000CPs) was prepared in the same manner as in 7-1 of example 7, except that 4-methoxypyridine was used in place of 4-t-butylpyridine.
9-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 7-2 of example 7.
[ example 10]
10-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 47000CPs) was prepared in the same manner as in 1-1 of example 1 above, except that TFDB: FODA: CHDA:6FDA was used in a molar ratio of 9:1:8:2, and 4-methoxypyridine was used in place of 4-t-butylpyridine.
10-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 11]
11-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 47000CPs) was produced in the same manner as in 1-1 of example 1.
11-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 320 ℃ for 1 hour.
[ example 12]
12-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 47000CPs) was produced in the same manner as in 1-1 of example 1.
12-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 350 ℃ for 1 hour.
[ example 13]
13-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 112000CPs) was prepared in the same manner as in 1-1 of example 1 above, except that TFDB: FODA: s-BPDA:6FDA was used in a molar ratio of 9:1:9:1 and 4-methoxypyridine was used in place of 4-t-butylpyridine.
13-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 14]
14-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 113000CPs) was prepared in the same manner as in 13-1 of example 13, except that 4-t-butylpyridine was used in place of 4-methoxypyridine.
14-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 15]
15-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 110000CPs) was prepared in the same manner as in 13-1 of example 13, except that 3-methylpyridine was used instead of 4-methoxypyridine.
15-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 16]
16-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 112000CPs) was prepared in the same manner as in 13-1 of example 13, except that 2, 3-lutidine was used in place of 4-methoxypyridine.
16-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 17]
17-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 119000CPs) was prepared in the same manner as in 13-1 of example 13, except that 2,3, 5-collidine was used in place of 4-methoxypyridine.
17-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 18]
18-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 52000CPs) was prepared in the same manner as in 1-1 of example 1 except that TFDB: FAPB: a-BPDA: ODPA was used in a molar ratio of 9:1:7:3, and 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
18-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 19]
19-1 preparation of Polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 52000CPs) was produced in the same manner as in 18-1 of example 18 above.
19-2 preparation of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 320 ℃ for 1 hour.
[ example 20]
20-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 52000CPs) was produced in the same manner as in 18-1 of example 18 above.
20-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 350 ℃ for 1 hour.
[ example 21]
21-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 83000CPs) was prepared in the same manner as in 1-1 of example 1 above, except that TFDB: DABA: CBDA: DSDA was used in a molar ratio of 8:2:8: 2.
21-2 preparation of transparent polyimide resin filmManufacture of
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 22]
22-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 81000CPs) was prepared in the same manner as in 21-1 of example 21, except that 2,3, 5-trimethylpyridine was used in place of 4-t-butylpyridine.
22-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 23]
23-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 82000CPs) was prepared in the same manner as in 21-1 of example 21, except that 4-methoxypyridine was used in place of 4-t-butylpyridine.
23-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 24]
24-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 61000CPs) was prepared in the same manner as in 1-1 of example 1 except that TFDB:4,4' -DDS: s-BPDA:6FDA was used in a molar ratio of 9:1:7:3, and 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
24-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 25]
25-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 61000CPs) was prepared in the same manner as in 24-1 of example 24.
25-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 350 ℃ for 1 hour.
[ example 26]
26-1 preparation of Polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 47000CPs) was prepared in the same manner as in 1-1 of example 1 except that TFDB:4,4'- (perfluoropropane-2, 2' -diyl) diphenylamine: CBDA:6FDA was used in a molar ratio of 9:1:7:3, and 4-methoxypyridine was used in place of 4-t-butylpyridine.
26-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 27]
27-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 107000CPs) was prepared in the same manner as in 1-1 of example 1, except that TFDB: FODA: s-BPDA: DSDA was used in a molar ratio of 9:1:9: 1.
27-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 28]
28-1 preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 89000CPs) was prepared in the same manner as in 1-1 of example 1 above, except that TFDB: FODA: s-BPDA: BTDA was used in a molar ratio of 9:1:9: 1.
28-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 29]
29-1 preparation of Polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 85000CPs) was prepared in the same manner as in 28-1 of example 28, except that 4-methoxypyridine was used in place of 4-t-butylpyridine.
