CN114773600B - Polyimide film and preparation method and application thereof - Google Patents
Polyimide film and preparation method and application thereof Download PDFInfo
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- CN114773600B CN114773600B CN202210505792.2A CN202210505792A CN114773600B CN 114773600 B CN114773600 B CN 114773600B CN 202210505792 A CN202210505792 A CN 202210505792A CN 114773600 B CN114773600 B CN 114773600B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 27
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 25
- 150000004985 diamines Chemical class 0.000 claims abstract description 22
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 3
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 claims description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- IWFSADBGACLBMH-UHFFFAOYSA-N 4-[4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenyl]phenoxy]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC(N)=CC=3)C(F)(F)F)=CC=2)C=C1 IWFSADBGACLBMH-UHFFFAOYSA-N 0.000 claims description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- -1 hexafluoroisopropylidene Chemical group 0.000 claims 2
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000011521 glass Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 229920001646 UPILEX Polymers 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—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
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Disclosed are a polyimide film having a thickness of 15 μm or more, which is prepared by the steps of: 1) Polymerizing anhydride monomers and diamine monomers through condensation reaction to generate polyamide acid, wherein the anhydride monomers comprise BPDA and PMDA, and the diamine monomers comprise pPDA; the PMDA accounts for 10-45 percent based on the molar amount of the anhydride monomer; 2) Coating the solution of the polyamic acid on a substrate; 3) The process was subjected to elevated temperature imidization as follows, which includes three heating stages: (i) heating at 30-100deg.C for 0.5-1.5 hr; (ii) heating at 190-250 ℃ for 0.5-1.5 hours; and (iii) heating at 350-450 ℃ for 0.5-1.5 hours.
Description
Technical Field
The present invention relates to a heat resistant polyimide film useful for preparing flexible display substrates, which film combines improved adhesion, coefficient of thermal expansion and light transmission properties. The invention also relates to a method for manufacturing the heat-resistant polyimide film and application of the heat-resistant polyimide film as a flexible display substrate.
Background
For the flexible display device with increasingly strong demands, compared with the glass material with high specific gravity and difficult bending, the high polymer material has small specific gravity, good flexibility, easy manufacturing of an ultrathin film and good surface flatness, and gradually becomes a main candidate material for replacing glass. In the Low Temperature Polysilicon (LTPS) process used in the fabrication of OLED displays, the process temperature can reach over 450 ℃ and even exceed 500 ℃. This requires that the flexible polymeric film substrate material must be able to withstand this high temperature process and that the material itself be maintained unchanged in chemical composition and relatively stable in dimensions during the process. Heat resistance of at least 450 ℃ is a great challenge for most polymeric materials. Polyimide (PI) is known for its excellent heat resistance, and is currently the main choice for flexible OLED display substrate materials.
As a polymer substrate material for flexible OLED devices, it is desirable to meet some of the key requirements at the same time. These requirements include:
1) The polymer solution has good leveling property on the glass substrate, and the formed film has good adhesion with the substrate and has a flat surface;
2) The heat-resistant polymer has extremely high heat-resistant stability, so that the pollution to devices caused by micromolecules generated by thermal decomposition in the high-temperature processing process is avoided, and the product yield is influenced;
3) Good mechanical properties, such as very high tensile strength and high elongation at break, make the devices made thinner and more gentle;
4) Has good dimensional stability and has a Coefficient of Thermal Expansion (CTE) similar to that of the glass substrate or semiconductor material to prevent bending, delamination and interfacial stress of the substrate due to the mismatch of the CTE; and
5) Has good light transmission performance.
Chinese patent application CN109422876 discloses a polyimide film, in one embodiment, the polyamic acid of which employs 19.8 parts BPDA/29.7 parts PMDA/47.5 parts pda/2.5 parts ODA, which has the characteristics of high solids content and relatively low viscosity, and which can be advantageously film-formed. Although good film forming property and adhesion can be obtained with this film, there is room for further improvement in optical transparency.
Ma Xinyu (Material science and Process, volume 27, 3 rd, 2019, 6 months) discloses a method for producing a polyimide film by using BPDA/PMDA/m-TB as a polymerization monomer, which is a gradient temperature rising method, namely, a method of standing at 80℃for 1 hour and at 120℃for 160℃for 200℃for 250℃for 300℃for 350℃for 0.5 hour, respectively, which is considered: increasing the proportion of PMDA increases the solubility of the polyamic acid and decreasing the proportion of PMDA increases the light transmittance. However, the document does not relate to the adhesion of the polyimide film to the substrate.
