CN109651630A - The manufacturing method of transparent polyimide film - Google Patents
The manufacturing method of transparent polyimide film Download PDFInfo
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- CN109651630A CN109651630A CN201710941223.1A CN201710941223A CN109651630A CN 109651630 A CN109651630 A CN 109651630A CN 201710941223 A CN201710941223 A CN 201710941223A CN 109651630 A CN109651630 A CN 109651630A
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- polyimide film
- transparent polyimide
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- 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
- 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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- 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)
Abstract
The present invention is a kind of manufacturing method of transparent polyimide film comprising the following steps: providing a fluorine-containing polyamic acid solution, fluorinated volume is greater than 12%；Dehydrating agent and catalyst are added in the fluorine-containing polyamic acid solution；And toasted in a manner of chemical imidization at 250 DEG C to 350 DEG C, it is greater than 30%, and transparent polyimide film of the b* value less than 3.5 of hue coordinate (CIELAB) to obtain elongation percentage.
Description
Technical field
A kind of manufacturing method of the present invention about transparent polyimide film is big by fluorinated volume in particular with chemical imidization method
Polyamic acid solution in 12% is made at 250 to 350 DEG C.
Background technique
The known mode for preparing polyimide film has thermal cyclization method (Thermal Imidization) and chemical imidization method
(Chemical Imidization) two ways, and increase polyimide film (Polyimide film, the PI film) transparency
Two kinds of means are generallyd use, one is the content for reducing aromatic structure in molecular structure, another kind is that addition fluorochemical monomer goes to hinder
Break or reduce intermolecular and intramolecular electron transition, and then obtains transparent polyimide film.
And general transparent polyimide film preparation is mostly prepared with thermal cyclization method at present.Under the conditions of thermal cyclization, technique
Temperature height will cause different as a result, the transparency in the lower thermal cyclization condition lower film of temperature is preferable, elongation percentage is poor；
But, color partially yellow poor transparency preferable in the elongation percentage of the higher thermal cyclization condition lower film of temperature.
And as transparent polyimide film be to accelerate to react using dehydrating agent and catalyst using chemical imidization legal system, if but adding
The ratio added it is bad or cyclisation temperature control it is bad, it is prepared come out transparent polyimide film generally also have elongation percentage compared with
The situation of difference or the partially yellow poor transparency of color degree generates.
Summary of the invention
The manufacturing method of transparent polyimide film of the invention, step are to include that one fluorine-containing polyamic acid of offer is molten
Liquid, fluorinated volume are greater than 12%；Dehydrating agent and catalyst are added in the fluorine-containing polyamic acid solution, the equivalents of dehydrating agent
More than or equal to 3；And toasted in a manner of chemical imidization at 250 DEG C to 350 DEG C, it is greater than 30%, and color to obtain elongation percentage
Transparent polyimide film of the b* value less than 3.5 of coordinate (CIELAB).
Detailed description of the invention
Fig. 1 is the flow chart of the manufacturing method of transparent polyimide film of the present invention.
Specific embodiment
Referring to Fig. 1, the manufacturing method of transparent polyimide film of the present invention, step is to include providing a fluorine-containing polyamides
Amino acid solution, fluorinated volume are greater than 12%；Dehydrating agent and catalyst are added in the fluorine-containing polyamic acid solution；And with chemistry
Cyclisation mode is toasted at 250 DEG C to 350 DEG C, is greater than 30% to obtain elongation percentage, and the b* value of hue coordinate (CIELAB) is small
In 3.5 transparent polyimide film.
The present invention can possess b* value less than 3.5, still maintain transparent when chemical imidization temperature higher (close to 350 DEG C)
Spend good characteristic；When being cyclized temperature lower (close to 250 DEG C), preferable ductility can be still maintained, using above-mentioned characteristic and then is made
The standby excellent elongation percentage having greater than 30%, and the b* value that can possess hue coordinate (CIELAB) is not easy the saturating of xanthochromia less than 3.5
Bright polyimide film.
Polyimide film of the present invention by fluorinated diamine monomer and fluoric dianhydride monomers, fluorinated diamine monomer and dianhydride monomer or
Diamine monomer and fluoric dianhydride monomers are through obtained by condensation reaction, the diamine monomer and the dianhydride monomer are about equimolar ratio.
In embodiment, which includes 2,2- bis- (trifluoromethyl) benzidine (TFMB) and the bis- [4- of 2,2-
(4- amino-benzene oxygen) phenyl] -1,1,1,3,3,3- hexafluoropropane (HFBAPP), further diamine monomer may include 2,2 ' -
Bis- (trifluoromethyl) -4,4 '-diamino-phenyl ethers (6FODA) and bis- (4- aminophenyl) fluorenes (BAFL) of 9,9-.