29-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 30]
30-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 87000CPs) was prepared in the same manner as in 28-1 of example 28 except that 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
30-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 31]
31-1 preparation of Polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 46000CPs) was prepared in the same manner as in 1-1 of example 1 except that TFDB:4,4' -DDS: s-BPDA:6FDA was used in a molar ratio of 8:2:7:3, and 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
31-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 32]
32-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 37000CPs) was prepared in the same manner as in 1-1 of example 1 except that TFDB:4,4' -DDS: bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic dianhydride: 6FDA was used in a molar ratio of 8:2:7: 3.
32-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 33]
33-1 preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 35000CPs) was prepared in the same manner as in 32-1 of example 32 except that 2,3, 5-collidine was used in place of 4-t-butylpyridine.
33-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 34]
34-1 preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 35000CPs) was prepared in the same manner as in 32-1 of example 32 except that 4-methoxypyridine was used in place of 4-t-butylpyridine.
34-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 35]
35-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 41000CPs) was prepared in the same manner as in 1-1 of example 1 above, except that TFDB: FODA: bicyclo [2.2.2] -7-octene-2, 3,5, 6-tetracarboxylic dianhydride: 6FDA was used in a molar ratio of 9:1:7: 3.
35-2 preparation of transparent polyimide resin filmManufacture of
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 36]
36-1 preparation of Polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 41000CPs) was prepared in the same manner as in 35-1 of example 35, except that 4-diazabicyclo [2.2.2] octane was used in place of 4-t-butylpyridine.
36-2 preparation of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
[ example 37]
37-1 preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 40000CPs) was prepared in the same manner as in 35-1 of example 35, except that 4-methoxypyridine was used in place of 4-t-butylpyridine.
37-2 production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of example 1.
Comparative example 1
1-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 82000CPs) was prepared in the same manner as in 1-1 of example 1, except that 19.987g of pyridine was used in place of 4-t-butylpyridine.
1-2. production of transparent polyimide resin film
The same procedure as in 1-2 of example 1 was followed, and thereafter separation of the film from the glass plate was attempted, but the entirety of the formed film was broken and no film was obtained.
Comparative example 2
2-1. production of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 80000CPs) was prepared in the same manner as in 1-1 of comparative example 1, except that isoquinoline was used instead of pyridine.
2-2. production of transparent polyimide resin film
The procedure was carried out in the same manner as in 1-2 of comparative example 1, except that the amount of isoquinoline remaining was too large to obtain a good film.
Comparative example 3
3-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 73000CPs) was prepared in the same manner as in 1-1 of comparative example 1, except that TFDB: BTDA:6FDA was used in a molar ratio of 10:7: 3.
3-2. production of transparent polyimide resin film
The same procedure as in 1-2 of example 1 was followed, and thereafter separation of the film from the glass plate was attempted, but the entirety of the formed film was broken and no film was obtained.
Comparative example 4
4-1. preparation of polyamic acid solution
A polyamic acid solution (solution viscosity at 25 ℃ C.: 73000CPs) was prepared in the same manner as in 35-1 of example 35.
4-2. production of transparent polyimide resin film
The imidization reaction was performed in the same manner as in 1-2 of example 1, except that the drying and the imidization reaction were performed while gradually raising the temperature in stages in a convection oven under a nitrogen atmosphere in such a manner that the temperature was increased at 80 ℃ for 30 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 1 hour, and at 350 ℃ for 1 hour. Then, the polyimide film was separated from the glass plate.
The compositions of the diamine mixtures, dianhydride mixtures and catalysts used in examples 1 to 37 and comparative examples 1 to 3 are shown in table 1 below.
[ Table 1]
*: partial injury (Fragile (britle))
Experimental example 1 evaluation of physical Properties of transparent polyimide resin film
The physical properties of the transparent polyimide resin films produced in examples 1 to 37 and comparative examples 1 to 4 were evaluated by the following methods, and the results are shown in table 2.
(1) Transmittance (T%) measurement
The measurement was carried out at a wavelength of 550nm using an ultraviolet-visible Spectrophotometer (UV-Vis NIR Spectrophotometer, Shimadzu, model name: UV-3150) according to ASTM E313-73, i.e. a C light source and a viewing angle of 2 ℃.
