CN111662473A - Preparation method of low-yellow-index colorless transparent polyimide film - Google Patents
Preparation method of low-yellow-index colorless transparent polyimide film Download PDFInfo
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- CN111662473A CN111662473A CN202010723516.4A CN202010723516A CN111662473A CN 111662473 A CN111662473 A CN 111662473A CN 202010723516 A CN202010723516 A CN 202010723516A CN 111662473 A CN111662473 A CN 111662473A
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- transparent polyimide
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 64
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 150000004985 diamines Chemical class 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 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 abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims description 36
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical group NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 29
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 26
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical group C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 claims description 15
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical group NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 15
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical group CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 11
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical group NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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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
-
- 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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
-
- 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)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method of a low-yellow-index colorless transparent polyimide film, which comprises the following preparation steps: s1: treating an N, N-dimethylacetamide solvent to obtain an N, N-dimethylacetamide solvent A and an N, N-dimethylacetamide solvent B; s2: mixing the processed diamine solid with an N, N-dimethylacetamide solvent A to prepare a mixed solution A; s3: taking a mono-anhydride compound and an N, N-dimethylacetamide solvent B to prepare a mixed solution B; s4: preparing a pretreated resin liquid from the treated dianhydride solid and the mixed solution A, and continuously adding the mixed solution B into a reaction vessel to prepare a polymer solution; s5: and coating the polymer solution on a glass plate, and drying to obtain the polyimide film. The yellow index of the finally prepared colorless transparent polyimide film is in a lower range, so that the quality of the product can be better controlled, and the requirements of higher-end industries are met.
Description
Technical Field
The invention relates to the field of polyimide films, in particular to a preparation method of a low-yellow-index colorless transparent polyimide film.
Background
At present, the flexible display screen industry is rapidly developed, and a plurality of panel manufacturers develop flexible display screen projects. Polyimide is a key material of a flexible display screen, and the yellow index is an important index of a polyimide film material. Polyimide materials are mostly polymerized from diamines and dianhydrides, but the diamine residues are susceptible to high temperatures, which causes polyimide films to be thermally yellowed. Therefore, the technology for preparing colorless transparent polyimide films with ultra-low yellow index still needs to be further improved.
Disclosure of Invention
Aiming at the defects that diamine residues in polyimide in the prior art are easy to be thermally yellowed and the like, the invention provides a novel preparation method of a low-yellow-index colorless transparent polyimide film.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of a low-yellow-index colorless transparent polyimide film comprises the following preparation steps:
s1: placing the N, N-dimethylacetamide solvent in a rotary evaporator for dehydration and purification treatment, pouring the N, N-dimethylacetamide solvent A and the N, N-dimethylacetamide solvent B into two dry glass flasks respectively after the dehydration and purification treatment is finished, and standing for later use;
s2: putting the diamine solid into a sublimer for purification treatment, mixing the diamine solid in X weight parts with N, N-dimethylacetamide solvent A in Z weight parts after the purification treatment is finished, and fully stirring for 5-30 minutes until the diamine solid is completely dissolved to prepare a mixed solution A;
s3: mixing a mono-anhydride compound and an N, N-dimethylacetamide solvent B according to a weight ratio of 0.05: 1-0.3: 1 to prepare a mixed solution B;
s4: putting dianhydride solid into a sublimator for purification treatment, after the purification treatment is finished, putting Y parts by weight of dianhydride solid and the mixed solution A into a reaction container, fully stirring for 5-24 hours to prepare a pre-treated resin solution, continuously adding the mixed solution B into the reaction container, and continuously stirring for 1-5 hours to fully perform a polymerization reaction, wherein the weight ratio of the mixed solution B to the pre-treated resin solution is 0.5: 100-5: 100, and a polymer solution with the viscosity coefficient of 5000-70000 mPa & s is prepared;
s5: and uniformly coating the polymer solution on a glass plate, heating to 120 ℃ and keeping the temperature for 30-50 minutes, then gradually heating to 220 ℃ in a gradient of 5-15 ℃, then drying for 30-50 minutes, and finally heating to 310 ℃ and keeping the temperature for 30-45 minutes to finally obtain the colorless transparent polyimide film with the thickness of 50-100 microns.
