CN112457493A - High-transparency low-expansion polyimide film and preparation method thereof - Google Patents
High-transparency low-expansion polyimide film and preparation method thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention particularly relates to a high-transparency low-expansion polyimide film and a preparation method thereof, belonging to the technical field of modification of high polymer materials. The high-transparency low-expansion polyimide film is prepared by carrying out polycondensation reaction on amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFBP and a nitrogen-containing aromatic diamine monomer; the polyimide has the following structural formula:
Description
Technical Field
The invention particularly relates to a high-transparency low-expansion polyimide film and a preparation method thereof, belonging to the technical field of polyimide modification.
Background
The 'foldable/full screen' and '5G' related technologies break through application innovation and are the two hottest elements in the 2019 consumer electronics industry. And the air outlets behind the tidal current point to the polyimide film material except for the hot spots. The polyimide material has excellent heat resistance and stability, and can bear high-temperature processes such as electrode film deposition, annealing treatment and the like in the processing process of photoelectric devices, and the technical key for realizing the flexibility of display devices is to use high-transparency low-expansion polymer as a cover plate material to replace the traditional hard glass. However, the light transmittance of the conventional aromatic polyimide in the visible light region is yellow, which cannot meet the requirement of the flexible display cover plate material on high transparency of the film, and the thermal expansion coefficients of the common polyimide are all about 35-80 ppm/DEG C, which is difficult to meet the requirement that the thermal expansion coefficient is less than 20 ppm/DEG C in the high-temperature process of the flexible display device.
The research and development difficulty of the high-transparency polyimide for the flexible display is mainly due to the fact that various performances of the high-transparency polyimide are difficult to balance and harmonize, heat resistance/low expansion and a design concept of a molecular structure of the transparent polyimide are contrary, and improvement of one performance necessarily affects other performances.
Researchers usually introduce bulky substituents, fluorine-containing groups, asymmetric structures, alicyclic structures, non-coplanar structures and the like into molecular chains to improve PI light transmittance. The chinese patent publication No. CN102911359A reports that a polyimide prepared by polycondensation of 1, 4-bis (3, 4-dicarboxyphenoxy) cyclohexane dianhydride and a primary diamine monomer, introducing cyclohexane into the molecular structure, improves the transparency of the polyimide (light transmittance at 450nm is 70% to 90%), and glass transition temperature is between 200 ℃ and 300 ℃) without reducing the reactivity, but the heat resistance is greatly reduced by a large amount of alicyclic structures, and the linear expansion coefficient is not mentioned.
The introduction of structures such as ester groups, amide groups, nitrogen-containing heterocycles and the like into the PI molecular chain can reduce the thermal expansion coefficient of the polyimide, but has certain defects in other properties. Hasegawa et al introduced amido and fluorine-containing groups into the polyimide molecular chain, the coefficient of thermal expansion can be reduced to 9.9, but the light transmittance at 400nm is only 43.4%.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the high-transparency low-expansion polyimide film has high light transmittance, low expansion and thermal stability; meanwhile, the invention provides a simple and feasible preparation method.
The high-transparency low-expansion polyimide film is prepared by carrying out polycondensation reaction on amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFBP and a nitrogen-containing aromatic diamine monomer;
the polyimide has the following structural formula:
wherein Ar represents a nitrogen-containing aromatic diamine residue; n represents polymerization degree, and n is more than or equal to 400.
The structural formula of the amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB or the ester type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFBP is as follows:
wherein, when X is-NH, the compound represents amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB;
and when X is-O, the fluorine-containing hydrogenated tetracarboxylic dianhydride represents ester type HTA-TFBP.
The amide type fluorine-containing hydrogenated tetracarboxylic dianhydride (HTA-TFMB) is synthesized by taking Hydrogenated Trimellitic Anhydride Chloride (HTAC) and 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB) as raw materials.
The ester type fluorine-containing hydrogenated tetracarboxylic dianhydride (HTA-TFBP) is synthesized by taking Hydrogenated Trimellitic Anhydride Chloride (HTAC) and 2,2 '-bis (trifluoromethyl) -4,4' -bisphenol (TFBP) as raw materials.
In order to prepare polyimide with high molecular weight, the diamine is selected from nitrogen-containing aromatic diamine with high activity. Preferably, the nitrogen-containing aromatic diamine monomer is any one of the following diamines:
the preparation method of the high-transparency low-expansion polyimide film comprises the following steps:
(1) adding nitrogen-containing aromatic diamine into an organic solvent for dissolving, adding amide type or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride in the obtained solution in batches, and carrying out polycondensation reaction to obtain a polyamide acid (PAA) solution;
(2) adding a catalyst and a dehydrating agent into the polyamic acid solution, and carrying out chemical imidization to obtain a polyimide solution;
(3) and (3) casting the polyimide solution on super-flat glass, and then placing the super-flat glass in an oven to dry and remove the solvent to obtain the high-transparency low-expansion polyimide film.
The molar ratio of the amide type or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride to the nitrogen-containing aromatic diamine is 1: 1-1.2.
The organic solvent is N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) or N, N-Dimethylformamide (DMF).
Preferably, the solid content of the polyamic acid solution is 10 to 30 wt%.
Preferably, the reaction temperature in step (1) is 10 to 50 ℃.
Preferably, the catalyst is a tertiary amine (e.g., pyridine, triethylamine) and the dehydrating agent is an anhydride (e.g., acetic anhydride, propionic anhydride).
Preferably, the molar ratio of the catalyst and the dehydrating agent to the polyamic acid is 2-5: 1.
Preferably, the temperature of the chemical imidization is 25-60 ℃.
In the step (3), the casting film forming temperature is 70-150 ℃, the preferable temperature is 100 ℃, and the casting film forming time is 10-48 h, the preferable time is 24 h.
In the invention, ester groups, amide groups and nitrogen-containing heterocycles are simultaneously introduced into a polyimide molecular chain, so that intermolecular force can be effectively increased through the synergistic effect, the thermal expansion coefficient of polyimide is reduced, and the heat resistance of polyimide is improved; meanwhile, the introduction of the ester group, the fluorine-containing group and the alicyclic structure destroys the coplanarity of the molecular structure, inhibits charge transfer in molecules and among molecules, improves the light transmittance of the polyimide, and solves the key problem that the polyimide has high transparency and low thermal expansion and is difficult to have simultaneously. Although the prior art discloses the advantages of introducing the groups, the problem that the polyimide has yellow color and a high thermal expansion coefficient cannot be solved by introducing a single group, a synergistic effect of various special groups is needed, Hasegawa and the like introduce amido groups and fluorine-containing groups into a polyimide molecular chain, the thermal expansion coefficient can be reduced to 9.9, and the light transmittance at 400nm is only 43.4%; at present, the fluorine-containing group only improves the light transmittance of PI in a larger wavelength range, but does not contribute to the light transmittance of polyimide in a near ultraviolet region (455-350 nm); the alicyclic structure can improve the light transmittance of the near ultraviolet region PI.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, nitrogen-containing aromatic diamine and fluorine-containing dianhydride amide type/ester type fluorine-containing hydrogenated tetracarboxylic dianhydride are used as raw materials, and a fluorine-containing group, an alicyclic structure and an ester/amide group are introduced into a polyimide molecular chain to prepare polyimide with a new structure, so that the polyimide has the characteristics of high transparency, low expansion and excellent thermal stability, and the problem that the existing polyimide film is difficult to have the excellent performances at the same time is solved;
(2) the high-transparency low-expansion polyimide film prepared by the invention has the light transmittance of more than 88% at 380-780 nm and more than 90% at 450nm, the thermal expansion coefficient is reduced to below 20 ppm/DEG C, and the glass transition temperature is 300-350 ℃;
(3) the high-transparency low-expansion polyimide film prepared by the invention can be used as a flexible display cover plate film, promotes the domestic development of the flexible display cover plate film, and provides a flexible cover plate material with reliable quality and up-to-standard performance for the development of the flexible display device industry in China.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.126g of 2- (4-amino-phenyl) -benzooxazol-5-aminediamine monomer was added to a four-necked flask containing 18.252g of DMAc and dissolved with stirring under a nitrogen atmosphere; weighing 3.437g of HTA-TFMB dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 88% within the range of 380 nm-780 nm, the light transmittance is 90% at 450nm, the thermal expansion coefficient is 15 ppm/DEG C, and the glass transition temperature is 330.7 ℃.
Example 2
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.121g of 2- (4-aminophenyl) -5-aminobenzimidazole diamine monomer was added to a four-necked flask containing 18.232g of DMAc, and the mixture was stirred and dissolved under a nitrogen atmosphere; weighing 3.437g of HTA-TFMB dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 89% within the range of 380 nm-780 nm, the light transmittance is 90% at 450nm, the thermal expansion coefficient is 16 ppm/DEG C, and the glass transition temperature is 325.8 ℃.
Example 3
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.311g of 2, 5-bis (4-aminophenyl) -pyrimidinediamine monomer was added to a four-necked flask containing 18.992g of DMAc, and the mixture was stirred and dissolved under nitrogen; weighing 3.437g of HTA-TFMB dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 88% within the range of 380 nm-780 nm, the light transmittance is 90% at 450nm, the thermal expansion coefficient is 14 ppm/DEG C, and the glass transition temperature is 335.5 ℃.
Example 4
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.126g of 2- (4-amino-phenyl) -benzooxazol-5-aminediamine monomer was added to a four-necked flask containing 18.292g of DMAc and dissolved by stirring under nitrogen; weighing 3.447g of HTA-TFBP dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 88% within the range of 380 nm-780 nm, the light transmittance is 91% at 450nm, the thermal expansion coefficient is 18 ppm/DEG C, and the glass transition temperature is 318.5 ℃.
Example 5
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.121g of 2- (4-aminophenyl) -5-aminobenzimidazole diamine monomer was added to a four-necked flask containing 18.272g of DMAc, and the mixture was stirred and dissolved under a nitrogen atmosphere; weighing 3.447g of HTA-TFBP dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 89% within the range of 380 nm-780 nm, the light transmittance is 91% at 450nm, the thermal expansion coefficient is 18.5 ppm/DEG C, and the glass transition temperature is 315.7 ℃.
Example 6
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.311g of 2, 5-bis (4-aminophenyl) -pyrimidinediamine monomer was added to a four-necked flask containing 19.032g of DMAc, and the mixture was stirred and dissolved under nitrogen; weighing 3.447g of HTA-TFBP dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 88% within the range of 380 nm-780 nm, the light transmittance is 91% at 450nm, the thermal expansion coefficient is 17 ppm/DEG C, and the glass transition temperature is 320.4 ℃.
Comparative example 1
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.121g of 2- (4-aminophenyl) -5-aminobenzimidazole diamine monomer was added to a four-necked flask containing 13.460g of DMAc, and the mixture was stirred and dissolved under a nitrogen atmosphere; weighing 2.244g of 6FDA dianhydride monomer, adding the weighed 6FDA dianhydride monomer into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is over 31 percent within the range of 380 nm-780 nm, the light transmittance is 70 percent at 450nm, the thermal expansion coefficient is 41 ppm/DEG C, and the glass transition temperature is 351.6 ℃.
Comparative example 2
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.121g of 2- (4-aminophenyl) -5-aminobenzimidazole diamine monomer was added to a four-necked flask containing 10.428g of DMAc, and the mixture was stirred and dissolved under a nitrogen atmosphere; weighing 1.486g of BPDA dianhydride monomer, adding the BPDA dianhydride monomer into the solution in batches under the stirring condition, stirring the solution for 4 hours at the temperature of 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance within the range of 380 nm-780 nm reaches more than 0 percent, when the light transmittance is 450nm, the light transmittance is 54 percent, the thermal expansion coefficient is 27 ppm/DEG C, and the glass transition temperature is 360.7 ℃.
Comparative example 3
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.601g of TFMB diamine monomer is added into a four-neck flask containing 20.152g of DMAc, and the mixture is stirred and dissolved under the protection of nitrogen; weighing 3.437g of HTA-TFMB dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 89% within the range of 380 nm-780 nm, the light transmittance is 91% at 450nm, the thermal expansion coefficient is 45 ppm/DEG C, and the glass transition temperature is 330.1 ℃.
Comparative example 4
The high-transparency low-expansion polyimide film is prepared according to the following method:
(1) 1.601g of TFMB diamine monomer is added into a four-neck flask containing 20.192g of DMAc, and the mixture is stirred and dissolved under the protection of nitrogen; weighing 3.447g of HTA-TFBP dianhydride monomer, adding into the solution in batches under the stirring condition, stirring for 4 hours at 40 ℃, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding 1.518g of catalyst triethylamine and 1.531g of dehydrating agent acetic anhydride into the polyamic acid solution for chemical imidization, and stirring for 8 hours at 40 ℃ to obtain a polyimide solution;
(3) and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in an oven at 100 ℃ for drying for 24 hours to obtain the high-transparency low-expansion polyimide film.
The obtained polyimide composite film is subjected to performance characterization, the light transmittance is up to more than 89% within the range of 380 nm-780 nm, the light transmittance is 92% at 450nm, the thermal expansion coefficient is 49 ppm/DEG C, and the glass transition temperature is 321.3 ℃.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A high-transparency low-expansion polyimide film is characterized in that: obtained by the polycondensation reaction of amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFBP and a nitrogen-containing aromatic diamine monomer;
the polyimide has the following structural formula:
wherein Ar represents a nitrogen-containing aromatic diamine residue; n represents polymerization degree, and n is more than or equal to 400.
2. The high-transparency low-expansion polyimide film according to claim 1, wherein: the structural formula of the amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB or the ester type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFBP is as follows:
wherein, when X is-NH, the compound represents amide type fluorine-containing hydrogenated tetracarboxylic dianhydride HTA-TFMB;
and when X is-O, the fluorine-containing hydrogenated tetracarboxylic dianhydride represents ester type HTA-TFBP.
3. The high-transparency low-expansion polyimide film according to claim 1, wherein: the nitrogen-containing aromatic diamine monomer is any one of the following diamines:
4. a method for producing a high-transparency low-expansion polyimide film according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) adding nitrogen-containing aromatic diamine into an organic solvent for dissolving, adding amide type or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride in the obtained solution in batches, and carrying out polycondensation reaction to obtain a polyamic acid solution;
(2) adding a catalyst and a dehydrating agent into the polyamic acid solution, and carrying out chemical imidization to obtain a polyimide solution;
(3) and (3) casting the polyimide solution, and then drying to obtain the high-transparency low-expansion polyimide film.
5. The method for preparing a highly transparent and low-expansion polyimide film according to claim 4, wherein: the molar ratio of the amide type or ester type fluorine-containing hydrogenated tetracarboxylic dianhydride to the nitrogen-containing aromatic diamine is 1: 1-1.2.
6. The method for preparing a highly transparent and low-expansion polyimide film according to claim 4, wherein: the organic solvent is N, N-dimethylacetamide, N-methylpyrrolidone or N, N-dimethylformamide.
7. The method for preparing a highly transparent and low-expansion polyimide film according to claim 4, wherein: in the step (1), the polycondensation reaction temperature is 10-50 ℃; the solid content of the polyamic acid solution is 10-30 wt%.
8. The method for preparing a highly transparent and low-expansion polyimide film according to claim 4, wherein: the catalyst is tertiary amine, and the dehydrating agent is anhydride.
9. The method for preparing a highly transparent and low-expansion polyimide film according to claim 4, wherein: the molar ratio of the catalyst to the dehydrating agent to the polyamic acid is 2-5: 1, and the temperature during chemical imidization is 25-60 ℃.
10. The method for preparing a highly transparent and low-expansion polyimide film according to claim 4, wherein: in the step (3), the casting film forming temperature is 70-150 ℃, and the casting film forming time is 10-48 h.
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