CN114702706A - 400 ℃ high-temperature-resistant colorless transparent polyimide film and preparation method thereof - Google Patents

400 ℃ high-temperature-resistant colorless transparent polyimide film and preparation method thereof Download PDF

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CN114702706A
CN114702706A CN202210160348.1A CN202210160348A CN114702706A CN 114702706 A CN114702706 A CN 114702706A CN 202210160348 A CN202210160348 A CN 202210160348A CN 114702706 A CN114702706 A CN 114702706A
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dianhydride
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冷劲松
肖鑫礼
刘彦菊
孔德艳
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Harbin Institute of Technology
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    • 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
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Abstract

The invention discloses a 400 ℃ high-temperature-resistant colorless transparent polyimide film and a preparation method thereof. The method comprises the following steps: dissolving mixed diamine in an aprotic polar solvent, adding mixed dianhydride in several times, performing polycondensation reaction to obtain a precursor polyamic acid solution, casting the precursor polyamic acid solution on a steel belt through a casting machine, and baking to reduce the content of the aprotic polar solvent to obtain a self-supporting film; carrying out thermal imidization and stretching treatment on the self-supporting film; finally, cooling and post-processing to obtain a CPI film; mixing diamine: 9, 9-bis- (3-fluoro-4-aminophenyl) fluorene: 2, 2' -bis (trifluoromethyl) diaminobiphenyl: 9, 9-bis- (4-aminophenyl) fluorene: 2, 2-bis (4-aminophenyl) hexafluoropropane; mixed dianhydride: 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride: 4,4' — (hexafluoroisopropylidene) diphthalic anhydride: 3,3 ', 4,4' -benzophenone tetracarboxylic dianhydride; the CPI film prepared by the invention has a cold-heat expansion ratio of not more than 0.20% at 400 ℃, and the light transmittance of a 75-micron thick film at 450nm is not less than 89%.

Description

400 ℃ high-temperature-resistant colorless transparent polyimide film and preparation method thereof
Technical Field
The invention relates to a 400 ℃ high-temperature-resistant colorless transparent polyimide film and a preparation method thereof.
Background
The flexible substrate is an important component of the whole flexible display device, plays an important role in protecting and supporting the flexible display device, has performance which directly affects the quality and service life of the flexible electronic device, is a key for realizing the flexible display technology, and is also a serious difficulty in the research process. At present, colored Polyimide (PI) suitable for Top-emission (Top-emission) devices has begun to be widely applied to flexible display devices due to its excellent high temperature, dimensional stability and good mechanical properties. However, the colored PI reduces the transmittance of the flexible electrode, affects the absorption and transmission of light, and reduces the performance of the device. In contrast, a colorless transparent polyimide (CPI) substrate suitable for both top-emission and Bottom-emission type (Bottom-emission) devices has a greater potential for application in the field of flexible displays. However, the conventional CPI has obvious defects in heat resistance level, high-temperature dimensional stability and high-temperature transparency.
CPI heat resistance requirements are considered based on process temperatures of key components in flexible devices, such as transistor (TFT) backplanes, which are most commonly low temperature poly-silicon (LTPS) process temperatures in TFT technology, often as high as 400 ℃, which is responsible for the CPI glass transition temperature (T ℃)g) Put forward a high demand, TgMust be higher than 400 deg.c. Secondly, if the flexible substrate can not maintain excellent dimensional stability in a high temperature process, the quality and reliability of the final display device will be seriously affected. For example, excessive dimensional changes of the substrate at high temperatures may cause deterioration of optical alignment accuracy and generation of internal stress at interfaces of material layers, resulting in reduction of display accuracy of the device and delamination between layers upon bending.
Disclosure of Invention
Based on the defects, the invention aims to provide the colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ and the preparation method thereof, and solves the problem that the current CPI cannot be used in a high-temperature process for manufacturing a flexible display device based on low-temperature polycrystalline silicon and needs to resist the high temperature of 400 ℃ in a short time.