(2) Measurement of Yellowness (YI)
The yellowness at 550nm was measured by means of a spectrocolorimeter (Konica Minolta, model name: CM-3700d) according to the ASTM E313 standard.
(3) Determination of mechanical Properties
Tensile Strength (Strength, MPa) and Modulus of elasticity (Modulus, GPa) were determined according to ISO 527-3 standard using UTM (Instron, model name: 5942).
[ Table 2]
Referring to tables 1 and 2, it is understood that the characteristics change depending on the composition of the transparent polyimide resin film produced.
First, from the results of examples 1 to 3, it is understood that when the same composition and the same catalyst are used but different curing temperatures are applied, the higher the curing temperature is, the worse the optical properties are, but the mechanical properties are not greatly different. That is, it was found that a transparent polyimide resin film having excellent properties can be obtained in the imidization step at a curing temperature of 280 ℃.
Further, from the results of examples 1 and 4 to 6, it is understood that a transparent polyimide resin film having excellent characteristics can be obtained by applying catalysts having different boiling points at the same curing temperature (280 ℃). However, in the case of example 5, it was confirmed that the obtained film was partially damaged.
Next, from the results of examples 7 to 37, it is understood that when a wide variety of basic catalysts having boiling points between 140 and 200 ℃ are used, a transparent polyimide resin film having excellent characteristics can be obtained even in the imidization step at 300 ℃ or less, which is a relatively low curing temperature. That is, it was confirmed that the high temperature process at the time of production could be improved.
From the above results, it was confirmed that the optical properties and mechanical properties can be adjusted by the combination of the composition, curing temperature, and catalyst type.
On the other hand, from the results of comparative examples 1 and 2, it was confirmed that a film could not be obtained when pyridine having a low boiling point of 115 ℃ was used as a catalyst with the same composition (comparative example 1), and when isoquinoline having a boiling point of 240 ℃ was used as a catalyst, although a film could be obtained, the remaining amount of the catalyst was large. For such a problem, it is obvious that a large problem is caused when the device is applied after mass production in a large amount.
From the results of comparative examples 3 to 4, it was confirmed that when a catalyst having a boiling point of 115 ℃ was used, a film could not be obtained at a low curing temperature of 280 ℃ (comparative example 3), and a film could be obtained at a curing temperature of 350 ℃, but partial damage occurred (comparative example 4).
As a result of analyzing the above results, it is understood that the transparent polyimide resin films of examples 1 to 37 of the present invention have not only excellent optical characteristics but also excellent mechanical characteristics such as increased tensile strength and elastic modulus.
Specifically, it is found that the transparent polyimide resin films of examples 1 to 37 have a transmittance of 88% or more, a yellowness index of 5.0 or less, an elastic modulus of 3 to 6GPa, and a strength of 120 to 160MPa, and have higher light transmittance and lower yellowness and excellent mechanical properties as compared with the transparent polyimide resin films of comparative examples 1 to 4, and satisfy the conditions for being applicable to flexible display materials.
As described above, it was confirmed that the transparent polyimide resin film produced from the polyamic acid solution of the present invention can be used as a material for a flexible display, a substrate, or a protective film because it is improved in a high-temperature process during production, and has high light transmittance, low yellowness, and excellent mechanical properties.
