CN110951077A - Transparent polyimide precursor and preparation method thereof - Google Patents
Transparent polyimide precursor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transparent polyimide precursor and a preparation method thereof, wherein the polyimide precursor is polyamic acid obtained by polymerization reaction of a diamine component and a dianhydride component, the diamine component comprises 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether, wherein the 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether accounts for more than 70% of the total molar weight of the diamine component; the dianhydride component comprises 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, wherein the 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride accounts for more than 60 percent of the total molar amount of the dianhydride component. The transparent polyimide film obtained by the present invention is excellent in stability, transparency and heat resistance, is easily peeled from a substrate, has a thermal expansion coefficient of 45ppm/K or less and is 5% or less at an irradiation light wavelength of 308nm and 75% or more at an irradiation light wavelength of 400nm, and can be used as a material for a transparent resin substrate.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a transparent polyimide precursor and a manufacturing method thereof, polyimide, a transparent polyimide film and a preparation method thereof.
Background
Electronic devices are becoming increasingly lighter and thinner with increasing performance, and also are required to have a low thermal expansion coefficient, and in order to achieve the effect of preventing warpage, the thermal expansion coefficient is preferably 45ppm/K or less. Polyimide is one of promising resin substrate materials because of its excellent heat resistance and dimensional stability.
In recent years, the following methods have been proposed for obtaining a thin polyimide substrate: a polyimide film is temporarily formed on a support base material made of a glass substrate, and then the polyimide film is peeled off after mounting an electronic component. The polyimide film is obtained by casting a polyimide precursor solution having a specific structure on an inorganic substrate, drying the solution, and imidizing the solution. However, the thermal expansion coefficients of the polyimides exceed 45ppm/K, and the difference from the thermal expansion coefficient of the glass substrate of 10ppm/K or less is large, and the shape stability is poor. Therefore, development of a transparent polyimide film that can replace a glass substrate and satisfy the property requirements such as dimensional stability has been the main research direction at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a transparent polyimide precursor and a preparation method thereof, polyimide, a transparent polyimide film and a preparation method thereof, wherein the prepared polyimide film can be used as a transparent resin substrate material and meets the requirements of high transparency, low thermal expansion coefficient and high heat resistance.
The polyimide precursor is obtainable by polymerization reaction of a diamine component and a dianhydride component, and can be represented by the following general formula (1):
[-OCX(COOH)2CO-HN-Y-NH-](1)
the polyimide obtained by imidizing the polyimide precursor can be represented by the following general formula (2):
[-N(OC)2X(CO)2N-Y-](2)
in the formulae (1) and (2), X is a tetravalent residue obtained by removing two anhydride groups from a dianhydride, and Y is a divalent residue obtained by removing two amino groups from a diamine.
The diamine component of the polyimide precursor of the present invention comprises 6FODA represented by the following formula (3), and the diamine structural unit (Y) comprising 6FODA has a structure represented by the following formula (3 a); preferably, the diamine component further comprises m-TB represented by the following formula (3 b):
the dianhydride component of the polyimide precursor of the present invention comprises HPMDA represented by the following formula (4), and a dianhydride structural unit (X) comprising HPMDA has a structure represented by the following formula (4 a):
thus, a polyimide precursor represented by the following formula (5) containing 6FODA and HPMDA is obtained, and imidized to obtain a polyimide represented by the following formula (6):
the polyimide precursor is polyamic acid obtained by polymerization reaction of a diamine component and a dianhydride component, wherein the diamine component comprises 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether, and the 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether accounts for more than 70% of the total molar weight of the diamine component; the dianhydride component comprises 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, wherein the 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride accounts for more than 60 percent of the total molar amount of the dianhydride component.
Preferably, the molar ratio of the diamine component to the dianhydride component is (0.95-1.05): 1.
preferably, the diamine component further comprises 2, 2 '-dimethyl-4, 4' -diaminobiphenyl.
Preferably, the dianhydride component further comprises at least one of 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride and 1, 2, 4, 5-pyromellitic dianhydride.
Preferably, the diamine component may further include 3, 3 ' -dimethyl-4, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4, 6-dimethyl-m-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, 3 ' -diaminodiphenylethane, 4' -diaminodiphenyl methane, 3 ' -diaminodiphenyl methane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobiphenyl, 3 ' -dimethyl-4, 4' -diaminobiphenyl, 2-dimethyldiphenylether, 4' -diaminodiphenyl ether, and mixtures thereof, 3, 3 ' -dimethoxy-4, 4' -diaminobiphenyl and 4, 4' -diamino-p-terphenyl.
Preferably, the dianhydride component may further include naphthalene-2, 3, 6, 7-tetracarboxylic dianhydride, naphthalene-1, 2, 5, 6-tetracarboxylic dianhydride, naphthalene-1, 2, 6, 7-tetracarboxylic dianhydride, pyromellitic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 2', 3, 3' -benzophenonetetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) -propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) -propane dianhydride, bis (2, 3-dicarboxyphenyl) ether dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride.
A polyimide precursor solution comprises the polyimide precursor and an organic solvent.
Preferably, the viscosity of the solution is 800-; preferably, the viscosity of the solution is 1200-1500P.
Preferably, the preparation method of the polyimide precursor solution comprises the following steps: under the protection of nitrogen, diamine is dissolved in an organic solvent, then dianhydride is added, and the reaction is carried out for 4-10h at room temperature, thus obtaining the diamine.
Preferably, the organic solvent is at least one of dimethylacetamide, N-dimethylacetamide, 2-butanone, diglyme, xylene, and γ -butyrolactone.
The polyimide precursor solution may further contain a filler, and for example, an inorganic fine particle filler such as silicon oxide, aluminum oxide, boron nitride, or aluminum nitride may be added for the purpose of improving the sliding property or the thermal conductivity.
The polyimide is prepared by imidizing the polyimide precursor solution.
The transparent polyimide film is prepared from the polyimide precursor solution through thermal imidization film preparation.
Preferably, the light transmittance of the film under the condition of 308nm is less than or equal to 5 percent, the light transmittance under the condition of 400nm is more than or equal to 75 percent, and the thermal expansion coefficient is less than or equal to 45 ppm/K; preferably, the film has a yellowness index of 5 or less.
A preparation method of a transparent polyimide film comprises the steps of coating a base material with the polyimide precursor solution, heating and imidizing to form a polyimide layer on the base material, then carrying out laser irradiation on the interface between the polyimide layer and the base material, and stripping the polyimide layer to obtain the transparent polyimide film.
The invention has the following beneficial effects:
the transparent polyimide precursor of the present invention can be imidized by heating to form a polyimide having excellent dimensional stability, transparency, and heat resistance. The polyimide film formed by coating the polyimide precursor of the present invention on the support substrate also has excellent laser film peeling characteristics, and therefore, the polyimide film can be obtained by a method using the support substrate for assistance, and the processing is convenient. Due to the characteristics, the polyimide film prepared by using the polyimide precursor as the raw material can meet the requirements of dimensional stability and the like, can replace a glass substrate of a display or a touch screen, and is a practical flexible heat-resistant transparent resin substrate material with application prospect.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
The following are the designations of the raw materials used in the specific examples:
HPMDA: 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride
6 FODA: 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether
CBDA: 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride
m-TB: 2, 2 '-dimethyl-4, 4' -diaminobiphenyl
And (3) PMDA: 1, 2, 4, 5-pyromellitic dianhydride
BPDA: 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride
DMAC: dimethylacetamide
Example 1
Under the protection of nitrogen, diamine component and 110g of DMAC are added into a 200mL separable flask, after dissolution, dianhydride component is added, and then the mixture is stirred at room temperature for 10 hours to carry out polymerization reaction, so that polyimide precursor solution is obtained. Wherein the diamine component is 10.08g of 6FODA and the dianhydride component is 6.72g of HPMDA.
Example 2
The diamine component is 9.072g of 6FODA and 0.636g m-TB, and the dianhydride component is 5.376g of HPMDA and 1.176g of CBDA, wherein the 6FODA accounts for 90 percent of the total molar amount of the diamine component, and the m-TB accounts for 10 percent of the total molar amount of the diamine component; the HPMDA accounts for 80% of the total molar amount of the dianhydride component, and the CBDA accounts for 20% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 3
The diamine component was 10.08g of 6FODA and the dianhydride component was 6.048g of HPMDA and 0.654g of PMDA, where HPMDA accounted for 90% and PMDA accounted for 10% of the total molar amount of dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 4
The diamine component was 9.072g of 6FODA and 0.636g m-TB and the dianhydride component was 4.71g of HPMDA and 1.764g of CBDA. Wherein 6FODA accounts for 90% of the total molar amount of the diamine component, and m-TB accounts for 10% of the total molar amount of the diamine component; the HPMDA accounts for 70% of the total molar amount of the dianhydride component, and the CBDA accounts for 30% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 5
The diamine component was 7.06g of 6FODA and 1.92g m-TB and the dianhydride component was 6.72g of HPMDA. Wherein 6FODA accounts for 70% of the total molar amount of the diamine component, and m-TB accounts for 30% of the total molar amount of the diamine component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 6
The diamine component was 8.064g of 6FODA and 1.272g m-TB, and the dianhydride component was 6.72g of HPMDA. Wherein 6FODA accounts for 80% of the total molar amount of the diamine component, and m-TB accounts for 20% of the total molar amount of the diamine component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 7
The diamine component was 10.08g of 6FODA and the dianhydride component was 5.376g of HPMDA and 1.308g of PMDA, where HPMDA accounted for 80% and PMDA accounted for 20% of the total molar amount of dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 8
The diamine component was 10.08g of 6FODA and the dianhydride component was 4.032g of HPMDA and 2.352g of CBDA, where HPMDA accounted for 60% and CBDA accounted for 40% of the total molar amount of dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 9
The diamine component was 9.07g of 6FODA and the dianhydride component was 6.05g of HPMDA. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 1
The diamine component is 6.048g of 6FODA and 2.544g m-TB, the dianhydride component is 4.704g of HPMDA and 1.962g of PMDA, wherein 6FODA accounts for 60% of the total molar amount of the diamine component, and m-TB accounts for 40% of the total molar amount of the diamine component; the HPMDA accounts for 70% of the total molar amount of the dianhydride component, and the PMDA accounts for 30% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 2
The diamine component is 6.048g of 6FODA and 2.544g m-TB, the dianhydride component is 4.032g of HPMDA and 2.616g of PMDA, wherein the 6FODA accounts for 60 percent of the total molar amount of the diamine component, and the m-TB accounts for 40 percent of the total molar amount of the diamine component; the HPMDA accounts for 60% of the total molar amount of the dianhydride component, and the PMDA accounts for 40% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 3
The diamine component is 5.04g of 6FODA and 3.18g m-TB, and the dianhydride component is 3.36g of HPMDA and 2.94g of CBDA, wherein 6FODA accounts for 50% of the total molar amount of the diamine component, and m-TB accounts for 50% of the total molar amount of the diamine component; the HPMDA accounts for 50% of the total molar amount of the dianhydride component, and the CBDA accounts for 50% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 4
The diamine component is 5.04g of 6FODA and 3.18g m-TB, the dianhydride component is 2.688g of HPMDA and 3.528g of CBDA, wherein 6FODA accounts for 50% of the total molar amount of the diamine component, and m-TB accounts for 50% of the total molar amount of the diamine component; the HPMDA accounts for 40% of the total molar amount of the dianhydride component, and the CBDA accounts for 60% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 5
The diamine component is 4.032g of 6FODA and 3.816g m-TB, the dianhydride component is 2.016g of HPMDA and 4.578g of PMDA, wherein the 6FODA accounts for 40 percent of the total molar amount of the diamine component, and the m-TB accounts for 60 percent of the total molar amount of the diamine component; the HPMDA accounts for 30% of the total molar amount of the dianhydride component, and the PMDA accounts for 70% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 6
The diamine component is 3.024g of 6FODA and 4.452g m-TB, the dianhydride component is 1.344g of HPMDA and 4.704g of CBDA, wherein 6FODA accounts for 30% of the total molar amount of the diamine component, and m-TB accounts for 70% of the total molar amount of the diamine component; the HPMDA accounts for 20% of the total molar amount of the dianhydride component, and the CBDA accounts for 80% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Comparative example 7
The diamine component is 1.008g of 6FODA and 5.724g m-TB, the dianhydride component is 0.672g of HPMDA and 5.886g of PMDA, wherein the 6FODA accounts for 10 percent of the total molar amount of the diamine component, and the m-TB accounts for 90 percent of the total molar amount of the diamine component; the HPMDA accounts for 10% of the total molar amount of the dianhydride component, and the PMDA accounts for 90% of the total molar amount of the dianhydride component. Polymerization was carried out in the same manner as in example 1 to obtain a polyimide precursor solution.