In step S1 of the present invention, the N, N-dimethylacetamide solvent contains a part of water, and the reduced pressure distillation is performed by using a rotary evaporator, so as to obtain the N, N-dimethylacetamide solvent a and the N, N-dimethylacetamide solvent B with higher purity, thereby preventing the water from interfering with the subsequent polymerization reaction.
In step S2 of the present invention, the diamine solid is an important monomer for producing polyimide, and has a very high purity, and the diamine solid can be purified by a sublimer to obtain a high purity diamine solid. Adding the diamine solid into the N, N-dimethylacetamide solvent A, and uniformly dispersing the diamine solid in the N, N-dimethylacetamide solvent A after fully stirring, so that the subsequent polymerization reaction is fully and completely facilitated.
In step S3 of the present invention, the monoanhydride compound is completely dissolved in the N, N-dimethylacetamide solvent B, which contributes to sufficient progress of the subsequent reaction.
In step S4 of the present invention, dianhydride solid is another important monomer for producing polyimide, and purification treatment using a sublimer can produce dianhydride solid with high purity. And adding the dianhydride solid into the mixed solution A and fully stirring to promote the dianhydride solid and the diamine solid to fully perform polymerization reaction. Before the polymerization reaction of the dianhydride solid and the diamine solid is finished, the mixed solution B containing the mono-anhydride compound is added, so that other groups are introduced, and redundant amino at the tail end of a molecular chain in the pretreated resin solution is reacted, so that the high-temperature yellowing effect of the amino in the polymer solution is weakened.
In step S5 of the present invention, a gradient thermal curing process is employed to ensure sufficient curing of the colorless transparent polyimide film, thereby improving the uniformity of film formation and reducing the surface defect rate.
According to the invention, the mono-anhydride compound is continuously added before the polymerization reaction is finished, so that other groups are introduced, and residual amino groups in diamine solid are converted into groups which are not affected by heat, thereby fundamentally solving the problem of high yellow index of the colorless transparent polyimide film.
Preferably, in the above method for preparing a low-yellow-index colorless transparent polyimide film, in the steps S2 and S4, the X parts by weight of diamine solids, the Y parts by weight of dianhydride solids, and the Z parts by weight of N, N-dimethylacetamide solvent a satisfy the following formula:
the invention adopts the components in the proportion to prepare the pretreated resin liquid, and can improve the success rate of molecular collision polymerization in the polymerization reaction process, thereby synthesizing a polymer with higher molecular weight and further improving the production efficiency of the later coating process.
Preferably, in the method for producing a low-yellow-index colorless transparent polyimide film, the monoanhydride compound contains one of an ethane residue, a propane residue, a cyclopropane residue, a cyclobutane residue, a cyclopentane residue, a cyclohexane residue, and a 1, 2-benzene residue.
The use of the above-mentioned monoanhydride compound in the present invention enables one of an ethane residue, a propane residue, a cyclopropane residue, a cyclobutane residue, a cyclopentane residue, a cyclohexane residue and a 1, 2-benzene residue to be preferably introduced into the polymerization reaction.
Preferably, in the above method for preparing a low-yellow-index colorless transparent polyimide film, in step S1, the water content of the N, N-dimethylacetamide solvent is 0-0.05% after dehydration and purification treatment.
The N, N-dimethylacetamide solvent is dehydrated and purified to obtain extremely high purity, and the hydrolysis condition in the polymer solution can be avoided.
Preferably, in the method for preparing a colorless and transparent polyimide film with a low yellow index, in the steps S2 and S4, the molar ratio of the dianhydride solid to the diamine solid is 0.95:1 to 1.05: 1.
The dianhydride solid and the diamine solid in the invention are prepared by adopting the molar ratio, so that the dianhydride solid and the diamine solid are equivalent in number during polymerization, the residual amount of the monomer is reduced to the maximum extent, and the polymer can obtain higher molecular weight.
Preferably, in the above method for preparing a colorless transparent polyimide film with a low yellow index, the molecular chain of the colorless transparent polyimide film contains a repeating unit structure of formula 1, and the repeating unit structure of formula 1 is as follows:
wherein R isaIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RbIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
The molecular chain of the finally prepared colorless transparent polyimide film contains the repeating unit structure shown in the formula 1, so that a conjugated system in the colorless transparent polyimide film is broken, and the problem of a charge transfer complex in the traditional polyimide is solved, so that the polyimide film is colorless and transparent.
Preferably, in the above method for preparing a low-yellow-index colorless transparent polyimide film, in step S4, the molecular chain of the pretreated resin solution contains a unit structure represented by formula 2, where the unit structure represented by formula 2 is as follows:
wherein R iscIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RdIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
The pretreatment resin liquid prepared by the invention contains the unit structure shown in the formula 2, so that a conjugated system in the pretreatment resin liquid is broken, and the problem that a finally prepared colorless transparent polyimide film has a charge transfer complex is solved.
Preferably, in the above method for preparing a low-yellow-index colorless transparent polyimide film, in step S4, the molecular chain of the pretreated resin solution further includes a unit structure represented by formula 3, where the unit structure represented by formula 3 is as follows:
wherein R iseIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RfIs 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4'One or more of-diaminodiphenyl sulfone residue, 3 ' -diaminodiphenyl sulfone residue, 2 ' -bis (trifluoromethyl) benzidine residue, 4 ' - (hexafluoroisopropylidene) diphenylamine residue, RgIs one or more of ethane residue, propane residue, cyclopropane residue, cyclobutane residue, cyclopentane residue, cyclohexane residue and 1, 2-benzene residue.
The prepared pretreated resin liquid contains a unit structure shown in a formula 3, the content of exposed amino groups in the pretreated resin liquid is reduced by introducing a unit structure system shown in the formula 3, and the yellow index of the finally prepared colorless transparent polyimide film can be greatly reduced by introducing the unit structure system shown in the formula 3 because the exposed amino groups are easily yellow due to the influence of heating high temperature.
Preferably, in the method for preparing the colorless transparent polyimide film with the low yellow index, the yellow index of the colorless transparent polyimide film is less than 2.
The yellow index of the finally prepared colorless transparent polyimide film is in a lower range, so that the quality of the product can be better controlled, and the requirements of higher-end industries are met.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments, but they are not intended to limit the invention:
example 1
A preparation method of a low-yellow-index colorless transparent polyimide film comprises the following preparation steps:
s1: placing the N, N-dimethylacetamide solvent in a rotary evaporator for dehydration and purification treatment, pouring the N, N-dimethylacetamide solvent A and the N, N-dimethylacetamide solvent B into two dry glass flasks respectively after the dehydration and purification treatment is finished, and standing for later use;
s2: putting the diamine solid into a sublimer for purification treatment, mixing the diamine solid in X weight parts with N, N-dimethylacetamide solvent A in Z weight parts after the purification treatment is finished, and fully stirring for 5 minutes until the diamine solid is completely dissolved to prepare mixed solution A;
s3: mixing a mono-anhydride compound with an N, N-dimethylacetamide solvent B according to a weight ratio of 0.05:1 to prepare a mixed solution B;
s4: putting dianhydride solid into a sublimator for purification treatment, after the purification treatment is finished, putting Y parts by weight of dianhydride solid and the mixed solution A into a reaction vessel, fully stirring for 5 hours to prepare pretreated resin liquid, continuously adding the mixed solution B into the reaction vessel, and continuously stirring for 1 hour to fully perform polymerization reaction, wherein the weight ratio of the mixed solution B to the pretreated resin liquid is 0.5:100, and a polymer solution with the viscosity coefficient of 5000 mPas is prepared;
s5: and (3) uniformly coating the polymer solution on a glass plate, heating to 120 ℃ and keeping the temperature for 30 minutes, then gradually heating to 220 ℃ in a gradient of 5 ℃, then drying for 30 minutes, and finally heating to 310 ℃ and keeping the temperature for 30 minutes to finally obtain the colorless transparent polyimide film with the thickness of 50 microns.
Preferably, in the steps S2, S4, the X parts by weight diamine solids, Y parts by weight dianhydride solids, and Z parts by weight N, N-dimethylacetamide solvent a satisfy the following formula:
preferably, the monoanhydride-based compound contains one of an ethane residue, a propane residue, a cyclopropane residue, a cyclobutane residue, a cyclopentane residue, a cyclohexane residue, and a 1, 2-benzene residue.
Preferably, in step S1, the water content of the N, N-dimethylacetamide solvent is 0 after dehydration and purification.
Preferably, in the steps S2 and S4, the molar ratio of the dianhydride solid to the diamine solid is 0.95: 1.
Preferably, the molecular chain of the colorless transparent polyimide film contains a repeating unit structure of formula 1, and the repeating unit structure of formula 1 is as follows:
wherein R isaIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RbIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
Preferably, in step S4, the molecular chain of the pretreated resin liquid contains a unit structure represented by formula 2, and the unit structure represented by formula 2 is as follows:
wherein R iscIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RdIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
Preferably, in step S4, the molecular chain of the pretreated resin liquid further includes a unit structure of formula 3, where the unit structure of formula 3 is as follows:
wherein R iseIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RfIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue, RgIs one or more of ethane residue, propane residue, cyclopropane residue, cyclobutane residue, cyclopentane residue, cyclohexane residue and 1, 2-benzene residue.
Preferably, the colorless transparent polyimide film has a yellow index < 2.
Example 2
A preparation method of a low-yellow-index colorless transparent polyimide film comprises the following preparation steps:
s1: placing the N, N-dimethylacetamide solvent in a rotary evaporator for dehydration and purification treatment, pouring the N, N-dimethylacetamide solvent A and the N, N-dimethylacetamide solvent B into two dry glass flasks respectively after the dehydration and purification treatment is finished, and standing for later use;
s2: putting the diamine solid into a sublimer for purification treatment, mixing the diamine solid in X weight parts with N, N-dimethylacetamide solvent A in Z weight parts after the purification treatment is finished, and fully stirring for 30 minutes until the diamine solid is completely dissolved to prepare mixed solution A;
s3: mixing a mono-anhydride compound with an N, N-dimethylacetamide solvent B according to a weight ratio of 0.3:1 to prepare a mixed solution B;
s4: putting dianhydride solid into a sublimer for purification treatment, putting Y parts by weight of dianhydride solid and the mixed solution A into a reaction vessel after the purification treatment is finished, fully stirring for 24 hours to prepare pretreated resin liquid, continuously adding the mixed solution B into the reaction vessel, and continuously stirring for 5 hours to fully perform polymerization reaction, wherein the weight ratio of the mixed solution B to the pretreated resin liquid is 5:100, and a polymer solution with the viscosity coefficient of 70000mPa & s is prepared;
s5: and (2) uniformly coating the polymer solution on a glass plate, heating to 120 ℃ and keeping the temperature for 50 minutes, then gradually heating to 220 ℃ in a gradient of 15 ℃, then drying for 50 minutes, and finally heating to 310 ℃ and keeping the temperature for 45 minutes to finally obtain the colorless transparent polyimide film with the thickness of 100 microns.
Preferably, in the steps S2, S4, the X parts by weight diamine solids, Y parts by weight dianhydride solids, and Z parts by weight N, N-dimethylacetamide solvent a satisfy the following formula:
preferably, the monoanhydride-based compound contains one of an ethane residue, a propane residue, a cyclopropane residue, a cyclobutane residue, a cyclopentane residue, a cyclohexane residue, and a 1, 2-benzene residue.
Preferably, in the step S1, the water content of the N, N-dimethylacetamide solvent after dehydration and purification is 0.05%.
Preferably, in the steps S2 and S4, the molar ratio of the dianhydride solid to the diamine solid is 1.05: 1.
Preferably, the molecular chain of the colorless transparent polyimide film contains a repeating unit structure of formula 1, and the repeating unit structure of formula 1 is as follows:
wherein R isaIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residuesSeveral kinds of, RbIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
Preferably, in step S4, the molecular chain of the pretreated resin liquid contains a unit structure represented by formula 2, and the unit structure represented by formula 2 is as follows:
wherein R iscIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RdIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
Preferably, in step S4, the molecular chain of the pretreated resin liquid further includes a unit structure of formula 3, where the unit structure of formula 3 is as follows:
wherein R iseIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RfIs 1, 4-cyclohexanedimethanolOne or more of an amine residue, a 1, 3-cyclohexanediamine residue, a norbornanediamine residue, a 1, 4-cyclohexanediamine residue, a 4,4 '-diaminodiphenyl sulfone residue, a 3, 3' -diaminodiphenyl sulfone residue, a 2,2 '-bis (trifluoromethyl) benzidine residue, and a 4, 4' - (hexafluoroisopropylidene) diphenylamine residue, RgIs one or more of ethane residue, propane residue, cyclopropane residue, cyclobutane residue, cyclopentane residue, cyclohexane residue and 1, 2-benzene residue.
Preferably, the colorless transparent polyimide film has a yellow index < 2.
Example 3
A preparation method of a low-yellow-index colorless transparent polyimide film comprises the following preparation steps:
s1: placing the N, N-dimethylacetamide solvent in a rotary evaporator for dehydration and purification treatment, pouring the N, N-dimethylacetamide solvent A and the N, N-dimethylacetamide solvent B into two dry glass flasks respectively after the dehydration and purification treatment is finished, and standing for later use;
s2: putting the diamine solid into a sublimer for purification treatment, mixing the diamine solid in X weight parts with N, N-dimethylacetamide solvent A in Z weight parts after the purification treatment is finished, and fully stirring for 15 minutes until the diamine solid is completely dissolved to prepare a mixed solution A;
s3: mixing a mono-anhydride compound with an N, N-dimethylacetamide solvent B according to a weight ratio of 0.15:1 to prepare a mixed solution B;
s4: putting dianhydride solid into a sublimator for purification treatment, putting Y parts by weight of dianhydride solid and the mixed solution A into a reaction vessel after the purification treatment is finished, fully stirring for 12 hours to prepare pretreated resin liquid, continuously adding the mixed solution B into the reaction vessel, and continuously stirring for 3 hours to fully perform polymerization reaction, wherein the weight part ratio of the mixed solution B to the pretreated resin liquid is 2.5:100, and a polymer solution with the viscosity coefficient of 35000mPa & s is prepared;
s5: and (2) uniformly coating the polymer solution on a glass plate, heating to 120 ℃ and keeping the temperature for 40 minutes, then gradually heating to 220 ℃ in a gradient of 10 ℃, then drying for 40 minutes, and finally heating to 310 ℃ and keeping the temperature for 40 minutes to finally obtain a colorless and transparent polyimide film with the thickness of 80 microns.
Preferably, in the steps S2, S4, the X parts by weight diamine solids, Y parts by weight dianhydride solids, and Z parts by weight N, N-dimethylacetamide solvent a satisfy the following formula:
preferably, the monoanhydride-based compound contains one of an ethane residue, a propane residue, a cyclopropane residue, a cyclobutane residue, a cyclopentane residue, a cyclohexane residue, and a 1, 2-benzene residue.
Preferably, in step S1, the water content of the N, N-dimethylacetamide solvent after dehydration and purification is 0.02%.
Preferably, in the steps S2 and S4, the molar ratio of the dianhydride solid to the diamine solid is 1: 1.
Preferably, the molecular chain of the colorless transparent polyimide film contains a repeating unit structure of formula 1, and the repeating unit structure of formula 1 is as follows:
wherein R isaIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RbIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
Preferably, in step S4, the molecular chain of the pretreated resin liquid contains a unit structure represented by formula 2, and the unit structure represented by formula 2 is as follows:
wherein R iscIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RdIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
Preferably, in step S4, the molecular chain of the pretreated resin liquid further includes a unit structure of formula 3, where the unit structure of formula 3 is as follows:
wherein R iseIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RfIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue, RgIs an ethane residue, a propane residue, a cyclopropane residue, a ringOne or more of butane residue, cyclopentane residue, cyclohexane residue, and 1, 2-benzene residue.
Preferably, the colorless transparent polyimide film has a yellow index < 2.
Example 4
The colorless and transparent polyimide films obtained in the above examples were used, and the conventional polyimide film of KOLON A-50-O type was used as a comparative example to test the transmittance and the yellow index, wherein the transmittance was measured according to ASTM D1003 and the yellow index was measured according to ASTM E313.
The colorless transparent polyimide film obtained in each example of the present invention and the comparative example have the performance parameters shown in table 1:
TABLE 1
| Sample (I) | Light transmittance | Yellow index |
| Example 1 | 90.2 | 1.5 |
| Example 2 | 91.1 | 1.4 |
| Example 3 | 90.9 | 1.6 |
| Comparative example 1 | 89.1 | 2.6 |
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a low-yellow-index colorless transparent polyimide film is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1: placing the N, N-dimethylacetamide solvent in a rotary evaporator for dehydration and purification treatment, pouring the N, N-dimethylacetamide solvent A and the N, N-dimethylacetamide solvent B into two dry glass flasks respectively after the dehydration and purification treatment is finished, and standing for later use;
s2: putting the diamine solid into a sublimer for purification treatment, mixing the diamine solid in X weight parts with N, N-dimethylacetamide solvent A in Z weight parts after the purification treatment is finished, and fully stirring for 5-30 minutes until the diamine solid is completely dissolved to prepare a mixed solution A;
s3: mixing a mono-anhydride compound and an N, N-dimethylacetamide solvent B according to a weight ratio of 0.05: 1-0.3: 1 to prepare a mixed solution B;
s4: putting dianhydride solid into a sublimator for purification treatment, after the purification treatment is finished, putting Y parts by weight of dianhydride solid and the mixed solution A into a reaction container, fully stirring for 5-24 hours to prepare a pre-treated resin solution, continuously adding the mixed solution B into the reaction container, and continuously stirring for 1-5 hours to fully perform a polymerization reaction, wherein the weight ratio of the mixed solution B to the pre-treated resin solution is 0.5: 100-5: 100, and a polymer solution with the viscosity coefficient of 5000-70000 mPa & s is prepared;
s5: and uniformly coating the polymer solution on a glass plate, heating to 120 ℃ and keeping the temperature for 30-50 minutes, then gradually heating to 220 ℃ in a gradient of 5-15 ℃, then drying for 30-50 minutes, and finally heating to 310 ℃ and keeping the temperature for 30-45 minutes to finally obtain the colorless transparent polyimide film with the thickness of 50-100 microns.
2. The method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: in the steps S2, S4, the X parts by weight diamine solids, Y parts by weight dianhydride solids, and Z parts by weight N, N-dimethylacetamide solvent a satisfy the following formula:
3. the method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: the mono-anhydride compound comprises one of ethane residue, propane residue, cyclopropane residue, cyclobutane residue, cyclopentane residue, cyclohexane residue and 1, 2-benzene residue.
4. The method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: in the step S1, the water content of the N, N-dimethylacetamide solvent is 0 to 0.05% after dehydration and purification.
5. The method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: in the steps S2 and S4, the molar ratio of the dianhydride solid to the diamine solid is 0.95:1 to 1.05: 1.
6. The method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: the molecular chain of the colorless transparent polyimide film comprises a repeating unit structure shown in formula 1, wherein the repeating unit structure shown in formula 1 is as follows:
wherein,Rais cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RbIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
7. The method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: in step S4, the molecular chain of the pretreated resin liquid contains a unit structure of formula 2, where the unit structure of formula 2 is as follows:
wherein R iscIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RdIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue.