Claims (11)
1. A polyamic acid solution comprising:
(a) a diamine mixture comprising a diamine represented by the following chemical formula 1 and a diamine represented by the following chemical formula 2, the diamine represented by the chemical formula 2 being selected from the group consisting of 4,4' - (1, 4-phenylenebis (oxy)) bis (3- (trifluoromethyl) aniline) (FAPB), 4' - (2,2' - (1, 4-phenylene) bis (1,1,1,3,3, 3-hexafluoropropane-2, 2-diyl) diphenylamine, 4' - (4,4' - (perfluoropropane-2, 2-diyl) bis (4, 1-phenylene)) bis (oxy) diphenylamine, 4' - (4,4' -sulfonylbis (4, 1-phenylene) bis (oxy)) diphenylamine, 4' - (1, 4' -sulfonylbis (4-phenylene) bis (oxy)) diphenylamine, 4-phenylenebis (oxy)) diphenylamine, 4'- (4,4' - (propane-2, 2-diyl) bis (4, 1-phenylene)) bis (oxy) diphenylamine, cyclohexane-1, 4-diamine, 4 '-methylenedicyclohexylamine and 4,4' -methylenebis (2-methylcyclohexylamine);
(b) a dianhydride mixture comprising a dianhydride represented by the following chemical formula 3 and a dianhydride represented by the following chemical formula 4;
(c) an alkaline catalyst having a boiling point in the range of 140 to 200 ℃; and
(d) an organic solvent, and a solvent mixture comprising an organic solvent,
the basic catalyst is more than one selected from the group consisting of 4-ethylpyridine, 2-methylpiperazine, 2, 6-dimethylpiperazine, 4-tert-butylpyridine, 4-methoxypyridine, 2-propylpyridine, 4-propylpyridine, 2,3, 5-trimethylpyridine, 2, 5-dimethylpyridine, 2, 6-dimethylpyridine, 2, 3-dimethylpyridine, 4-diazabicyclo [2.2.2] octane, 3-ethylpyridine, 3-methylpyridine, 2, 3-dimethylpyrazine and 2, 5-dimethylpyrazine,
chemical formula 1
In the chemical formula 1, the metal oxide is represented by,
a is selected from the group consisting of a single bond, -C (═ O) -, -C (═ O) NH-and C6～C20Is a group consisting of arylene groups of (a),
X1and X2Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
wherein, when A is a single bond, X1And X2At least one of them being halogen or C substituted with halogen atom1～C6The alkyl group of (a) is,
said C is6～C20The arylene group of (A) may be halogen or C substituted with a halogen atom1～C6The substitution of the alkyl group is carried out,
m is an integer of 0 to 2,
chemical formula 2
In the chemical formula 2, the first and second organic solvents,
b is selected from a single bond, C1～C6Alkylene, C having one or more hydrogens replaced by halogen atoms1～C6Alkylene, -O-, -S (═ O)2-, -C (═ O) NH-and C6～C20Of arylene groupThe composition of the components is shown in the specification,
X3and X4Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
said C is6～C20Arylene of (A) may be substituted by halogen, C1～C6Alkyl or C substituted by halogen atoms1～C6The substitution of an alkyl group is carried out,
chemical formula 3
In the chemical formula 3, the first and second organic solvents,
c is selected from C with 4 valence6～C20Aromatic ring radical and 4-valent C4～C20A group consisting of an aliphatic ring group,
c of said 4 valence6～C20The aromatic ring group may be substituted by C1～C6The substitution of the alkyl group is carried out,
the C may be a plurality of rings, in which case the plurality of rings may be the same as or different from each other, and the plurality of rings may be substituted with each other by a group selected from the group consisting of-C (═ O) -, -C (═ O) NH-, -C (═ O) -O-, and-S (═ O)2-one or more linking groups of the group are linked,
chemical formula 4
In the chemical formula 4, the first and second organic solvents,
d is selected from C1～C6Alkylene, C having one or more hydrogens replaced by halogen atoms1～C6Alkylene, -O-, -S-, -C (═ O) -and-S (═ O)2-a group of components selected from the group consisting of,
X5and X6Are the same or different from each other and are each independently selected from hydrogen, halogen, C1～C6And C in which one or more hydrogen atoms are substituted by halogen atoms1～C6Of an alkyl group of (a) or (b),
n is an integer of 1 to 3.
2. The polyamic acid solution of claim 1, said X1～X6Each independently F or CF as an electron withdrawing group EWG3。
3. The polyamic acid solution according to claim 1, wherein A is selected from a group of substituents represented by the following chemical formula,
among the substituents mentioned above, the group of the substituted,
means a site linked to said chemical formula 1,
R1～R3are the same or different from each other and are each independently selected from the group consisting of hydrogen, F and CF3Group (d) of (a).
4. The polyamic acid solution according to claim 1, wherein C is selected from a group of substituents represented by the following chemical formula,
among the substituents mentioned above, the group of the substituted,
means a site linked to said chemical formula 3,
R4～R6are the same or different from each other and are each independently selected from hydrogen or C1～C6Alkyl group of (1).
5. The polyamic acid solution according to claim 1, wherein the diamine represented by chemical formula 1 is contained in an amount of 50 to 99.9 mol% based on 100 mol% of the diamine mixture,
the content of the diamine represented by chemical formula 2 is 0.1 to 50 mol% based on 100 mol% of the diamine mixture.
