CN116253880B - Polyamic acid resin and preparation method thereof, black polyimide film and preparation method thereof - Google Patents
Polyamic acid resin and preparation method thereof, black 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 application discloses a polyamic acid resin and a preparation method thereof, a black polyimide film and a preparation method thereof, belonging to the technical field of polyimide films, and the technical scheme is that the polyamic acid resin comprises the following preparation raw materials: the organic-inorganic composite material comprises (by weight) 1 (0.992-1.005) of aromatic diamine, 3-25% of aromatic dianhydride, and 0.5-2% of black filler; the black filler comprises carbon black, so that the electrical strength and mechanical property of the polyimide film are improved while the content of black pigment is reduced on the premise of ensuring the covering property of the polyimide film.
Description
Technical Field
The application relates to the technical field of polyimide films, in particular to polyamide acid resin and a preparation method thereof, a black polyimide film and a preparation method thereof.
Background
The black polyimide film has excellent mechanical property, chemical stability, heat resistance and the like of the polyimide film, and also has good covering property, heat conductivity and antistatic property, and is widely applied to the packaging field, the semiconductor packaging field, the high-temperature-resistant label and covering film industry.
The preparation of the existing black polyimide film mainly comprises two methods: the first is to coat an organic or inorganic paint with good light-shielding property on the surface of a polyimide film, and then cure the paint to obtain a black polyimide film; and secondly, adding black pigment into the polyamic acid resin solution, and then carrying out tape casting and high-temperature imidization treatment to obtain the black polyimide film. In the two preparation methods, the first preparation method has complex procedures and high cost, and the black coating is easy to peel off from the base material polyimide film under the condition of severe use environment; in order to achieve good black covering effect, the second preparation method has a large pigment addition amount (generally about 5%), so that the electrical strength and mechanical properties of the polyimide film are greatly reduced, and further application of the black polyimide film is restricted.
Disclosure of Invention
The application provides a polyamide acid resin and a preparation method thereof, and a black polyimide film and a preparation method thereof, wherein the electrical strength and mechanical properties of the polyimide film are improved while the content of black pigment is reduced on the premise of ensuring the covering performance of the polyimide film.
The first aspect of the present application provides a polyamic acid resin, which adopts the following technical scheme:
a polyamic acid resin, comprising the following preparation raw materials: the organic-inorganic composite material comprises (by weight) 1 (0.992-1.005) of aromatic diamine, 3-25% of aromatic dianhydride, and 0.5-2% of black filler; wherein the black filler comprises carbon black.
Preferably, the content of the phenoxy phosphazene organic matter is 10-25wt% of the total amount of aromatic diamine and aromatic dianhydride.
Preferably, the phenoxy phosphazene organic matter is phenoxy polyphosphazene or phenoxy cyclophosphazene.
Preferably, the molecular weight of the phenoxy polyphosphazene is 693-1617, and the molecular weight of the phenoxy cyclophosphazene is 693.
Preferably, the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the black filler further comprises carbon nanotubes, and the weight ratio of the carbon black to the carbon nanotubes is 10: (1-1.5).
Preferably, the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
In a second aspect, the present application provides a process for producing, for example, a polyamic acid resin, comprising the steps of:
adding black filler into a solvent to disperse to obtain pre-dispersed black slurry;
preparation of polyamide acid resin: (1) Adding aromatic diamine into a solvent, and stirring to completely dissolve the aromatic diamine to form an amine solution;
(2) Adding the phenoxy phosphazene organic matter into the amine solution in the step (1), and stirring to completely dissolve the phenoxy phosphazene organic matter;
(3) Adding the pre-dispersed black paste into the amine solution obtained in the step (2), and continuously stirring;
(4) Adding aromatic dianhydride into the amine solution obtained in the step (3) in batches at the temperature of 30-45 ℃ to enable the dianhydride to react completely;
(5) And (3) carrying out vacuum defoaming on the solution obtained in the step (4) to obtain the polyamic acid resin.
The third aspect of the present application provides a method for preparing a black polyimide film, wherein the polyamic acid resin solution obtained above is cast to form a film, so as to obtain a polyamic acid film, and then the film is imidized for 2 to 15 minutes at a high temperature within the range of 360 to 450 ℃ to obtain the black polyimide film.
A fourth aspect of the present application is to provide a black polyimide film obtained by the above-described production method.
In summary, the application has the following beneficial effects:
the cast polyamic acid film is placed in an imine furnace at normal temperature, the imidization of the polyamic acid film is started along with the temperature rise of the imine furnace, the imidization stage is started when the temperature rises to 360 ℃, the imidization of the relatively thin polyimide film is finished for 2-5 minutes (for example, the thickness is 7.5 mu m), the imidization of the polyimide film with the thickness of 25 mu m and above is finished for 10-15 minutes, the phenoxy phosphazene organic matters in the polyamic acid film are also started along with the temperature rise of imidization in the imidization process, the phenoxy phosphazene organic matters are gradually decomposed, P-O bond fracture and dehydrogenation are carried out, a large number of carbon-carbon double bonds are formed, and finally, the phosphazene organic matters form a stable heat-resistant annular structure, and meanwhile, the color of the phosphazene organic matters is changed from white to reddish brown to black. For the preparation of the black polyimide film, the addition of the phenoxy phosphazene organic matters can effectively reduce the use amount of the black filler compared with the traditional technology of using a large amount of black filler for color development, and can also improve the mechanical properties, particularly the puncture strength, of the polyimide film.
Although the polyimide film prepared by adding the phenoxy phosphazene organic matter is black, the transparency of the polyimide film is relatively high, so that the polyimide film has a certain covering and dyeing effect after a small amount of black filler is added, the light transmittance of the polyimide film is further reduced, and the covering performance is effectively improved.
According to the application, after the black filler is selected from the combination of carbon black and carbon nanotubes, the unique network structure of the carbon nanotubes further improves the mechanical properties of the polyimide film and further widens the application range of the polyimide film under the requirement of ensuring the covering property of the polyimide film.
The viscosity of the finally prepared polyamide acid resin is 15-30 ten thousand centipoise, so when the phenoxy phosphazene organic matter and the pre-dispersed black slurry are added into the amine solution, the solubility of the phenoxy phosphazene organic matter and the dispersion of the black filler can be effectively ensured, and the surface of the finally obtained polyimide film has no black spots or bright spots, and the quality of the polyimide film can be ensured; in addition, the molecular weight of the phenoxy polyphosphazene is 693-1617, and if the molecular weight exceeds the limit of the application, the problem that the dissolution and the dispersibility of the phenoxy polyphosphazene in a solvent are poor due to the excessive molecular weight is caused. In addition, the reaction of the aromatic dianhydride and the aromatic diamine belongs to exothermic reaction, after the aromatic dianhydride is added for a small amount and a plurality of times, the reaction of the aromatic dianhydride and the aromatic diamine can be ensured to be complete, and meanwhile, the reaction temperature can be better controlled.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the embodiment and the comparative example are all from the market, wherein the aromatic diamine can be one or a combination of a plurality of ODA (4, 4' -diaminodiphenyl ether), PDA (p-phenylenediamine) and MDA (4, 4' -diaminodiphenyl methane), and the aromatic dianhydride can be one or a combination of PMDA (pyromellitic dianhydride), BPDA (biphenyl tetracarboxylic dianhydride) and ODPA (4, 4' -oxydiphthalic anhydride), and because the reaction speed of the biphenyl tetracarboxylic dianhydride is low, when the pyromellitic dianhydride and the biphenyl tetracarboxylic dianhydride are combined for use, the biphenyl tetracarboxylic dianhydride needs to be added first for complete reaction, and then the pyromellitic dianhydride needs to be added.
Example 1
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 90g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 2.3g of phenoxy polyphosphazene with the molecular weight of 693 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxy polyphosphazene;
(4) Adding 7.4g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 12.2g of pyromellitic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride is completely reacted to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the pyromellitic dianhydride is 1:1;
the phenoxy polyphosphazene accounts for 10% of the mass sum of the 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
the carbon black accounts for 1.5 percent of the mass sum of the 4,4' -diaminodiphenyl ether and the pyromellitic dianhydride.
Example 2
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 90g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 0.7g of phenoxy polyphosphazene with the molecular weight of 693 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxy polyphosphazene;
(4) Adding 9.83g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 12.2g of pyromellitic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride is completely reacted to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the pyromellitic dianhydride is 1:1;
the phenoxy polyphosphazene accounts for 3% of the mass sum of the 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
the carbon black accounts for 2 percent of the mass sum of the 4,4' -diaminodiphenyl ether and the pyromellitic dianhydride.
Example 3
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 103.9g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 3.5g of phenoxycyclophosphazene with the molecular weight of 693 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxycyclophosphazene;
(4) Adding 4.9g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 12.2g of pyromellitic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride is completely reacted to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the pyromellitic dianhydride is 1:1;
the phenoxy cyclophosphazene accounts for 15% of the mass sum of the 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
the carbon black accounts for 1% of the mass sum of the 4,4' -diaminodiphenyl ether and the pyromellitic dianhydride.
Example 4
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 115.1g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 5.85g of phenoxycyclophosphazene with the molecular weight of 693 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxycyclophosphazene;
(4) Adding 2.46g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 12.2g of pyromellitic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride is completely reacted to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the pyromellitic dianhydride is 1:1;
the phenoxy cyclophosphazene accounts for 25% of the mass sum of the 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
the carbon black accounts for 0.5 percent of the mass sum of the 4,4' -diaminodiphenyl ether and the pyromellitic dianhydride.
Example 5
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black and 1g of carbon nano tube into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 104g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 3.5g of phenoxycyclophosphazene with the molecular weight of 693 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxycyclophosphazene;
(4) Adding 4.91g of the pre-dispersed black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 12.2g of pyromellitic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride is completely reacted to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the pyromellitic dianhydride is 1:1;
the phenoxy cyclophosphazene accounts for 15% of the mass sum of the 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
the black filler accounts for 1.1 percent of the mass sum of the 4,4' -diaminodiphenyl ether and the pyromellitic dianhydride.
Example 6
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black and 1.5g of carbon nano tubes into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 115g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 4.91g of phenoxycyclophosphazene with the molecular weight of 693 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxycyclophosphazene;
(4) Adding 4.16g of the pre-dispersed black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 4.9g of diphenyl tetracarboxylic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and fully stirring to ensure complete dissolution reaction, then adding 8.47g of pyromellitic dianhydride for many times and slowly stirring to ensure complete reaction of the dianhydride and obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the dianhydride is 1:0.992;
the phenoxy cyclophosphazene accounts for 20% of the mass sum of the 4,4' -diaminodiphenyl ether and the dianhydride;
the black filler accounts for 0.92% of the mass sum of the 4,4' -diaminodiphenyl ether and the dianhydride.
Example 7
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 121.79g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 4.15g of phenoxy polyphosphazene with the molecular weight of 1617 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxy polyphosphazene;
(4) Adding 7.57g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 16.54g of biphenyl tetracarboxylic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride reacts completely to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the biphenyl tetracarboxylic dianhydride is 1:1.005;
the phenoxy polyphosphazene accounts for 15% of the mass sum of the 4,4' -diaminodiphenyl ether and the biphenyl tetracarboxylic dianhydride;
the black filler accounts for 1.3 percent of the mass sum of the 4,4' -diaminodiphenyl ether and the biphenyl tetracarboxylic dianhydride.
Example 8
A method for preparing polyamide acid resin, comprising the following steps:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 1.21g of p-phenylenediamine and 8.96g of 4,4' -diaminodiphenyl ether were added to 107.58g of N, N-dimethylacetamide and stirred to dissolve completely to form an amine solution;
(3) Adding 4.34g of phenoxy polyphosphazene with molecular weight of 1155 into the amine solution in the step (2), and continuously stirring to completely dissolve the phenoxy polyphosphazene;
(4) Adding 8.1g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (3);
(5) Adding 6.6g of diphenyl tetracarboxylic dianhydride into the amine solution obtained in the step (4) for a small amount for many times at the temperature of 30-45 ℃, fully stirring to ensure that the diphenyl tetracarboxylic dianhydride is completely dissolved, then adding 7.33g of pyromellitic dianhydride for many times, and slowly stirring to ensure that the dianhydride is completely reacted to obtain a solution with certain viscosity;
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of diamine to dianhydride is 1:1.002;
the phenoxy polyphosphazene accounts for 18% of the mass sum of diamine and dianhydride;
the black filler accounts for 1.6% of the mass sum of diamine and dianhydride.
Example 9
A method for producing a polyamic acid resin was different from example 7 in that the molecular weight of phenoxy polyphosphazene was 1848, and the rest was the same as in example 7.
Comparative example 1
The difference from example 1 is that the polyamic acid resin was produced without adding a phenoxy phosphazene organic compound, and the carbon black was 4% of the mass sum of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride.
Comparative example 2
The difference from example 1 is that the amount of pyromellitic dianhydride added in step (5) was 13.42g, i.e., the molar ratio of 4,4' -diaminodiphenyl ether to pyromellitic dianhydride was 1:1.1, and the amounts of the other substances added were the same as in example 1.
Comparative example 3
The difference from example 1 is that the amount of pyromellitic dianhydride added in step (5) was 10.98g, i.e., the molar ratio of 4,4' -diaminodiphenyl ether to pyromellitic dianhydride was 1:0.9, and the amounts of the other substances added were the same as in example 1.
Comparative example 4
The difference from example 1 is that the phenoxy polyphosphazene added in step (3) was 7.02g, i.e., the ratio of phenoxy polyphosphazene to the sum of the masses of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride was 30%, and the amounts of the remaining substances added were the same as in example 1.
Comparative example 5
The difference from example 1 is that the phenoxy polyphosphazene added in step (3) was 0.468g, i.e., the ratio of phenoxy polyphosphazene to the sum of the masses of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride was 2%, and the amounts of the remaining substances added were the same as in example 1.
Comparative example 6
The difference from example 1 was that 12.285g of the pre-dispersed carbon black slurry obtained in step (4) was added to the amine solution obtained in step (3), and the addition amounts of the remaining substances having a mass sum of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride ratio of 2.5% of carbon black were the same as those in example 1.
Comparative example 7
The difference from example 1 is that 1.97g of the pre-dispersed carbon black slurry obtained in the step (4) was added to the amine solution obtained in the step (3), and the addition amounts of the remaining substances having a mass sum of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride ratio of carbon black of 0.4% were the same as those in example 1.
Comparative example 8
The difference from example 1 is that a method for preparing a polyamic acid resin comprises the steps of:
(1) Adding 10g of carbon black into 200g of N, N-dimethylacetamide, and forming stable pre-dispersed carbon black slurry through grinding and dispersing;
(2) 11.2g of 4,4' -diaminodiphenyl ether was added to 90g of N, N-dimethylacetamide and stirred to be completely dissolved, thereby forming an amine solution;
(3) Adding 12.2g of pyromellitic dianhydride into the amine solution obtained in the step (2) for a plurality of times at the temperature of 30-45 ℃ and slowly stirring to ensure that the dianhydride reacts completely to obtain a solution with certain viscosity;
(4) Adding 2.3g of phenoxy polyphosphazene with the molecular weight of 693 into the amine solution in the step (3), and continuously stirring to completely dissolve the phenoxy polyphosphazene;
(5) Adding 7.4g of the pre-dispersed carbon black slurry obtained in the step (1) into the amine solution obtained in the step (4);
(6) Carrying out vacuum defoaming on the solution obtained in the step (5) to obtain a polyamic acid resin solution;
wherein the molar ratio of the 4, 4-diaminodiphenyl ether to the pyromellitic dianhydride is 1:1;
the phenoxy polyphosphazene accounts for 10% of the mass sum of the 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
the carbon black accounts for 1.5 percent of the mass sum of the 4,4' -diaminodiphenyl ether and the pyromellitic dianhydride.
Application examples 1 to 9
The polyamic acid resin solutions obtained in examples 1 to 9 were cast to form a film, and then high-temperature imidized at a temperature in the range of 360 to 450℃to obtain a black polyimide film having a thickness of 25. Mu.m, wherein the polyamic acid resins obtained in examples 1 to 6 were imidized for 10 minutes and the polyamic acid resins obtained in examples 7 to 9 were imidized for 15 minutes.
Comparative application examples 1 to 8
The same procedure as in application example 1 was followed.
Performance detection
The polyimide films obtained in the above application examples and comparative examples were subjected to detection of puncture strength, electrical strength, light transmittance, etc., and the detection results are shown in table 1, wherein the electrical strength detection standard is GB/T13542.2-2009, the puncture strength detection standard is GB/T37841-2019, the light transmittance detection standard is GB/T2410-2008, the tensile strength detection standard is GB/T13542.2-2009, and the elongation at break detection standard is GB/T13542.2-2009.
TABLE 1 polyimide film Performance test results Table
| Project | Tensile Strength/Mpa | Elongation at break/% | Modulus of elasticity/Mpa | Electrical intensity KV/mm | Puncture strength N/mm | Transmittance/% |
| Application example 1 | 124.7 | 13.8 | 3156.7 | 128.4 | 420.8 | 0.18 |
| Application example 2 | 126.2 | 15.0 | 3177.4 | 110.2 | 471.3 | 0.20 |
| Application example 3 | 147.4 | 11.9 | 3737.5 | 138.3 | 482.2 | 0.22 |
| Application example 4 | 147.7 | 11.6 | 4349.3 | 140.2 | 500.4 | 0.18 |
| Application example 5 | 150.7 | 12.0 | 3006.7 | 171.4 | 510.8 | 0.22 |
| Application example 6 | 165.2 | 22.1 | 4587.4 | 160.0 | 521.3 | 0.20 |
| Application example 7 | 157.4 | 30.9 | 3507.5 | 130.3 | 532.2 | 0.22 |
| Application example 8 | 167.7 | 24.6 | 4579.3 | 128.2 | 510.2 | 0.18 |
| Application example 9 | 132.8 | 20.3 | 3302.5 | 120.5 | 475.8 | 0.17 |
| Comparative application example 1 | 110.0 | 11.2 | 2960.2 | 65.3 | 338.0 | 0.12 |
| Comparative application example 2 | 103.3 | 10.8 | 2970.4 | 112.5 | 365.4 | 0.20 |
| Comparative application example 3 | 108.9 | 9.7 | 2974.6 | 113.4 | 380.6 | 0.19 |
| Comparative application example 4 | 95.6 | 9.4 | 2974.5 | 107.6 | 360.3 | 0.16 |
| Comparative application example 5 | 100.3 | 12.0 | 2966.8 | 82.3 | 360.5 | 0.26 |
| Comparative application example 6 | 80.3 | 8.2 | 2980.6 | 58.2 | 304.6 | 0.10 |
| Comparative application example 7 | 116.3 | 12.4 | 2970.6 | 112.6 | 386.6 | 0.32 |
| Comparative application example 8 | 112.4 | 9.0 | 3002.4 | 115.3 | 382.6 | 0.30 |
As can be seen from table 1:
the lower the light transmittance, the better the covering property of the polyimide film, and the tensile strength, the elongation at break, the elastic modulus, the electrical strength and the puncture strength of the polyimide films obtained from application examples 1 to 9 are better than those obtained from comparative application example 1, which shows that the addition of the phenoxy phosphazene organic compound can not only reduce the addition amount of carbon black, but also improve the tensile strength, the elongation at break, the elastic modulus, the electrical strength and the puncture strength of the polyimide film. The lower the light transmittance, the better the covering property of the polyimide film, and the better the covering property is, although the light transmittance is relatively higher compared with the comparative application example 1, the covering property is good, and meanwhile, the other mechanical properties of the polyimide film are also effectively improved.
Comparative examples 2 to 7 when the molar ratio of the aromatic diamine to the aromatic dianhydride, the content of the phenoxyphosphazene organic matter and the content of the black filler are not within the range defined by the present application, the tensile strength, the elongation at break, the elastic modulus, the electrical strength, the puncture strength of the polyimide film obtained in comparative examples 2 to 7 are inferior to those of the polyimide film obtained in example 1, and it is further illustrated that the contents of the respective substances in the present application are within the range defined by the present application, and the respective properties of the polyimide film can be effectively improved.
Compared with the application example 1, the application example 8 is unfavorable for the dispersion of phenoxy polyphosphazene, especially carbon black slurry, when dianhydride and diamine are reacted, so that the mechanical property of the polyimide film is reduced, the light transmittance is increased, and the covering property is also reduced.
The embodiments of the present application are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (7)
1. A preparation method of polyamide acid resin is characterized by comprising the following preparation steps:
adding black filler into a solvent to disperse to obtain pre-dispersed black slurry;
preparation of polyamide acid resin: (1) Adding aromatic diamine into a solvent, and stirring to completely dissolve the aromatic diamine to form an amine solution;
(2) Adding the phenoxy phosphazene organic matter into the amine solution in the step (1), and stirring to completely dissolve the phenoxy phosphazene organic matter;
(3) Adding the pre-dispersed black paste into the amine solution obtained in the step (2), and continuously stirring;
(4) Adding aromatic dianhydride into the amine solution obtained in the step (3) in batches at the temperature of 30-45 ℃ to enable the dianhydride to react completely;
(5) Carrying out vacuum defoaming on the solution obtained in the step (4) to obtain polyamide acid resin;
the molar ratio of the aromatic diamine to the aromatic dianhydride is 1 (0.992-1.005), the content of the phenoxy phosphazene organic matter is 3-25wt% of the total amount of the aromatic diamine and the aromatic dianhydride, and the content of the black filler is 0.5-2wt% of the total amount of the aromatic diamine and the aromatic dianhydride;
wherein the black filler comprises carbon black;
the phenoxy phosphazene organic matter is phenoxy polyphosphazene or phenoxy cyclophosphazene; the molecular weight of the phenoxy polyphosphazene is 693-1617, and the molecular weight of the phenoxy cyclophosphazene is 693.
2. The method for producing a polyamic acid resin according to claim 1, wherein: the content of the phenoxy phosphazene organic matter is 10-25wt% of the total amount of aromatic diamine and aromatic dianhydride.
3. The method for producing a polyamic acid resin according to claim 1, wherein: the solvent adopts any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
4. The method for producing a polyamic acid resin according to claim 1, wherein: the black filler also comprises carbon nanotubes, and the weight ratio of the carbon black to the carbon nanotubes is 10: (1-1.5).
5. The process for producing a polyamic acid resin according to claim 4, wherein: the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
6. A preparation method of a black polyimide film is characterized in that: casting the polyamic acid resin solution obtained in any one of claims 1 to 5 to obtain a polyamic acid film, and then imidizing at a high temperature in the range of 360 to 450 ℃ for 2 to 15min to obtain a black polyimide film.
7. A black polyimide film obtained by the process for producing a black polyimide film according to claim 6.
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| JP2018012791A (en) * | 2016-07-21 | 2018-01-25 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board |
| CN109575285A (en) * | 2018-12-11 | 2019-04-05 | 中国地质大学（北京） | A kind of PI matrix resin and its flame retardant type transparent polyimide film of preparation |
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