In embodiment, which is that 4,4 '-(4,4 '-isopropyl diphenoxies) are bis- (biphenyl dicarboxylic acid acid anhydride)
(BPADA), further dianhydride monomer includes 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids；Hexafluorodianhydride (6FDA) (6FDA), 3,3 ', 4,
4 '-bibenzene tetracarboxylics (BPDA) and cyclobutanetetracarboxylic dianhydride (CBDA) etc..
In embodiment, dehydrating agent includes acetic anhydride and tertiary amine, such as triethylamine.
In embodiment, catalyst includes pyridine, picoline and isoquinolin etc..
Common solvent, which can be used alone, one of which or to be used in mixed way, such as N- crassitude copper (NMP), dimethyl formyl
Amine (DMF), dimethyl acetamide (DMAc), γ-fourth lactones etc..
The preparation of fluorine-containing polyamic acid (PAA) solution
Fluorine-containing polyamic acid A
By in the DMAc merging reaction flask of about 45g, the TFMB and 9.29g of 5.71g (0.0178mole) is added
The BPADA of (0.0178mole), stirring continue stir about and are allowed to be reacted for 16 hours, form viscosity about to being completely dissolved
The fluorine-containing polyamic acid solution A of 170,000cps.
Fluorine-containing polyamic acid B
By in the DMAc merging reaction flask of about 45g, the HFBAPP and 7.51g of 7.49g (0.0145mole) is added
The BPADA of (0.0145mole), stirring continue stir about and are allowed to be reacted for 16 hours, form viscosity about to being completely dissolved
The fluorine-containing polyamic acid B solution of 100,000cps.
Embodiment 1
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 3 equivalents (2.6g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and be put into baking oven with 80 DEG C constant temperature 30 minutes,
It is warming up to 250 DEG C again about 2 hours, the solution is made to dry film forming, later remove the film from glass plate, that is, obtains of the invention saturating
Bright Kapton.
Embodiment 2
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 2 equivalents (1.8g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and be put into baking oven with 80 DEG C constant temperature 30 minutes,
It is warming up to 260 DEG C again about 2 hours, the solution is made to dry film forming, later remove the film from glass plate, that is, obtains of the invention saturating
Bright Kapton.
Embodiment 3
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 3 equivalents (2.6g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and be put into baking oven with 80 DEG C constant temperature 30 minutes,
It is warming up to 260 DEG C again about 2 hours, the solution is made to dry film forming, later remove the film from glass plate, that is, obtains of the invention saturating
Bright Kapton.
Embodiment 4
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 2 equivalents (1.8g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and be put into baking oven with 80 DEG C constant temperature 30 minutes,
It is warming up to 350 DEG C again about 2 hours, the solution is made to dry film forming, later remove the film from glass plate, that is, obtains of the invention saturating
Bright Kapton.
Embodiment 5
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 3 equivalents (2.6g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and be put into baking oven with 80 DEG C constant temperature 30 minutes,
It is warming up to 350 DEG C again about 2 hours, the solution is made to dry film forming, later remove the film from glass plate, that is, obtains of the invention saturating
Bright Kapton.
Embodiment 6
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 4 equivalents (3.5g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and it is put into baking oven and is divided with about 80 DEG C of constant temperature 30
Clock, then it is warming up to 370 DEG C about 2 hours, so that the solution is dried film forming, the film is removed from glass plate later, that is, obtains the present invention
Transparent polyimide film.
Embodiment 7
The fluorine-containing polyamic acid solution A of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 3 equivalents (2.6g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and it is put into baking oven and is divided with about 80 DEG C of constant temperature 30
Clock, then it is warming up to 220 DEG C about 2 hours, so that the solution is dried film forming, the film is removed from glass plate later, that is, obtains the present invention
Transparent polyimide film.
Comparative example 1
The fluorine-containing polyamic acid B solution of the gained of 30g is placed in the reaction flask of about 100mL, the DMAc that about 20g is added is carried out
The dehydrating agent acetic anhydride of 3 equivalents (2.6g) and the catalyst of 1 equivalent (0.8g) is added after deepfreeze about 30 minutes in dilution
Picoline mixing.With scraper by the solution in being coated as a layer on glass plate, and it is put into baking oven and is divided with about 80 DEG C of constant temperature 30
Clock, then it is warming up to 260 DEG C about 2 hours, so that the solution is dried film forming, the film is removed from glass plate later, that is, obtains the present invention
Transparent polyimide film.