6. The polyamic acid solution according to claim 1, wherein the dianhydride represented by chemical formula 3 is contained in an amount of 10 to 95 mol% based on 100 mol% of the dianhydride mixture.
7. The polyamic acid solution according to claim 1, wherein the content ratio of the diamine mixture (a) to the dianhydride mixture (b) is 1: 0.1-10 by weight.
8. The polyamic acid solution according to claim 1, having a viscosity of 1,000 to 500,000 cps.
9. A transparent polyimide resin film produced by imidizing the polyamic acid solution according to any one of claims 1 to 8.
10. The transparent polyimide resin film according to claim 9, which satisfies the following physical property conditions (i) to (v):
a transmittance at a wavelength of 550nm of 88% or more at a film thickness of 100 μm or less,
(ii) a yellowness index of 5.0 or less according to ASTM E313,
(iii) a haze of 1.0 or less,
(iv) an elastic modulus in the range of 3 to 6GPa,
(v) the tensile strength is in the range of 120 to 200 MPa.
11. A transparent substrate comprising the transparent polyimide resin film according to claim 9 or 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170177752A KR102471861B1 (en) | 2017-12-22 | 2017-12-22 | Polyamic acid solution and transparent polyimide film using the same |
| KR10-2017-0177752 | 2017-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109957109A CN109957109A (en) | 2019-07-02 |
| CN109957109B true CN109957109B (en) | 2021-08-03 |
Family
ID=67023364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811573922.6A Active CN109957109B (en) | 2017-12-22 | 2018-12-21 | Polyamide acid solution, transparent polyimide resin film using same, and transparent substrate |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JP2019112632A (en) |
| KR (1) | KR102471861B1 (en) |
| CN (1) | CN109957109B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606949B (en) * | 2019-08-16 | 2020-12-11 | 深圳瑞华泰薄膜科技股份有限公司 | Colorless transparent polyimide film containing fluorine and Cardo structure and preparation method thereof |
| CN114599739A (en) * | 2019-10-31 | 2022-06-07 | 住友化学株式会社 | Optical film and flexible display device |
| CN110951077A (en) * | 2019-11-14 | 2020-04-03 | 安徽国风塑业股份有限公司 | Transparent polyimide precursor and preparation method thereof |
| KR20210075610A (en) * | 2019-12-13 | 2021-06-23 | 주식회사 두산 | Polyimide film having excellent weather resistance |
| KR20210075665A (en) * | 2019-12-13 | 2021-06-23 | 주식회사 두산 | Polyimide film having high yield strain |
| KR20220123394A (en) * | 2019-12-27 | 2022-09-06 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resins, varnishes and polyimide films |
| WO2021153379A1 (en) * | 2020-01-31 | 2021-08-05 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| JP7469088B2 (en) * | 2020-03-18 | 2024-04-16 | 住友化学株式会社 | Optical film and flexible display device |
| US20210301132A1 (en) * | 2020-03-27 | 2021-09-30 | Zhongtian Electronic Materials Co.,LTD. | Transparent and tint-free polyimide film, preparation method thereof and optical polyimide film |
| CN111363354A (en) * | 2020-03-27 | 2020-07-03 | 中天电子材料有限公司 | Polyimide colorless transparent film, preparation method thereof and optical PI film |
| JPWO2022054765A1 (en) * | 2020-09-10 | 2022-03-17 | ||
| KR102485698B1 (en) * | 2021-02-05 | 2023-01-06 | 주식회사 두산 | Polyimide film having excellent optical property |
| KR102493648B1 (en) * | 2021-03-04 | 2023-01-31 | 주식회사 두산 | Polyimide film having excellent resilence property |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006095924A1 (en) * | 2005-03-11 | 2006-09-14 | Nippon Shokubai Co., Ltd. | Production method of polyimide solution and fluorinated polyimide solution |
| JP2008115378A (en) * | 2006-10-10 | 2008-05-22 | Nippon Steel Chem Co Ltd | Method for forming polyimide resin layer |
| JP2011148955A (en) * | 2010-01-25 | 2011-08-04 | Kaneka Corp | Method for producing polyimide film, and the resultant polyimide film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028417A (en) * | 2004-07-20 | 2006-02-02 | Jsr Corp | Method for manufacturing polyimide |