Example 10
Adding solvent DMAC into the polyimide precursor solution obtained in the embodiment 1 to dilute the solution until the viscosity is 800P, then coating the solution on a polyimide film substrate with the thickness of 75 microns, heating the solution at 100 ℃ for 15min, then heating the solution from room temperature to 130 ℃ at the heating rate of 3 ℃/min in a nitrogen environment, preserving the temperature for 10min, then heating the solution to 300 ℃ at the heating rate of 3 ℃/min to form a polyimide layer, and stripping the polyimide layer to obtain the polyimide film with the thickness of 24 microns.
Example 11
The polyimide precursor solution obtained in example 2 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 25 μm.
Example 12
The polyimide precursor solution obtained in example 3 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 23 μm.
Example 13
The polyimide precursor solution obtained in example 4 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 24 μm.
Example 14
The polyimide precursor solution obtained in example 5 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 25 μm.
Example 15
The polyimide precursor solution obtained in example 6 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 24 μm.
Example 16
The polyimide precursor solution obtained in example 7 was processed in the same manner as in example 10 to obtain a polyimide film having a film thickness of 9.9 μm.
Example 17
The polyimide precursor solution obtained in example 8 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 10.3 μm.
Example 18
The polyimide precursor solution obtained in example 9 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 10.1 μm.
Comparative example 8
The polyimide precursor solution obtained in comparative example 1 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 25 μm.
Comparative example 9
The polyimide precursor solution obtained in comparative example 2 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 23 μm.
Comparative example 10
The polyimide precursor solution obtained in comparative example 3 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 24 μm.
Comparative example 11
The polyimide precursor solution obtained in comparative example 4 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 25 μm.
Comparative example 12
The polyimide precursor solution obtained in comparative example 5 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 23 μm.
Comparative example 13
The polyimide precursor solution obtained in comparative example 6 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 10.2 μm.
Comparative example 14
The polyimide precursor solution obtained in comparative example 7 was processed in the same manner as in example 10 to obtain a polyimide film having a thickness of 10.5 μm.
TABLE 1 composition of diamine and dianhydride in the raw materials of the examples (weight unit: g)
Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
6FODA | 10.08 | 9.072 | 10.08 | 9.072 | 7.06 | 8.064 | 10.08 | 10.08 | 9.07 |
m-TB | 0.636 | 0.636 | 1.92 | 1.272 | |||||
HPMDA | 6.72 | 5.376 | 6.048 | 4.71 | 6.72 | 6.72 | 5.376 | 4.032 | 6.05 |
PMDA | 0.654 | 1.308 | |||||||
CBDA | 1.176 | 1.764 | 2.352 |
TABLE 2 concrete composition (weight unit: g) of diamine and dianhydride in the raw materials of each comparative example
Test examples
The measurement method and evaluation method of physical properties were as follows:
transmittance and Yellowness (YI)
The transmittances at 308nm, 355nm, 400nm and 430nm (T308, T355, T400 and T430) were determined using Shimadzu (SHIMADZU) UV-3600 spectrophotometer on polyimide films (50 mm. times.50 mm, thickness 10 μm to 15 μm). YI (yellowness) was calculated based on the following calculation formula.
YI=100×(1.2879X-1.0592Z)/Y
X, Y, Z denotes the tristimulus value of the test piece, and is defined in Japanese Industrial Standard (JIS) Z8722.
Coefficient of thermal expansion
The polyimide film having a size of 3mm × 15mm was heated from 30 ℃ to 280 ℃ at a constant heating rate (10 ℃/min) while applying a load of 5.0g to the film by a thermomechanical analyzer (TMA) and then cooled from 250 ℃ to 100 ℃, and the thermal expansion coefficient was measured from the elongation (linear expansion) of the polyimide film at the time of cooling.
Glass transition temperature (Tg)
The dynamic viscoelasticity at a temperature of 5 ℃/min from 23 ℃ to 500 ℃ was measured on a polyimide film (5 mm. times.70 mm) by a dynamic thermomechanical analyzer, and the glass transition temperature (. degree.C.) was determined.
Thermal decomposition temperature (Td1)
The weight change of a polyimide film having a weight of 10mg to 20mg when the temperature was raised from 30 ℃ to 550 ℃ at a constant rate was measured by a thermogravimetric analyzer TG/DTA6200 under a nitrogen atmosphere, and the temperature at which the weight at 200 ℃ was zero and the weight loss rate was 1% was set to the thermal decomposition temperature (Td 1).