The technical scheme adopted by the invention is as follows: a preparation method of a colorless transparent polyimide film resistant to high temperature of 400 ℃ comprises the following steps: dissolving mixed diamine in an aprotic polar solvent, adding mixed dianhydride for polycondensation reaction in several times to obtain a precursor polyamic acid solution, casting the precursor polyamic acid solution on a steel belt through a casting machine, and baking to reduce the content of the aprotic polar solvent to obtain a self-supporting film; carrying out thermal imidization and stretching treatment on the self-supporting film; finally, cooling and post-processing to obtain the CPI film, which is characterized in that mixed diamine is added into an aprotic polar solvent and stirred in a nitrogen atmosphere until the mixed diamine is completely dissolved to obtain a mixed diamine solution; the solid-liquid ratio of the mixed diamine to the aprotic polar solvent is 12.0-18.0 Kg: 150L; the mixed diamine is prepared by mixing the following raw materials in a molar ratio:
9, 9-bis- (3-fluoro-4-aminophenyl) fluorene: 2, 2' -bis (trifluoromethyl) diaminobiphenyl: 9, 9-bis- (4-aminophenyl) fluorene: 2, 2-bis (4-aminophenyl) hexafluoropropane 1 to 17: 1-17: 1-17: 1-12;
adding mixed dianhydride into the mixed diamine solution for multiple times, introducing nitrogen, and stirring at room temperature;
the mixed dianhydride is prepared by mixing the following raw materials in a molar ratio:
9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride: 4,4' — (hexafluoroisopropylidene) diphthalic anhydride: 3,3 ', 4,4' -benzophenone tetracarboxylic dianhydride 1-16: 1-14: 1-12;
the molar ratio of the added mixed dianhydride to the added mixed diamine is 0.95: 1-1.06: 1.
The invention also has the following technical characteristics:
1. the aprotic polar solvent is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone
2. The upwind temperature of the steel belt of the casting machine is 80-120 ℃, and the downwind temperature of the steel belt is 100-150 ℃.
3. Synchronous or asynchronous bidirectional stretching treatment is adopted; the synchronous biaxial stretching has a longitudinal stretching ratio of 1.00-1.40 and a transverse stretching ratio of 1.00-1.30; the asynchronous biaxial stretching has a longitudinal stretching ratio of 1.00-1.50 and a transverse stretching ratio of 1.00-1.30.
4. The temperature in the imidization furnace is controlled to be 350-380 ℃.
5. A colorless transparent polyimide film prepared by the preparation method described above.
6. The colorless transparent polyimide film has a glass transition temperature of 410 deg.C or higher, a cold/hot expansion ratio of 0.20% or higher at 400 deg.C, and a light transmittance of 89% or higher at 450nm for a thick film of 75 μm.
The principle of the invention is as follows: the invention selects a plurality of special monomers for copolymerization to obtain the CPI film capable of bearing the high temperature of 400 ℃, wherein four diamine monomers are respectively 9, 9-bis- (3-fluoro-4-aminophenyl) fluorene (FFDA) with fluorine atoms in the ortho-position of amino groups and large-volume aromatic ring substituent groups, 2' -bis (trifluoromethyl) diaminobiphenyl (TFDB) with trifluoromethyl in the meta-position of amino groups, 9-bis- (4-aminophenyl) Fluorene (FDA) with large-volume aromatic ring substituent groups and 2, 2-bis (4-aminophenyl) hexafluoropropane (FA) containing hexafluoroisopropyl. The three dianhydride monomers are respectively 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride (BPAF) containing a main chain with a large group, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) containing hexafluoroisopropyl and 3,3 ', 4,4' -benzophenonetetracarboxylic dianhydride (BTDA) with stronger rigidity. The principle of the invention is as follows: the invention adopts four diamine monomers and three dianhydride monomers with special structures to carry out random copolymerization to obtain the CPI film which can resist the high temperature of 400 ℃. The trifluoromethyl group in the 2,2 '-bis (trifluoromethyl) diaminobiphenyl (TFDB) is in a meta position of an amino group, on one hand, the trifluoromethyl group strongly adsorbs amino electrons to reduce the CTC effect of the 2, 2' -bis (trifluoromethyl) diaminobiphenyl (TFDB), and on the other hand, the trifluoromethyl group is positioned to prevent charge transfer to reduce the CTC effect, so that the transparency is improved. Meanwhile, the strong rigidity caused by the direct connection of two benzene rings and the difficulty of molecular chain movement caused by the large-volume trifluoromethyl side group lead to the CPI has a very high Tg. However, TFDB is very rigid, and a pure TFDB easily causes that a complete film cannot be formed. Thus, other flexible diamines were introduced. The isopropyl bis-trifluoromethyl strong electronegativity and isopropyl structure of 2, 2-bis (4-aminophenyl) hexafluoropropane (FA) can effectively hinder the effect of a Charge Transfer Complex (CTC) and reduce the color of the CTC; the hexafluoroisopropyl macro group can block the free movement of molecular chain and has higher TgAnd meanwhile, certain flexibility is brought to the film so that the film is easy to form into a complete film. The fluorine atom with high electronegativity in 9, 9-bis- (3-fluoro-4-aminophenyl) fluorene (FFDA) is adjacent to the amino group, so that an electron pair on the amino group can be effectively adsorbed, and the CTC effect is reduced to lighten the color of the FFDA; at the same time, fluorine atoms can also form intermolecular hydrogen bonds to improve Tg(ii) a Two amino para-positions are connected with a tert-butyl carbon atom of polycyclic aromatic hydrocarbon fluorene, and the bulky side group destroys a coplanar structure, so that the CTC effect is reduced and the color is reduced; meanwhile, the molecular chain movement is hindered by the bulky side group, so that high T is generatedg. Two amino para-positions in 9, 9-bis- (4-aminophenyl) Fluorene (FDA) are connected with tertiary butyl carbon atom of polycyclic aromatic hydrocarbon fluorene, and the polycyclic aromatic hydrocarbon structure of fluorene ensures that the fluorene has high Tg(ii) a Meanwhile, the bulky side group also destroys the coplanar structure, and reduces the CTC effect to lighten the color of the CTC. The structure of 9, 9-bis (3, 4-dicarboxylic acid phenyl) fluorene dianhydride (BPAF) in the three dianhydride monomers is characterized in that two benzene ring anhydrides are directly connected with a tertiary butyl carbon atom of polycyclic aromatic hydrocarbon fluorene, and the polycyclic aromatic hydrocarbon structure ensures that the fluorene dianhydride has high Tg(ii) a Meanwhile, the polycyclic aromatic hydrocarbon serving as a bulky side group also destroys a coplanar structure, and reduces the CTC effect to lighten the color of the composite material. The isopropyl bis-trifluoromethyl strong electronegativity and isopropyl structure of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) effectively hinder the CTC effect, so that the color of the obtained CPI is reduced; meanwhile, the hexafluoroisopropyl macro group blocks the free movement of molecular chains, so that the hexafluoroisopropyl macro group has higher Tg. Ketone bonds in the middle of molecules in 3,3 ', 4,4' -benzophenonetetracarboxylic dianhydride (BTDA) hinder the strong CTC effect when benzene rings are directly connected, so that the color is reduced; meanwhile, two benzene rings are connected through ketone, and the rigidity is higher, so that the T is highergHigher. Thus, in the present invention, 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (4-aminophenyl) hexafluoropropane, 9-bis- (3-fluoro-4-aminophenyl) fluorene (FFDA) are mentioned,The light transmittance is more than or equal to 89% when the thickness of the random copolymerization CPI of the four diamines of 9, 9-bis- (4-aminophenyl) Fluorene (FDA), 9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 3,3 ', 4,4' -benzophenonetetracarboxylic dianhydride is 75 microns, the cold-heat expansion ratio at the high temperature of 400 ℃ is less than or equal to 0.20%, and the high-temperature requirement of low-temperature polysilicon manufacturing is met.
The invention has the following beneficial effects and advantages: the CPI film prepared by the invention has excellent thermal stability, dimensional stability and optical performance, the glass transition temperature is not lower than 410 ℃, the cold-hot expansion ratio at 400 ℃ is not higher than 0.20%, the light transmittance of a 75-micron thick film at 450nm is not less than 89%, and the CPI film has wide application prospect in flexible display.
Drawings
FIG. 1 is a chart of the 400 ℃ high temperature CPI infrared spectrum of example 11;
FIG. 2 is a chart of the UV-Vis spectra of CPI prepared in example 11 for 400 deg.C resistance.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of solvent was added to a 300L dissolution vessel equipped with mechanical stirring and nitrogen inlet/outlet: n, N-Dimethylacetamide (DMAc) was purged with nitrogen. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA to 2:3:2: 3; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 16Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 6:3: 1.
The molar ratio of the added mixed dianhydride to the added mixed diamine is 1.06:1, and the PAA solution is obtained after polymerization reaction for 22 hours under the conditions of room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 150 ℃. After steel strip baking, the self-supporting PAA film is obtained, wherein the content of DMAc solvent is 25%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
And sixthly, synchronously performing bidirectional stretching by synchronously stretching in the longitudinal direction and the transverse direction, wherein the longitudinal stretching ratio is 1.00, the transverse stretching ratio is 1.00, and the highest control temperature of stretching in an imidization furnace is 350 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 600mm and the thickness of 75 mu m, wherein the T of the CPI filmgIt was 415 ℃.
Example 2
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
firstly, 150L of N, N-dimethylformamide is added into a 300L dissolving kettle provided with a mechanical stirring and a nitrogen inlet and outlet, and nitrogen is introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA to 17:1:1: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent is 12.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions at a mass ratio of 6FDA: BTDA: BPAF: 16:2: 2.
The molar ratio of the added mixed dianhydride to the added mixed diamine is 0.95:1, and the PAA solution is obtained after polymerization reaction for 20 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 80 ℃, and the downwind temperature of the steel belt is 150 ℃. And (3) obtaining the self-supporting PAA film after baking the steel strip, wherein the content of N, N-dimethylformamide is 25%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, asynchronous bidirectional stretching is carried out step by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.40, the transverse stretching ratio is 1.18, and the highest control temperature for stretching in an imidization furnace is 380 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1100mm and the thickness of 75 mu m, wherein the T of the CPI filmgIt was 417 ℃.
Example 3
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
firstly, 150 LN-methyl pyrrolidone is added into a 300L dissolving kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet, and nitrogen is introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 1:17:1: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 13Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:14: 3. The molar ratio of the added mixed dianhydride to the mixed diamine is 1.04:1, and the PAA solution is obtained after polymerization reaction for 22 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 150 ℃. Obtaining the self-supporting PAA film after baking the steel strip, wherein the content of N-methyl pyrrolidone is 21 percent.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
And sixthly, synchronously performing bidirectional stretching by synchronously stretching in the longitudinal direction and the transverse direction, wherein the longitudinal stretching ratio is 1.20, the transverse stretching ratio is 1.28, and the highest control temperature of stretching in an imidization furnace is 360 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1220mm and the thickness of 70 mu m, wherein the T of the CPI filmgThe temperature was 418 ℃.
Example 4
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 1:1:17: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent is 15Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirrer and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 4:4: 12. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1.03:1, and the PAA solution is obtained after the polymerization reaction for 12 hours under the conditions of room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 80 ℃, and the downwind temperature of the steel belt is 100 ℃. After baking the steel strip, a self-supporting PAA film was obtained, in which the DMAc solvent content was 28%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the film by using a stainless steel clamp, and then entering the imidization furnace through a guide roller.
And sixthly, synchronously performing bidirectional stretching by synchronously stretching in the longitudinal direction and the transverse direction, wherein the longitudinal stretching ratio is 1.40, the transverse stretching ratio is 1.30, and the highest control temperature of stretching in an imidization furnace is 370 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1200mm and the thickness of 60 mu m, wherein the T of the CPI filmgIt was 417 ℃.
Example 5
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 2:2:4: 12; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent is 18Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:2: 5. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1.02:1, and the PAA solution is obtained after the polymerization reaction for 16 hours under the conditions of room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 110 ℃, and the downwind temperature of the steel belt is 150 ℃. After baking the steel strip, a self-supporting PAA film was obtained, in which the DMAc solvent content was 28%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, asynchronous bidirectional stretching is carried out step by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.00, the transverse stretching ratio is 1.00, and the highest control temperature for stretching in an imidization furnace is 380 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 500mm and the thickness of 75 mu m, wherein the T of the CPI filmgThe temperature was 420 ℃.
Example 6
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA to 3:2:3: 2; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 14.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA and BPAF mixed dianhydride is added into the resin kettle in multiple times, and the mass ratio of the mixed dianhydride is 6FDA, BTDA and BPAF is 8:0.5: 1.5. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1.01:1, and the PAA solution is obtained after polymerization reaction for 8 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 130 ℃. After steel strip baking, a self-supporting PAA film is obtained, wherein the content of DMAc solvent is 19%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
And sixthly, synchronously performing bidirectional stretching by synchronously stretching in the longitudinal direction and the transverse direction, wherein the longitudinal stretching ratio is 1.30, the transverse stretching ratio is 1.20, and the highest control temperature of stretching in an imidization furnace is 360 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1100mm and the thickness of 65 mu m, wherein the T of the CPI filmgIt was 421 ℃.
Example 7
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 3:3:3: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the volume of the aprotic polar solvent is 12Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 4:1: 5. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1:1, and the PAA solution is obtained after the polymerization reaction for 12 hours under the conditions of room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 90 ℃, and the downwind temperature of the steel belt is 120 ℃. After baking the steel strip, a self-supporting PAA film was obtained, in which the DMAc solvent content was 28%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, synchronous biaxial stretching is synchronously carried out by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.25, the transverse stretching ratio is 1.20, and the highest control temperature of stretching in an imidization furnace is 370 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 700mm and the thickness of 80 mu m, wherein the T of the CPI filmgThe temperature was 423 ℃.
Example 8
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 3:2:2: 3; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent is 15Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:3: 4. The molar ratio of the added mixed dianhydride to the added mixed diamine is 0.99:1, and the PAA solution is obtained after polymerization reaction for 25 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the PAA solution after defoaming on a stainless steel belt which circularly runs through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 140 ℃. After steel strip baking, the self-supporting PAA film is obtained, wherein the content of DMAc solvent is 22%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the film by using a stainless steel clamp, and then entering the imidization furnace through a guide roller.
Sixthly, asynchronous bidirectional stretching is carried out step by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.50, the transverse stretching ratio is 1.30, and the highest control temperature for stretching in an imidization furnace is 360 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1100mm and the thickness of 70 mu m, wherein the T of the CPI filmgAt 422 ℃.
Example 9
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 2:1:1: 6; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 16.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:3: 4. The molar ratio of the added mixed dianhydride to the added mixed diamine is 0.98:1, and the PAA solution is obtained after polymerization reaction for 18 hours at room temperature under the condition of high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 130 ℃. After steel strip baking, the self-supporting PAA film is obtained, wherein the content of DMAc solvent is 22%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, synchronous biaxial stretching is synchronously carried out by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.16, the transverse stretching ratio is 1.28, and the highest control temperature of stretching in an imidization furnace is 370 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1100mm and the thickness of 65 mu m, wherein the T of the CPI filmgIt was 425 ℃.
Example 10
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 2:2:4: 2; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 16.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:2: 5. The molar ratio of the added mixed dianhydride to the added mixed diamine is 0.97:1, and the PAA solution is obtained after the polymerization reaction for 19 hours under the conditions of room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 110 ℃, and the downwind temperature of the steel belt is 150 ℃. After steel strip baking, a self-supporting PAA film is obtained, wherein the content of DMAc solvent is 26%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
And sixthly, synchronously performing bidirectional stretching in the longitudinal direction and the transverse direction synchronously, wherein the longitudinal stretching ratio is 1.15, the transverse stretching ratio is 1.15, and the highest control temperature of stretching in an imidization furnace is 360 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1200mm and the thickness of 75 mu m, wherein the T of the CPI filmgIt was 419 ℃.
Example 11
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 2:2:3: 3; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 15.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirrer and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:3: 4. The molar ratio of the added mixed dianhydride to the added mixed diamine is 0.99:1, and the PAA solution is obtained after polymerization reaction for 15 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 110 ℃, and the downwind temperature of the steel belt is 150 ℃. After steel strip baking, a self-supporting PAA film is obtained, wherein the content of DMAc solvent is 26%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, synchronous biaxial stretching is synchronously carried out by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.10, the transverse stretching ratio is 1.18, and the highest control temperature of stretching in an imidization furnace is 370 ℃.
Seventhly, after the biaxial tension treatment at high temperature, the film is cooled, cut and rolled to prepare the CPI film with the width of 600mm and the thickness of 75 mu m, and the T of the CPI filmgThe temperature was 420 ℃.
The infrared spectrum of the CPI prepared in this example is shown in FIG. 1, and the characteristic absorption peaks indicate that the CPI has been highly imidized.
The UV-Vis spectrum of the CPI prepared in this example is shown in FIG. 2, from which it can be seen that the average light transmission of a 75 μm thick CPI film was 89.5%. The cold-heat expansion ratio of the film after being cooled to room temperature in a high-temperature environment of 400 ℃ for 120s is 0.20%.
Example 12
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 2:1:6: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 16.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 3:3: 4. The molar ratio of the added mixed dianhydride to the added mixed diamine is 0.96:1, and the PAA solution is obtained after polymerization reaction for 20 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the PAA solution after defoaming on a stainless steel belt which circularly runs through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 140 ℃. After baking the steel strip, a self-supporting PAA film is obtained, wherein the DMAc solvent content is 22 percent.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the film by using a stainless steel clamp, and then entering the imidization furnace through a guide roller.
Sixthly, asynchronous bidirectional stretching is carried out step by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.20, the transverse stretching ratio is 1.25, and the highest control temperature for stretching in an imidization furnace is 380 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 650mm and the thickness of 75 mu m, wherein the T of the CPI filmgAt 426 ℃.
The 75 μm thick CPI film prepared in this example had an average light transmission of 88.2% and a cold-to-hot stretch ratio of 0.18% when the film was cooled to room temperature in a high temperature environment of 400 ℃ for 120 seconds.
Example 13
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA to is 4:2:3: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of diamine to the volume of aprotic polar solvent was 17.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF: 4:3: 3. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1.02:1, and the PAA solution is obtained after polymerization reaction for 20 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 150 ℃. After steel strip baking, the self-supporting PAA film is obtained, wherein the content of DMAc solvent is 22%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, asynchronous bidirectional stretching is carried out step by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.25, the transverse stretching ratio is 1.28, and the highest control temperature for stretching in an imidization furnace is 360 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1100mm and the thickness of 70 mu m, wherein the T of the CPI filmgAt 417 deg.C.
The 70 μm thick CPI film prepared in this example had an average light transmission of 88.6% and a cold to hot stretch ratio of 0.20% at 400 deg.C for 120 seconds and then cooled to room temperature.