| JP5899940B2 (en) * | 2012-01-13 | 2016-04-06 | 宇部興産株式会社 | Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition |
| TWI468440B (en) * | 2012-11-27 | 2015-01-11 | Ind Tech Res Inst | Transparent electrochromic polyimide, method for manufacturing the same, and electrochromic device utilizing the same |
| KR102430647B1 (en) * | 2015-12-24 | 2022-08-09 | 주식회사 두산 | Polyamic acid composition comprising novel diamine monomer and trasparent polyimide film using the same |
| JP6900152B2 (en) * | 2016-04-07 | 2021-07-07 | 株式会社カネカ | Film for glass replacement material |
-
2017
- 2017-12-22 KR KR1020170177752A patent/KR102471861B1/en active IP Right Grant
-
2018
- 2018-12-21 CN CN201811573922.6A patent/CN109957109B/en active Active
- 2018-12-21 JP JP2018239483A patent/JP2019112632A/en active Pending
-
2020
- 2020-12-18 JP JP2020210061A patent/JP7112476B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006095924A1 (en) * | 2005-03-11 | 2006-09-14 | Nippon Shokubai Co., Ltd. | Production method of polyimide solution and fluorinated polyimide solution |
| JP2008115378A (en) * | 2006-10-10 | 2008-05-22 | Nippon Steel Chem Co Ltd | Method for forming polyimide resin layer |
| JP2011148955A (en) * | 2010-01-25 | 2011-08-04 | Kaneka Corp | Method for producing polyimide film, and the resultant polyimide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7112476B2 (en) | 2022-08-03 |
| KR20190076170A (en) | 2019-07-02 |
| KR102471861B1 (en) | 2022-11-29 |
| CN109957109A (en) | 2019-07-02 |
| JP2019112632A (en) | 2019-07-11 |
| JP2021055104A (en) | 2021-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109957109B (en) | Polyamide acid solution, transparent polyimide resin film using same, and transparent substrate | |
| JP7163437B2 (en) | Polyamic acid composition with improved adhesion and polyimide film containing the same | |
| JP6899830B2 (en) | A polyamic acid solution to which a diamine monomer having a novel structure is applied and a polyimide film containing the same. | |
| KR101968258B1 (en) | Poly(amide-imide) block copolymer, article including same, and display device including the article | |
| KR102417428B1 (en) | Polyamic acid composition comprising alicyclic monomer and trasparent polyimide film using the same | |
| CN109897180B (en) | Polyamide acid solution, transparent polyimide resin film using same, and transparent substrate | |
| JP2018522105A (en) | Polyamide-imide precursor, polyamide-imide film, and display element including the same | |
| JP7387742B2 (en) | Polyamic acid composition and transparent polyimide film using the same | |
| US20180134848A1 (en) | Polyimide resin and film using same | |
| KR101837946B1 (en) | Polyimide Resin and Film Thereof | |
| JP2024028411A (en) | Polyamic acid composition and transparent polyimide film using the same | |
| CN112204085A (en) | Polyimide-based polymer film, and substrate for display device and optical device using same | |
| KR102293180B1 (en) | Diamine compound, polyimide precursor and polyimide film prepared by using same | |
| KR20170100794A (en) | Polyamic acid, Polyimide Resin, Polyimide Film and Display Device Comprising Thereof | |
| KR102390851B1 (en) | Polyimide copolymer and molded article using same | |
| KR20200072418A (en) | Diamine compound, polyimide precursor and polyimide film prepared by using same | |
| KR20200061707A (en) | A Method for manufacturing crosslinked polyimide film using polyhydric amine | |
| KR102224986B1 (en) | Diamine compound, polyimide precursor and polyimide film prepared by using same | |
| KR20210108756A (en) | Tetracarboxylic acid dianhydride, polyamic acid composition and polyimide film | |
| KR20210108755A (en) | Tetracarboxylic acid dianhydride, polyamic acid composition and polyimide film | |
| JP2022103036A (en) | Polyimide and film formed therefrom | |
| KR20200075759A (en) | Diamine compound, polyimide precursor and polyimide film prepared by using same | |
| KR20200059960A (en) | Diamine compound and polyimide precursor and polyimide film prepared by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |