WO2022228449A1 - Procédé de préparation de résine de polyimide et film mince de celle-ci - Google Patents

Procédé de préparation de résine de polyimide et film mince de celle-ci Download PDF

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WO2022228449A1
WO2022228449A1 PCT/CN2022/089436 CN2022089436W WO2022228449A1 WO 2022228449 A1 WO2022228449 A1 WO 2022228449A1 CN 2022089436 W CN2022089436 W CN 2022089436W WO 2022228449 A1 WO2022228449 A1 WO 2022228449A1
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bis
dianhydride
batch
polyimide resin
viscosity
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PCT/CN2022/089436
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English (en)
Chinese (zh)
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程跃
吴超
吕凯
刘倩倩
庄志
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上海瑞暨新材料科技有限公司
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Publication of WO2022228449A1 publication Critical patent/WO2022228449A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present disclosure relates to the field of polyimide films, in particular to a preparation method of polyimide resin and a film thereof.
  • polyamic acid is synthesized by low-temperature polycondensation by first diamine and then dianhydride in an equimolar amount in a suitable organic solvent, and then by casting a film on the substrate, and finally thermal imidization to form a film.
  • this preparation method makes the polymer It is difficult to control the apparent viscosity of amic acid within an ideal range of higher viscosity, the length of polymer molecular segments is not balanced, the resin viscosity is difficult to stabilize, and the amount of resin bubbles is large, and the experimental process found that when the dianhydride and diamine are close When the molar ratio is equal, the viscosity will show a similar exponential jump.
  • the present disclosure provides a preparation method of polyimide with stable performance and viscosity under long-term storage, which specifically includes the following steps:
  • the low temperature environment in step S1 is -20-30°C.
  • the added amount of the second batch of polyvalent diamines in step S2 is 5-10% of the total molar amount of the first batch of polyvalent diamines
  • the specific operation of batch addition is: adding in a temperature gradient of 30-35 °C 40% of the total molar amount of the second batch of polyvalent diamines, adding 25% of the total molar amount of the second batch of polyvalent diamines in a temperature gradient of 45-50 °C, adding the second batch of polyvalent diamines in a temperature gradient of 65-70 °C Add 20% of the total amount of polydiamine in the 75-80 °C temperature gradient, add 10% of the total molar amount of the second batch of polydiamine, continue to stir and monitor the viscosity of the resin solution, if the resin viscosity is stable at 180000-200000cps, then stop feeding, otherwise, then Continue adding the remaining second batch of polydiamine until the resin viscosity stabilizes at 50,000-70,000 cps.
  • the total molar amount of the fluorine-containing capping agent plus the molar amount of the first batch of polybasic diamine and the second batch of polyvalent diamine is approximately equal to the molar amount of polybasic dianhydride.
  • the polydiamines include p-phenylenediamine and its ring fluorinated compounds, benzidine and its ring fluorinated compounds, 4,4'-oxydiphenylamine, 1,3-bis( 4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(2-aminophenoxy)benzene, 4,4'-bis(3-aminobenzene) oxy) biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(5-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy) base)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(2-aminophenoxy)phenyl)sulfone, 4,4'-diaminodiphenyl Ethane, 4,4'-
  • the polybasic dianhydride includes pyromellitic dianhydride, 2,3,6,7-tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 3,4,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane Dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarbox
  • the fluorine-containing capping agent includes a fluorine-containing monoamine aromatic organic compound.
  • the fluorine-containing capping agent includes m-bis(trifluoromethyl)aniline, 4-(4'-fluorophenyl)benzonitrile, p-trifluoromethylaniline, 2,6-difluoromethylaniline Fluoro-3-methylaniline, cyanoacetyl-p-trifluoromethylaniline, 4-methyl-2-(trifluoromethyl)aniline, 3-fluoro-2-(trifluoromethyl)aniline, 5-fluoro -2-trifluoromethylaniline, 4-fluoro-2-nitro-5-(trifluoromethyl)-aniline, 2,2'-bis(trifluoromethyl)diaminobiphenyl, trifluoroaniline, N-ethyl-2,3,5-trifluoroaniline, 2,2'-bis(3,4,5-trifluorophenyl)-4,4'-benzidinediamine, 2,3,4- Any of trifluorophenylacetamide and 2,3,4-trifluorophen
  • the solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, cyclohexane, methylcyclohexane, tetrahydrofuran, isohexane , n-heptane, dichloromethane, trichloroethylene, carbon tetrachloride, epichlorohydrin, methyl methacrylate, dimethyl sulfoxide.
  • the present disclosure also provides the polyimide resin prepared by the above-mentioned preparation method.
  • the present disclosure also provides the use of the polyimide resin in a film.
  • the present disclosure also provides a film, the preparation method comprising: selecting the above-mentioned polyimide resin, sequentially adding a catalyst and a dehydrating agent to the polyimide resin, and coating the film on at least one side of the base film.
  • the catalyst includes pyridazine, pyrimidine, pyridine, phthalazine, 1,10-phenanthroline.
  • the mass ratio of the catalyst to the polyimide resin solution is 1:95-105.
  • the base film includes carbon nanofiber copper foil, carbon nanofiber silver foil, carbon nanofiber aluminum foil, and carbon nanofiber gold foil.
  • the present disclosure provides a preparation method of a polyimide resin, comprising the following steps:
  • the first batch of polybasic diamine and polybasic dianhydride are firstly polymerized into a low-viscosity resin solution at a low temperature, and then gradually heated at 30-80°C.
  • the present disclosure emphasizes the second The batch of polyvalent diamines is added to the resin solution gradually by the differential method in different temperature gradients, so that the polymer segments are continuously reformed, homogenized and then lengthened. When the lengths of all segments are kept balanced, the chain
  • the polyimide resin solution prepared by this preparation method is homogeneous and stable, as shown in Table 1. Compared with the polyimide resin solution prepared by the current technology, it can last for a long time.
  • the polyimide resin solution can be stored for a long time; at the same time, the fluorine-containing end-capping agent can effectively reduce the hydrolysis of the end chain of the polyimide resin solution, and further improve the viscosity stability of the polyimide resin solution.
  • the structure of the film is more stable, the tensile strength of the film will be enhanced accordingly, and the fluorine-containing compound also has the effect of reducing the dielectric constant. leakage, heat generation and capacitance effects between wires.
  • the monitoring method of the above-mentioned monitoring resin is not limited to any method that can grasp the viscosity of the polyimide resin at any time.
  • the total molar amount of the first batch of polyvalent diamines and the second batch of polyvalent diamines in the present disclosure is similar to the total molar amount of polyvalent dianhydrides.
  • the ratio of the total molar amount of the first batch of polyvalent diamine and the second batch of polyvalent diamine to the total molar amount of polyvalent dianhydride is 0.9-1.0:1.0 , for example, 0.92-1.0:1.0, 0.92-0.98:1.0, or 0.94-0.96:1.0.
  • the low temperature environment in the step S1 of the present disclosure is -20-30°C.
  • the reaction is a reaction that increases the exothermic entropy, so the low temperature helps the molecular chain segment
  • the polymerization reaction promotes the reaction to proceed in the forward direction, so that the molecular segments continue to grow and the viscosity increases. Therefore, in some typical embodiments, the low temperature environment can be -20-10°C, -10-0°C, 0- 10°C, 10-30°C.
  • the second batch of polyvalent diamines is added in batches in the S2 step in batches.
  • the second batch of polyvalent diamines is added in an amount of 5-10% of the molar total amount of the first batch of polyvalent diamines, such as 6-9 %, 6-8% or 7-8%, added in batches
  • the specific operation is: 30-35 °C (such as 31-35 °C, 31-34 °C or 32-33 °C) temperature gradient adding the second batch of polydiamine 40% of the total molar amount, 25% of the total molar amount of the second batch of polydiamines was added within a temperature gradient of 45-50°C (such as 46-50°C, 46-48°C or 46-47°C), 65-70°C ( Add 20% of the total molar amount of the second batch of polydiamine within a temperature gradient such as 66-69°C, 66-68°C or 66-67°C, 75-80°C (such as 76-79°C,
  • the total molar amount of the fluorine-containing end-capping agent plus the first batch of polyvalent diamine and the second batch of polyvalent diamine can be further limited to be approximately equal to the molar amount of polyvalent dianhydride.
  • thermo expansion coefficient of the prepared polyimide resin solution after film formation can be equal to that of the base film, so as to avoid the phenomenon of curling at the edge of the film due to a large difference in the expansion coefficient.
  • n ⁇ 2 as shown in Table 1, under the same polybasic diamine and polybasic dianhydride, by changing the ratio between polybasic diamines and the ratio between polybasic dianhydrides Mixing ratios can obtain polyimide films with different thermal expansion coefficients.
  • the present disclosure has no special restrictions on the diamine, which can be any well-known diamine in the art, specifically, p-phenylenediamine and its ring fluorinated compound, benzidine and its ring fluorinated compound, 4, 4'-Oxydiphenylamine, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(2-aminophenoxy) ) benzene, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(5-aminophenoxy) ) biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(2-aminophenoxy) phenyl) sulfone
  • dianhydride in the present disclosure, can be any dianhydride known in the art, and specific examples include pyromellitic dianhydride, 2,3,6,7-tetracarboxylic dianhydride, 3,3' ,4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2 -Bis(3,4-dicarboxyphenyl)propane dianhydride, 3,4,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)propane dianhydride, 1,1-bis (2,3-Dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, bis(2,3-dicarboxy
  • the fluorine-containing end-capping agent of the present disclosure is a fluorine-containing monoamine aromatic organic compound, which reacts with the end-chain anhydride structure of the polyimide resin solution to perform end-chain end-capping, so that the end-chain structure of the polyimide resin solution is
  • the amino structure of the fluorine-containing end-capping agent so as to avoid the hydrolysis of the polyimide resin solution, the fluorine-containing end-capping agent can be listed as m-bis(trifluoromethyl)aniline, 4-(4'-fluorophenyl)benzyl Nitrile, p-trifluoromethylaniline, 2,6-difluoro-3-methylaniline, cyanoacetyl p-trifluoromethylaniline, 4-methyl-2-(trifluoromethyl)aniline, 3-fluoro -2-(trifluoromethyl)aniline, 5-fluoro-2-trifluoromethylaniline, 4-fluoro-2-nitro-5-(trifluor
  • solvents which can be listed as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, cyclohexane, methylcyclohexane, tetrahydrofuran , isohexane, n-heptane, dichloromethane, trichloroethylene, carbon tetrachloride, epichlorohydrin, methyl methacrylate, dimethyl sulfoxide.
  • solvents which can be listed as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, cyclohexane, methylcyclohexane, tetrahydrofuran , isohexane, n-heptane, dichloromethane, trichloroethylene, carbon tetrachloride, epichlorohydrin, methyl methacrylate, dimethyl sulfoxide.
  • a catalyst and a dehydrating agent are sequentially added to the solution to rapidly dehydrate and imidize the polyimide acid to form a film, so as to improve the production efficiency.
  • the tensile strength of the film is increased.
  • the present disclosure also expands the catalyst types that are not currently used in the art.
  • the catalyst can be a monocyclic or condensed ring compound, such as pyridazine, pyrimidine, pyridine, phthalazine
  • 1,10-phenanthroline as shown in Table 1, when the catalyst emphasized in this disclosure is selected, a polyimide film with more excellent tensile strength can be obtained.
  • a combination of pyridazine and pyridine can be selected. The catalytic performance is the best, and the mass ratio of the two catalysts is 1:4.
  • the optimal ratio of the controllable catalyst and the polyimide resin solution is to control the mass ratio of the two within the range of 1:95-105.
  • the above-mentioned base films are not particularly limited, and can be base films commonly used in the field, such as carbon nanofiber copper foil, carbon nanofiber silver foil, carbon nanofiber aluminum foil, carbon nanofiber gold foil, but due to the excellent heat dissipation performance of carbon nanofiber copper foil , high strength, extremely stable chemical properties, low price and other characteristics can solve the problem of heat dissipation and oxidation of circuit boards, and save costs, so in some typical embodiments, the base film can be carbon nanofiber copper foil.
  • the preparation method provided by the present disclosure can make the polyimide stable in performance and viscosity under long-term storage.
  • the preparation method of the present disclosure solves the problems of viscosity control and viscosity stability.