The influence of a heating method on the imidization process is studied by the synthesis of polyamic acid and the imidization process of any Philippine et al (university of Dalian university of Industrial journal, volume 27, fourth stage, month 12 of 2008), and the imidization by adopting an isothermal gradient change method is considered to be reasonable.
Although various studies have been made on polyimide films in the prior art, when the thickness of the film reaches a certain level, it is always difficult for the conventional method to compromise the transparency of the film (low PMDA amount) and the film adhesion.
Therefore, there is still a need in the art to develop a method for producing polyimide films that can achieve a good compromise between film transparency (low PMDA content) and film adhesion when the thickness of the film is to some extent.
Disclosure of Invention
An object of the present invention is to provide a method for producing a polyimide film, which can give good consideration to the contradiction between the transparency of the film (low PMDA content) and the film adhesion when the film thickness reaches a certain level.
Another object of the present invention is to provide a polyimide film produced by the method of the present invention.
It is a further object of the present invention to provide the use of the polyimide film produced by the process of the present invention.
Accordingly, one aspect of the present invention relates to a polyimide film having a thickness of 15 μm or more, which is prepared by:
1) Polymerizing an anhydride monomer and a diamine monomer to form polyamic acid through a condensation reaction, wherein the anhydride monomer comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA), and the diamine monomer comprises p-phenylenediamine (pPDA); the 1,2,4, 5-pyromellitic dianhydride (PMDA) accounts for 10-45 percent based on the molar amount of the anhydride monomer;
2) Coating the solution of the polyamic acid on a substrate;
3) The method comprises the following three heating sections:
(i) Heating at 30-100deg.C for 0.5-1.5 hr;
(ii) Heating at 190-250deg.C for 0.5-1.5 hr; and
(iii) Heating at 350-450 deg.C for 0.5-1.5 hr.
Another aspect of the present invention relates to a method for producing a polyimide film having a thickness of 15 μm or more, comprising:
1) Polymerizing an anhydride monomer and a diamine monomer to form polyamic acid through a condensation reaction, wherein the anhydride monomer comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA), and the diamine monomer comprises p-phenylenediamine (pPDA); the 1,2,4, 5-pyromellitic dianhydride (PMDA) accounts for 10-45 percent based on the molar amount of the anhydride monomer;
2) Coating the solution of the polyamic acid on a substrate;
3) The method comprises the following three heating sections:
(i) Heating at 30-100deg.C for 0.5-1.5 hr;
(ii) Heating at 190-250deg.C for 0.5-1.5 hr; and
(iii) Heating at 350-450 deg.C for 0.5-1.5 hr.
In yet another aspect, the invention relates to the use of the polyimide film in the manufacture of a display.
Detailed Description
For polyimide films for displays, reducing the content of 1,2,4, 5-pyromellitic dianhydride (PMDA) helps to improve the light transmission of the film (see "synthesis and performance studies of thermoplastic copolyimide films" for Ma Xinyu et al (materials science and technology, 27, 3 rd, 2019, 6 th month)), which does not cause any sticking problems for low film thicknesses (e.g., film thicknesses less than 15 microns). However, if the film thickness exceeds 15 microns, a low 1,2,4, 5-pyromellitic dianhydride (PMDA) content may cause the film to roll up off, affecting normal use. In order to solve this problem, the inventors of the present invention have studied to find that, if a special program heating method is adopted, good film adhesion can be maintained at a high film thickness and a low 1,2,4, 5-pyromellitic dianhydride (PMDA) content. The present invention has been completed based on this finding.
Accordingly, the present invention provides a polyimide film having a thickness of 15 microns or more, preferably 16 to 50 microns, more preferably 17 to 45 microns, and most preferably 18 to 40 microns.
In one example of the present invention, the polyimide film has a 1% weight loss on heat temperature of greater than 550 ℃, a tensile elongation at break at room temperature of greater than 15%, and/or a Coefficient of Thermal Expansion (CTE) of less than 15ppm/°c between room temperature and 450 ℃, and a Coefficient of Thermal Expansion (CTE) of less than 10ppm/°c between room temperature and 400 ℃.
The method for manufacturing the polyimide film comprises the following steps:
1. formation of polyamic acid
The method of forming the polyamic acid according to the present invention is not particularly limited, and may be a conventional method known in the art. In one example of the present invention, the method of forming a polyamic acid includes polymerizing an anhydride monomer including 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA) and a diamine monomer including p-phenylenediamine (pda) by a condensation reaction to form a polyamic acid. In order to improve the light transmittance of the polyimide film formed, the amount of 1,2,4, 5-pyromellitic dianhydride (PMDA) is 10 to 45%, preferably 11 to 40%, more preferably 12 to 38%, most preferably 13 to 33%, and most preferably 14 to 28% based on the molar amount of the acid anhydride monomer.
In one embodiment of the present invention, the polyamic acid solution (10% by weight of solid content) has a viscosity in the range of 10000 to 30000cP, preferably 10500 to 29500cP, more preferably 11000 to 29000cP.
The polycondensation reaction may be carried out in a solvent. The solvent to be used is not particularly limited and may be any conventional solvent known in the art. In one example of the present invention, the solvent is selected from the group consisting of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylsulfoxide (DMSO), hexamethylphosphoramide (HMPA), and combinations of two or more thereof.
In one embodiment of the present invention, the polyamic acid may include other optional anhydride and/or diamine monomers in addition to the dianhydride and diamine monomers described above.
Non-limiting examples of suitable optional anhydride monomers are, for example: monoether dianhydrides such as 3,3'4,4' -diphenyl ether dianhydride (ODPA); hexafluorodianhydride such as 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA); diphenyl sulfone dianhydrides such as 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA); bisphenol a diether dianhydrides such as 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (bisda); benzophenone dianhydrides such as 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), or combinations of two or more thereof formed in any ratio.
In one embodiment of the invention, the amount of said optional monomer is not more than 10%, preferably not more than 8%, more preferably not more than 5% based on the total molar amount of anhydride monomers.
Non-limiting examples of suitable diamine monomers are, for example, m-phenylenediamine (mPDA), 4' -diaminodiphenyl ether (ODA), 3,4' -diaminodiphenyl ether (3, 4' -ODA), 4' -diaminodiphenyl sulfone (DDS) 3,3' -diaminodiphenyl ether (3, 3' -DDS), 2' -dimethyl-4, 4' -diaminodiphenyl ether (oTOL), 4' -diaminodiphenyl Methane (MDA), 4' -diaminobenzophenone 4,4' -diaminodiphenyl-2, 2-hexafluoropropane, 9-bis- (4-aminophenyl) fluorene, 9-bis- (3-fluoro-4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (PFMB), bis- (2-trifluoromethyl-4-aminophenoxy) biphenyl, or a combination of two or more thereof formed in any ratio.
In one embodiment of the present invention, the optional diamine monomer is added at a ratio of no greater than 20%, preferably no greater than 15%, more preferably no greater than 10% based on the total moles of diamine monomer.
In one embodiment of the present invention, the polymerization temperature may be controlled between 30℃and 80℃and preferably between 35℃and 75℃and more preferably between 40℃and 70 ℃.
In one embodiment of the invention, one of the forward and reverse feeding sequences can be selected as the feeding method according to the reactivity of dianhydride or diamine monomers in the polymerization process. In the normal feed sequence, one or more diamine monomers are first dissolved in the reaction solvent, followed by the addition of one or more dianhydride monomers to initiate the polycondensation reaction. In the back-feed sequence, one or more dianhydride monomers are added preferentially to a quantity of solvent, followed by the desired diamine monomer.
2. Coating the solution of the polyamic acid on a substrate
The applicable solution coating method is not particularly limited and may be any conventional method known in the art. In one example of the present invention, the coating method is selected from brushing, casting, knife coating, and the like.
The substrate to be used is not particularly limited, and may be a conventional substrate known in the art, and it may be, for example, a plastic substrate, a metal substrate, a glass substrate, or the like, preferably a glass substrate.
3. The method comprises the following three heating sections:
(i) Heating (or maintaining) at 30-100deg.C, preferably 40-90deg.C, more preferably 50-80deg.C for 0.5-1.5 hr, preferably 0.6-1.2 hr, more preferably 0.8-1 hr;
(ii) Heating (or maintaining) at 190-250deg.C, preferably 200-240 deg.C, more preferably 210-230deg.C for 0.5-1.5 hr, preferably 0.6-1.2 hr, more preferably 0.8-1 hr; and
(iii) Heating at 350-450deg.C, preferably 360-440 deg.C, more preferably 370-430 deg.C for 0.5-1.5 hr, preferably 0.6-1.2 hr, more preferably 0.8-1 hr.
The rate of temperature rise for temperature rise between the respective heat-retaining stages is not particularly limited. In one embodiment of the invention, the coating material is heated from one holding stage to the next at a heating rate of 1-10 c/min, preferably 2-5 c/min.
The method adopts a method of multi-monomer copolymerization to prepare the polyamic acid copolymer, adopts an improved procedure baking mode to form a film for the prepared polyamic acid solution, and the obtained polyimide film has better adhesion with a glass substrate, thus obtaining the polyimide film with good shape. At the same time, the CTE of the film can be tuned by a combination of different monomers. The polyimide copolymer film provided by the invention still maintains good thermal/mechanical properties.
The heat-resistant polyimide film of the invention shows excellent heat resistance, dimensional stability and base adhesiveness in a wide high temperature range, and after imidization by baking at a programmed temperature, the polyimide copolymer film is well bonded on a glass substrate without defects and is free from curling after peeling. Meanwhile, the film forming property of the polyimide film is greatly improved, the polyimide film has good laminating property with a substrate, the flatness is good, and meanwhile, the CTE value can be regulated and controlled. The polyimide film can be used as a substrate material of a flexible display device and a substrate and packaging material of a flip-chip film.
Examples
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
Test method
Solution viscosity test:
solution viscosity was measured using a Brookfield DV-type I viscometer at 25 ℃.
Dimensional stability test:
the change in film size with temperature was measured by a thermo-mechanical analyzer (TMA) model TA-Q400, and the sample was heated from 0deg.C to 500deg.C at a rate of 10deg.C/min in a nitrogen atmosphere.
Film forming performance test:
the state of the polyimide film on the glass substrate and the adhesion of the polyimide film to the glass substrate were observed.
Thermal stability test:
film thermal stability was measured by thermogravimetric analyzer (TGA) model TA-Q50 and the sample was heated from room temperature to 650 ℃ in a nitrogen atmosphere at a rate of 20 ℃/min.
Mechanical property test:
the mechanical properties of the film samples were measured by an INSTRON stretcher INSTRON 5969 series, with 10 to 20 micrometer film samples at room temperature at a 10 millimeter per minute stretch rate, starting at a length of 100 millimeters.
Example 1
Polyimide film prepared from BPDA/PMDA/pPDA copolymer by adopting temperature programming method of the invention
The solution of polyamide acid is prepared by adopting a normal feeding method, BPDA and PMDA with corresponding molar amounts are added into a glass bottle filled with N-methylpyrrolidone (NMP) and inflated with nitrogen atmosphere, pPDA monomer with corresponding molar amounts is added after stirring for 15 minutes at room temperature, NMP solvent is continuously added to ensure that the inner wall of the container has no residual monomer, and the solution is diluted until the solid content in the solution is 10wt%. The molar ratios of the monomers are shown in Table 1.
The resulting polyamic acid solution was cast on a glass substrate, and the glass substrate with the polyamic acid film was placed in an oven at 75 ℃, 230 ℃, 400 ℃ for 1.0h, and 1.5h, respectively.
The polyimide films were tested for properties and the results are shown in table 1 below.
TABLE 1.1 Heat resistance and film Forming adhesion of BPDA/PMDA/pPDA copolymer under temperature programmed method
TABLE 1.2 mechanical Properties of BPDA/PMDA/pPDA copolymer under temperature programmed method
From the above test results, it can be seen that polyimide films formed using the imidization conditions of the present invention can have good adhesion in the case of thick films, both with high PMDA content and low PMDA content as low as 10 mole%, but are excluded from the scope of the present invention because polyimide with high PMDA content has slightly poor light transmittance.
Comparative example 1
Polyimide film prepared from BPDA/PMDA/pPDA copolymer by non-inventive temperature programming method
The procedure of example 1 was repeated, but the imidization conditions were as follows:
the glass substrate with the polyamic acid film was placed in an oven at 75℃and 165℃and 320℃for 1.0h, 1.0h and 1.5h, respectively.
The polyimide films were tested for properties and the results are shown in table 2 below.
TABLE 2 Heat resistance and film Forming Fit of BPDA/PMDA/pPDA copolymer
From the above test results, it was found that when the imidization method different from the method of the present invention was used, good adhesion was obtained for all polyimides having PMDA content at a low film thickness. However, after a film thickness of greater than 16 microns, only polyimide films having PMDA contents in excess of 50 mole% can be bonded to glass substrates. However, the light transmittance of the film is not satisfactory.
Comparative example 2
Preparation of polyimide film from BPDA/PMDA/pPDA copolymer by gradient-free continuous heating method
The procedure of example 1 was repeated, but the imidization conditions were as follows:
the continuous temperature rise is carried out at a temperature rise rate of 2 ℃/min within the range of 40-400 ℃ and the temperature stays at 400 ℃ for 0.5h.
The polyimide films were tested for properties and the results are shown in table 3 below.
TABLE 3 preparation of BPDA/PMDA/pPDA copolymer by continuous temperature rising method
From the above test results, it was found that when imidization was performed by a continuous temperature rising method, good adhesion was obtained for all polyimides having PMDA content at a low film thickness. However, after a film thickness of greater than 16 microns, only polyimide films having PMDA contents in excess of 50 mole% can be bonded to glass substrates. However, the light transmittance of the film is not satisfactory.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (25)
1. A polyimide film having a thickness of 15 μm or more, the polyimide film being produced by:
1) Polymerizing an anhydride monomer and a diamine monomer to form polyamic acid through a condensation reaction, wherein the anhydride monomer comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA), and the diamine monomer comprises p-phenylenediamine (pPDA); the 1,2,4, 5-pyromellitic dianhydride (PMDA) accounts for 10-45 percent based on the molar amount of the anhydride monomer;
2) Coating the solution of the polyamic acid on a substrate;
3) The process was subjected to elevated temperature imidization as follows, which includes three heating stages:
(i) Heating at 30-100deg.C for 0.5-1.5 hr;
(ii) Heating at 190-250deg.C for 0.5-1.5 hr; and
(iii) Heating at 350-450 deg.C for 0.5-1.5 hr.
2. The polyimide film according to claim 1, which has a thickness of 16 to 50 μm.
3. The polyimide film according to claim 1, which has a thickness of 17 to 45 μm.
4. The polyimide film according to claim 1, which has a thickness of 18 to 40 μm.
5. The polyimide film of claim 1, wherein the elevated temperature imidization comprises three heating stages:
(i) Preserving heat for 0.5-1.5 hours at the temperature of 40-90 ℃;
(ii) Preserving heat for 0.5-1.5 hours at 200-240 ℃; and
(iii) Preserving heat for 0.5-1.5 hours at 360-440 ℃.
6. The polyimide film of claim 1, wherein the elevated temperature imidization comprises three heating stages:
(i) Preserving heat for 0.6-1.2 hours at 50-80 ℃;
(ii) Preserving heat for 0.6-1.2 hours at 210-230 ℃; and
(iii) Preserving heat for 0.6-1.2 hours at 370-430 ℃.
7. The polyimide film of claim 1, wherein the elevated temperature imidization comprises three heating stages:
(i) Preserving heat for 0.8-1 hour at 40-90 ℃;
(ii) Preserving heat for 0.8-1 hour at 200-240 ℃; and
(iii) Preserving heat for 0.8-1 hour at 360-440 ℃.
8. The polyimide film according to any one of claims 1 to 7, wherein 1,2,4, 5-pyromellitic dianhydride (PMDA) is 11 to 40% based on the molar amount of the acid anhydride monomer.
9. The polyimide film according to any one of claims 1 to 7, wherein the 1,2,4, 5-pyromellitic dianhydride (PMDA) is present in an amount of 12 to 38% based on the molar amount of the acid anhydride monomer.
10. The polyimide film according to any one of claims 1 to 7, wherein the 1,2,4, 5-pyromellitic dianhydride (PMDA) accounts for 13 to 33% based on the molar amount of the acid anhydride monomer.
11. The polyimide film according to any one of claims 1 to 7, wherein the 1,2,4, 5-pyromellitic dianhydride (PMDA) accounts for 14 to 28% based on the molar amount of the acid anhydride monomer.
12. The polyimide film according to any one of claim 1 to 7, wherein the polyamic acid may further comprise other optional acid anhydride and/or diamine monomer in addition to the above dianhydride and diamine monomer,
the optional anhydride monomer is selected from monoether dianhydride, hexafluorodianhydride, diphenyl sulfone dianhydride, bisphenol A diether dianhydride, benzophenone dianhydride, or a combination of two or more of them formed in any proportion;
the diamine monomer is selected from m-phenylenediamine (mPDA), 4' -diaminodiphenyl ether (ODA), 3,4' -diaminodiphenyl ether (3, 4' -ODA), 4' -diaminodiphenyl sulfone (DDS) 3,3' -diaminodiphenyl ether (3, 3' -DDS), 2' -dimethyl-4, 4' -diaminodiphenyl ether (oTOL), 4' -diaminodiphenyl Methane (MDA), 4' -diaminobenzophenone 4,4' -diaminodiphenyl-2, 2-hexafluoropropane, 9-bis- (4-aminophenyl) fluorene, 9-bis- (3-fluoro-4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (PFMB), bis- (2-trifluoromethyl-4-aminophenoxy) biphenyl, or a combination of two or more thereof formed in any ratio.
13. The polyimide film of claim 12, wherein the optional anhydride monomer is selected from the group consisting of 3,3'4,4' -diphenyl ether dianhydride (ODPA), 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA), 4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (bisda), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), or a combination of two or more thereof formed in any ratio.
14. A method for producing a polyimide film having a thickness of 15 μm or more, comprising:
1) Polymerizing an anhydride monomer and a diamine monomer to form polyamic acid through a condensation reaction, wherein the anhydride monomer comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA), and the diamine monomer comprises p-phenylenediamine (pPDA); the 1,2,4, 5-pyromellitic dianhydride (PMDA) accounts for 10-45 percent based on the molar amount of the anhydride monomer;
2) Coating the solution of the polyamic acid on a substrate;
3) The method comprises the following three heating sections:
(i) Heating at 30-100deg.C for 0.5-1.5 hr;
(ii) Heating at 190-250deg.C for 0.5-1.5 hr; and
(iii) Heating at 350-450 deg.C for 0.5-1.5 hr.
15. The method of claim 14, wherein the polyimide film has a thickness of 16 to 50 microns.
16. The method of claim 14, wherein the polyimide film has a thickness of 17 to 45 microns.
17. The method of claim 14, wherein the polyimide film has a thickness of 18 to 40 microns.
18. The method of claim 14, wherein said elevated temperature imidization comprises three heating stages:
(i) Preserving heat for 0.5-1.5 hours at the temperature of 40-90 ℃;
(ii) Preserving heat for 0.5-1.5 hours at 200-240 ℃; and
(iii) Preserving heat for 0.5-1.5 hours at 360-440 ℃.
19. The method of claim 14, wherein said elevated temperature imidization comprises three heating stages:
(i) Preserving heat for 0.6-1.2 hours at 50-80 ℃;
(ii) Preserving heat for 0.6-1.2 hours at 210-230 ℃; and
(iii) Preserving heat for 0.6-1.2 hours at 370-430 ℃.
20. The method of claim 14, wherein said elevated temperature imidization comprises three heating stages:
(i) Preserving heat for 0.8-1 hour at 40-90 ℃;
(ii) Preserving heat for 0.8-1 hour at 200-240 ℃; and
(iii) Preserving heat for 0.8-1 hour at 360-440 ℃.
21. The process according to any one of claims 14 to 20, characterized in that 1,2,4, 5-pyromellitic dianhydride (PMDA) comprises 11 to 40% by mole of the anhydride monomers.
22. The process according to any one of claims 14 to 20, characterized in that 1,2,4, 5-pyromellitic dianhydride (PMDA) comprises 12 to 38% based on the molar amount of the anhydride monomer.
23. The process according to any one of claims 14 to 20, characterized in that 1,2,4, 5-pyromellitic dianhydride (PMDA) comprises 13 to 33% based on the molar amount of the anhydride monomer.
24. The process according to any one of claims 14 to 20, characterized in that 1,2,4, 5-pyromellitic dianhydride (PMDA) comprises 14 to 28% by mole of the anhydride monomer.
25. Use of a polyimide film according to any one of claims 1 to 13 for the manufacture of a display.
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| KR20160098833A (en) * | 2015-02-11 | 2016-08-19 | 코오롱인더스트리 주식회사 | Polyamic acid, And Polyimide Resin And Polyimide Film |
| CN109423047A (en) * | 2017-08-28 | 2019-03-05 | 苏州聚萃材料科技有限公司 | Heat-proof polyimide film and its display base plate of preparation |
| KR20190044312A (en) * | 2017-10-20 | 2019-04-30 | 타이미드 테크 인코퍼레이티드 | Method for manufacturing transparent polyimide film |
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| CN104672901A (en) * | 2015-02-28 | 2015-06-03 | 重庆杰博科技有限公司 | Transparent polyimide film and preparation method thereof |
| CN109423047A (en) * | 2017-08-28 | 2019-03-05 | 苏州聚萃材料科技有限公司 | Heat-proof polyimide film and its display base plate of preparation |
| KR20190044312A (en) * | 2017-10-20 | 2019-04-30 | 타이미드 테크 인코퍼레이티드 | Method for manufacturing transparent polyimide film |
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