Stripping property: LED (light emitting diode)
This is a laser irradiation energy density (mJ/cm) until the polyimide layer can be peeled off from the support base (glass substrate)2) (code number: an LED). The irradiation conditions are similar to the "peelability" described in the following paragraphs: laser Lift Off (LLO) "is the same. The higher the energy density, the more difficult it is to peel. Also in view of the life of the laser irradiation device, it is preferable that the irradiation energy density is small. The upper limit of the measurement is 300mJ/cm2Will be at 300mJ/cm2The following non-strippable one is "x".
Stripping property: laser lift-off (LLO)
A laser beam having a beam size of 14mm × 1.2mm, a traveling speed of 6mm/s, and an overlap ratio of 80% was irradiated from the side of a support substrate (glass) by an excimer laser processing machine (wavelength 308nm), and a state where the support substrate and a polyimide layer were completely separated (a separation range was determined by a dicing blade, and a polyimide film was naturally separated from the glass after a one-round cut) was defined as "○", and a state where the support substrate and the polyimide layer were not separated from each other over the entire surface or a part thereof, or a state where the polyimide layer was discolored was defined as "x".
The polyimide films obtained in examples 10 to 18 and comparative examples 8 to 14 were subjected to the tests for the coefficient of thermal expansion CTE, light transmittance, yellowness YI, thermal decomposition temperature Td1, and glass transition temperature Tg in the above-described manner, respectively. The test results are shown in tables 3 and 4:
table 3 performance test results of the polyimide films of the respective examples
Table 4 performance test results of polyimide films of comparative examples
Comparative example | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
Thickness (μm) | 25 | 23 | 24 | 25 | 23 | 10.2 | 10.5 |
CTE(ppm/k) | 47 | 44 | 49 | 40 | 38 | 35 | 28 |
YI | 1.9 | 1.7 | 3.1 | 2.8 | 4.6 | 3.6 | 1.4 |
T308 | 0 | 0.5 | 0 | 0 | 0.1 | 0 | 0.9 |
T355 | 49.2 | 46.0 | 0 | 0 | 21.6 | 0 | 44.2 |
T400 | 74.2 | 70.1 | 47.2 | 49.6 | 54.8 | 42.3 | 67 |
T430 | 85.1 | 84.1 | 80.9 | 76.2 | 77.0 | 83.9 | 88.6 |
Tg(℃) | 386 | 386 | 376 | 301 | 369 | 381 | 388 |
Td1(℃) | 378 | 380 | 386 | 428 | 381 | 367 | 387 |
LED(mJ/cm2) | 200 | × | 240 | × | 240 | 200 | 190 |
LLO | × | × | × |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A transparent polyimide precursor is characterized in that the polyimide precursor is polyamic acid obtained by polymerization reaction of a diamine component and a dianhydride component, wherein the diamine component comprises 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether, and the 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether accounts for more than 70% of the total molar weight of the diamine component; the dianhydride component comprises 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, wherein the 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride accounts for more than 60 percent of the total molar amount of the dianhydride component.
2. The transparent polyimide precursor according to claim 1, wherein the diamine component further comprises 2, 2 '-dimethyl-4, 4' -diaminobiphenyl.
3. The transparent polyimide precursor according to claim 1 or 2, wherein the dianhydride component further comprises at least one of 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 4, 5-pyromellitic dianhydride.
4. The transparent polyimide precursor according to any one of claims 1 to 3, wherein the molar ratio of the diamine component to the dianhydride component is (0.95 to 1.05): 1.
5. a polyimide precursor solution comprising the transparent polyimide precursor according to any one of claims 1 to 4 and an organic solvent.
6. The polyimide precursor solution according to claim 5, wherein the viscosity of the solution is 800-; preferably, the viscosity of the solution is 1200-1500P.
7. A polyimide obtained by imidizing the polyimide precursor solution according to claim 5 or 6.
8. A transparent polyimide film obtained by forming a film from the polyimide precursor solution according to claim 5 or 6 by thermal imidization.
9. The transparent polyimide film according to claim 8, wherein the film has a light transmittance of 5% or less at 308nm, a light transmittance of 75% or more at 400nm, and a thermal expansion coefficient of 45ppm/K or less; preferably, the film has a yellowness index of 5 or less.
10. A method for producing a transparent polyimide film, comprising applying the polyimide precursor solution according to claim 5 or 6 to a substrate, heating to imidize the solution to form a polyimide layer on the substrate, and then irradiating an interface between the polyimide layer and the substrate with laser light to peel off the polyimide layer, thereby obtaining a transparent polyimide film.
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