Example 14
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMAc solvent was placed in a 300L dissolution vessel equipped with mechanical stirring and a nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 4:3:2: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 13.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 4:5: 1. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1.03:1, and the PAA solution is obtained after polymerization reaction for 8 hours at room temperature and high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 90 ℃, and the downwind temperature of the steel belt is 130 ℃. After steel strip baking, the self-supporting PAA film is obtained, wherein the content of DMAc solvent is 22%.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, synchronous biaxial stretching is carried out by synchronously stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.20, the transverse stretching ratio is 1.26, and the highest control temperature of stretching in an imidization furnace is 370 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 600mm and the thickness of 65 mu m, wherein the T of the CPI filmgIt was 421 ℃.
The 65 μm thick CPI film prepared in this example had an average light transmission of 90.1% and a cold to hot stretch ratio of 0.18% at 400 deg.C for 120 seconds and then cooled to room temperature.
Example 15
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of DMF solvent was added to a 300L dissolution vessel equipped with mechanical stirring and nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 3:3:4: 1; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 16.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA and BPAF mixed dianhydride is added into the resin kettle in multiple times, and the mass ratio of the mixed dianhydride is 6FDA, BTDA and BPAF is 5:3: 2. The molar ratio of the added mixed dianhydride to the mixed diamine is 1.01:1, and the PAA solution is obtained after polymerization reaction for 8 hours at room temperature and under the condition of high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 80 ℃, and the downwind temperature of the steel belt is 150 ℃. Obtaining the self-supporting PAA film after baking the steel strip, wherein the content of DMF solvent is 22 percent.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
Sixthly, asynchronous bidirectional stretching is carried out step by adopting stretching in the longitudinal direction and the transverse direction, the longitudinal stretching ratio is 1.12, the transverse stretching ratio is 1.15, and the highest control temperature for stretching in an imidization furnace is 370 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 1100mm and the thickness of 60 mu m, wherein the T of the CPI filmgAt 422 ℃.
The 60 μm thick CPI film produced in this example had an average light transmission of 89.6% and a cold-hot stretch ratio of 0.20% when the film was heated at 400 deg.C for 120 seconds and then cooled to room temperature.
Example 16
The colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ of the embodiment is prepared by the following steps:
first, 150L of NMP solvent was added to a 300L dissolution vessel equipped with mechanical stirring and nitrogen inlet and outlet, and nitrogen was introduced. Adding four diamine monomers including FFDA, TFDB, FDA and FA into a dissolving kettle, wherein the molar ratio of the substances is FFDA to TFDB to FDA to FA is 3:2:2: 3; stirring until the diamine is completely dissolved to obtain a mixed diamine solution; the volume ratio of the weight of the diamine to the aprotic polar solvent was 17.0Kg to 150L.
Secondly, the mixed diamine solution in the dissolution kettle is completely pressed into a 300L resin kettle which is provided with a mechanical stirring and a nitrogen inlet and outlet through a pressure pump, and nitrogen is introduced. Then 6FDA, BTDA, BPAF mixed dianhydride was added to the resin kettle in portions in a mass ratio of 6FDA: BTDA: BPAF to 5:4: 1. The molar ratio of the added mixed dianhydride to the added mixed diamine is 1:1, and the PAA solution is obtained after polymerization reaction for 28 hours at room temperature and under the condition of high-speed stirring.
And thirdly, pressing the PAA solution into a 400L defoaming kettle by a pressure pump, and filtering, standing and defoaming to obtain a uniform solution.
And fourthly, uniformly casting the defoamed PAA solution on a circularly operated stainless steel belt through an extrusion die head, wherein the upwind temperature of the steel belt is 100 ℃, and the downwind temperature of the steel belt is 130 ℃. The self-supporting PAA film is obtained after steel strip baking, wherein the content of NMP solvent is 21 percent.
And fifthly, peeling the self-supporting PAA film from the steel belt, fixing the self-supporting PAA film by using a stainless steel clamp, and then feeding the self-supporting PAA film into an imidization furnace through a guide roller.