8. The method for preparing a low-yellowness index colorless transparent polyimide film according to claim 7, wherein: in step S4, the molecular chain of the pretreated resin solution further includes a unit structure of formula 3, where the unit structure of formula 3 is as follows:
wherein R iseIs cyclobutane residue, cyclopentane residue, 4 ' - (hexafluoroisopropylidene) diphenyl residue, diphenyl sulfone residue, norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 ' -norbornane-5, 5 ', 6,6 ' -tetracarboxylic dianhydride residue, bicyclo [ 2.2.2.2]One or more of octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride residues, RfIs one or more of 1, 4-cyclohexanediamine residue, 1, 3-cyclohexanediamine residue, norbornanediamine residue, 1, 4-cyclohexanediamine residue, 4 '-diaminodiphenyl sulfone residue, 3' -diaminodiphenyl sulfone residue, 2 '-bis (trifluoromethyl) benzidine residue and 4, 4' - (hexafluoroisopropylidene) diphenylamine residue, RgIs one or more of ethane residue, propane residue, cyclopropane residue, cyclobutane residue, cyclopentane residue, cyclohexane residue and 1, 2-benzene residue.
9. The method for preparing a low-yellow-index colorless transparent polyimide film according to claim 1, wherein the method comprises the following steps: the colorless transparent polyimide film has a yellowness index < 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646183A (en) * | 2020-12-22 | 2021-04-13 | 宁波长阳科技股份有限公司 | Polyimide material and preparation method and application thereof |
| CN112812335A (en) * | 2020-12-23 | 2021-05-18 | 宁波长阳科技股份有限公司 | Colorless transparent polyimide film with high dimensional stability and mechanical strength and preparation method thereof |
| CN115537729A (en) * | 2022-09-06 | 2022-12-30 | 深圳市氟德特科技有限公司 | Process method for reducing yellow index of transparent CPI base film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382303A (en) * | 2011-08-16 | 2012-03-21 | 中国科学院宁波材料技术与工程研究所 | Colorless and transparent polyimide resin material and preparation method thereof |
| US20180208766A1 (en) * | 2015-07-16 | 2018-07-26 | Ube Industries, Ltd. | Polyamic acid solution composition and polyimide film |
| CN108586744A (en) * | 2018-05-08 | 2018-09-28 | 深圳飞世尔新材料股份有限公司 | A kind of transparent polyimide film and preparation method thereof |
| CN110437613A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of transparent polyimide film |
-
2020
- 2020-07-24 CN CN202010723516.4A patent/CN111662473A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382303A (en) * | 2011-08-16 | 2012-03-21 | 中国科学院宁波材料技术与工程研究所 | Colorless and transparent polyimide resin material and preparation method thereof |
| US20180208766A1 (en) * | 2015-07-16 | 2018-07-26 | Ube Industries, Ltd. | Polyamic acid solution composition and polyimide film |
| CN108586744A (en) * | 2018-05-08 | 2018-09-28 | 深圳飞世尔新材料股份有限公司 | A kind of transparent polyimide film and preparation method thereof |
| CN110437613A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of transparent polyimide film |
Non-Patent Citations (1)
| Title |
|---|
| 李智杰等: ""无色透明聚酰亚胺薄膜的研究进展"", 《合成技术及应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646183A (en) * | 2020-12-22 | 2021-04-13 | 宁波长阳科技股份有限公司 | Polyimide material and preparation method and application thereof |
| CN112812335A (en) * | 2020-12-23 | 2021-05-18 | 宁波长阳科技股份有限公司 | Colorless transparent polyimide film with high dimensional stability and mechanical strength and preparation method thereof |
| CN112812335B (en) * | 2020-12-23 | 2022-10-04 | 宁波长阳科技股份有限公司 | Colorless transparent polyimide film with high dimensional stability and mechanical strength and preparation method thereof |
| CN115537729A (en) * | 2022-09-06 | 2022-12-30 | 深圳市氟德特科技有限公司 | Process method for reducing yellow index of transparent CPI base film |
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