Experiment test table
Shown in above table, fluorinated volume be greater than 12%, dehydrating agent equivalents be greater than 3, baking temperature between 250 to
At 350 DEG C, elongation can be obtained greater than 30%, and preferable transparent polyamides of the b* value of hue coordinate (CIELAB) less than 3.5 is sub-
Amine film.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (6)
1. a kind of manufacturing method of transparent polyimide film comprising the following steps:
A fluorine-containing polyamic acid solution is provided, fluorinated volume is greater than 12%；
Dehydrating agent and catalyst are added in the fluorine-containing polyamic acid solution, dehydrating agent equivalents is more than or equal to 3；And
It is toasted in a manner of chemical imidization at 250 DEG C to 350 DEG C, to obtain the transparent polyimide film.
2. the manufacturing method of transparent polyimide film as described in claim 1, wherein the fluorine-containing polyamic acid solution contains
Fluorine diamine monomer and fluoric dianhydride monomers.
3. the manufacturing method of transparent polyimide film as claimed in claim 2, wherein diamine monomer may include 2,2- bis- (three
Methyl fluoride) benzidine (TFMB) and bis- [4- (4- amino-benzene oxygen) phenyl] -1 of 2,2-, 1,1,3,3,3- hexafluoropropane
(HFBAPP), further diamine monomer may include 2,2 '-bis- (trifluoromethyl) -4,4 '-diamino-phenyl ethers (6FODA) and 9,
Bis- (4- aminophenyl) fluorenes (BAFL) of 9-.
4. the manufacturing method of clear polyimides as claimed in claim 2, wherein the dianhydride monomer is that 4,4 '-(4,4 '-is different
Two phenoxy group of propyl) bis- (biphenyl dicarboxylic acid acid anhydride) (BPADA), further dianhydride monomer includes 4,4 '-(hexafluoro isopropyl alkene) two
Anhydride phthalic acid；Hexafluorodianhydride (6FDA) (6FDA), 3,3 ', 4,4 '-bibenzene tetracarboxylics (BPDA) and cyclobutanetetracarboxylic dianhydride (CBDA) etc..
5. the manufacturing method of transparent polyimide film as described in claim 1, wherein the dehydrating agent is acetic anhydride.
6. the manufacturing method of transparent polyimide film as described in claim 1, wherein the catalyst is picoline, isoquinoline
Quinoline.
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| CN201710941223.1A CN109651630A (en) | 2017-10-11 | 2017-10-11 | The manufacturing method of transparent polyimide film |
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| CN201710941223.1A CN109651630A (en) | 2017-10-11 | 2017-10-11 | The manufacturing method of transparent polyimide film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759775A (en) * | 2019-10-21 | 2021-05-07 | 达迈科技股份有限公司 | Method for manufacturing continuous transparent polyimide film for display |
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|---|---|---|---|---|
| US20130274394A1 (en) * | 2010-12-31 | 2013-10-17 | Kolon Industries, Inc. | Transparent polyimide film and preparation method thereof |
| CN103467985A (en) * | 2013-09-22 | 2013-12-25 | 株洲时代电气绝缘有限责任公司 | Polyimide thin film |
| CN103788650A (en) * | 2013-12-31 | 2014-05-14 | 杭州福斯特光伏材料股份有限公司 | Colorless and transparent polyimide film and preparation method thereof |
| CN104558608A (en) * | 2015-01-08 | 2015-04-29 | 江汉大学 | Polyimide with novel structure and preparation method of transparent polyimide film |
| CN106928707A (en) * | 2015-12-31 | 2017-07-07 | 株式会社东进世美肯 | Polyimide polymer composition, method for producing same, and polyimide film |
-
2017
- 2017-10-11 CN CN201710941223.1A patent/CN109651630A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130274394A1 (en) * | 2010-12-31 | 2013-10-17 | Kolon Industries, Inc. | Transparent polyimide film and preparation method thereof |
| CN103467985A (en) * | 2013-09-22 | 2013-12-25 | 株洲时代电气绝缘有限责任公司 | Polyimide thin film |
| CN103788650A (en) * | 2013-12-31 | 2014-05-14 | 杭州福斯特光伏材料股份有限公司 | Colorless and transparent polyimide film and preparation method thereof |
| CN104558608A (en) * | 2015-01-08 | 2015-04-29 | 江汉大学 | Polyimide with novel structure and preparation method of transparent polyimide film |
| CN106928707A (en) * | 2015-12-31 | 2017-07-07 | 株式会社东进世美肯 | Polyimide polymer composition, method for producing same, and polyimide film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759775A (en) * | 2019-10-21 | 2021-05-07 | 达迈科技股份有限公司 | Method for manufacturing continuous transparent polyimide film for display |
| CN112759775B (en) * | 2019-10-21 | 2023-12-26 | 达迈科技股份有限公司 | Continuous transparent polyimide film manufacturing method for display |
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Application publication date: 20190419 |