And sixthly, synchronously performing bidirectional stretching by synchronously stretching in the longitudinal direction and the transverse direction, wherein the longitudinal stretching ratio is 1.26, the transverse stretching ratio is 1.30, and the highest control temperature of stretching in an imidization furnace is 380 ℃.
Seventhly, after the biaxial tension treatment at high temperature, cooling, trimming and rolling the film to finally prepare the CPI film with the width of 600mm and the thickness of 65 mu m, wherein the T of the CPI filmgIt was 419 ℃.
The 65 μm thick CPI film prepared in this example had an average light transmission of 89.2% and a cold to hot stretch ratio of 0.19% at 400 deg.C for 120 seconds and then cooled to room temperature.

Claims (7)

1. A preparation method of a colorless transparent polyimide film resistant to high temperature of 400 ℃ comprises the following steps: dissolving mixed diamine in an aprotic polar solvent, adding mixed dianhydride in several times, performing polycondensation reaction to obtain a precursor polyamic acid solution, casting the precursor polyamic acid solution on a steel belt through a casting machine, and baking to reduce the content of the aprotic polar solvent to obtain a self-supporting film; carrying out thermal imidization and stretching treatment on the self-supporting film; finally, cooling and post-processing to obtain the CPI film, which is characterized in that mixed diamine is added into an aprotic polar solvent and stirred in a nitrogen atmosphere until the mixed diamine is completely dissolved to obtain a mixed diamine solution; the solid-liquid ratio of the mixed diamine to the aprotic polar solvent is 12.0-18.0 Kg: 150L; the mixed diamine is prepared by mixing the following raw materials in a molar ratio:
9, 9-bis- (3-fluoro-4-aminophenyl) fluorene: 2, 2' -bis (trifluoromethyl) diaminobiphenyl: 9, 9-bis- (4-aminophenyl) fluorene: 2, 2-bis (4-aminophenyl) hexafluoropropane 1 to 17: 1-17: 1-17: 1-12;
adding mixed dianhydride into the mixed diamine solution for multiple times, introducing nitrogen, and stirring at room temperature; the mixed dianhydride is prepared by mixing the following raw materials in a molar ratio:
9, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride: 4,4' — (hexafluoroisopropylidene) diphthalic anhydride: 3,3 ', 4,4' -benzophenone tetracarboxylic dianhydride 1-16: 1-14: 1-12;
the molar ratio of the added mixed dianhydride to the added mixed diamine is 0.95: 1-1.06: 1.
2. The method for preparing the colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ according to claim 1, wherein the method comprises the following steps: the aprotic polar solvent is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
3. The method for preparing the colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ according to claim 2, wherein the method comprises the following steps: the upwind temperature of the steel belt of the casting machine is 80-120 ℃, and the downwind temperature of the steel belt is 100-150 ℃.
4. The method for preparing the colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ according to claim 2, wherein the method comprises the following steps: synchronous or asynchronous bidirectional stretching treatment is adopted; the synchronous biaxial stretching has a longitudinal stretching ratio of 1.00-1.40 and a transverse stretching ratio of 1.00-1.30; the asynchronous biaxial stretching has a longitudinal stretching ratio of 1.00-1.50 and a transverse stretching ratio of 1.00-1.30.
5. The method for preparing the colorless transparent polyimide film capable of resisting the high temperature of 400 ℃ according to claim 2, wherein the method comprises the following steps: the temperature in the imidization furnace is controlled to be 350-380 ℃.
6. The colorless transparent polyimide film prepared by the preparation method of the colorless transparent polyimide film with the high temperature resistance of 400 ℃ according to any one of claims 1 to 5.
7. The colorless transparent polyimide film according to claim 6, wherein: the glass transition temperature is not lower than 410 ℃, the cold-heat expansion ratio at 400 ℃ is not higher than 0.20%, and the light transmittance of a 75-micron thick film at 450nm is not less than 89%.
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