  • the polyimide resin obtained by the preparation method is uniform and stable, and can be stored in a natural environment at normal temperature and pressure for a long time without changing the viscosity and performance;
  • the end agent solves the problem that the acid anhydride of the end chain is easy to be hydrolyzed.
  • the end chain is capped by adding a suitable molar ratio of monoamine aromatic organic compounds.
  • the end chain structure is an amino structure, which completely avoids the problem of the end group being hydrolyzed.
  • the problem of high dielectric constant of imine resins is because fluorine-containing compounds have the effect of reducing the dielectric constant. Therefore, by adding an appropriate amount of fluorine-containing amine organic compounds, the dielectric constant can be effectively reduced, thereby reducing the leakage, heat generation of integrated circuits and between wires. capacitive effect.
  • the formed polyimide coating has strong thermal stability, and the thermal expansion coefficient is close to that of the base film.
  • the film edge is prone to curling.
  • the prepared mixed solution adopts the principle of adding more first and then less multiple times, adding 40% at 30°C-35°C, adding 25% at 45°C-50°C, adding 20% at 65°C-70°C, and adding at 75°C-80°C 10%, the remaining part is added at a temperature of 80 °C and stirred for 1 hour, depending on the viscosity.
  • the stirring rate is 15rad/min.
  • the water bath was heated to 80°C, and 0.00438mol p-phenylenediamine and 0.00438mol 4,4'-diphenyletherdiamine were weighed and dissolved in 4g N,N-dimethylformamide under nitrogen atmosphere.
  • the difference method is used to add more first and then less. Add 40% at 30°C-35°C, 25% at 45°C-50°C, 20% at 65°C-70°C, and 10% at 75°C-80°C. %, the remaining part is added at a temperature of 80 °C and stirred for 1 hour depending on the viscosity.
  • the stirring rate is 15rad/min.
  • Fluoromethyl)aniline fully reacted for 60min, cooled to room temperature, weighed 107.57g N,N-dimethylformamide to gradually dilute the resin viscosity to 50000cP, took 100g of the diluted resin, added 0.2g pyridazine and 0.8g g pyridine, stir at a constant speed for 5 min, and then rapidly defoam in high vacuum.
  • Coat the glass substrate and carbon nanofiber copper foil by casting method (the thickness of the film is controlled at about 20 ⁇ m).
  • the acetic anhydride and solvent were removed in a vacuum oven. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the water bath was heated to 80°C, and 0.00500mol p-phenylenediamine and 0.00333mol 4,4'-diphenyletherdiamine were weighed and dissolved in 4g N,N-dimethylformamide under nitrogen atmosphere.
  • the difference method is used to add more first and then less. Add 40% at 30°C-35°C, 25% at 45°C-50°C, 20% at 65°C-70°C, and 10% at 75°C-80°C. %, the remaining part is added at a temperature of 80 °C and stirred for 1 hour depending on the viscosity.
  • the stirring rate is 15rad/min.
  • Fluoromethyl)aniline fully reacted for 60min, cooled to room temperature, weighed 166.37g N,N-dimethylformamide to gradually dilute the resin viscosity to 50000cP, took 100g of the diluted resin, added 0.2g pyridazine and 0.8g Pyridine, stirred at a constant speed for 5 minutes, then rapidly degassed in high vacuum, and coated on glass substrate and carbon nanofiber copper foil by casting method (film thickness was controlled at about 20 ⁇ m), and after chemical imidization, oxygen-free vacuum at 250 °C was used. The oven removes acetic anhydride and solvent. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the water bath was heated to 80°C, and 0.00334mol p-phenylenediamine and 0.00500mol 4,4'-diphenyletherdiamine were weighed and dissolved in 4g N,N-dimethylformamide under nitrogen atmosphere.
  • the difference method is used to add more first and then less. Add 40% at 30°C-35°C, 25% at 45°C-50°C, 20% at 65°C-70°C, and 10% at 75°C-80°C. %, the remaining part is added at a temperature of 80 °C and stirred for 1 hour depending on the viscosity.
  • the stirring rate is 15 rad/min.
  • Fluoromethyl)aniline fully reacted for 60min, cooled to room temperature, weighed 106.95g N,N-dimethylformamide to gradually dilute the resin viscosity to 50000cP, took 100g of the diluted resin, added 0.2g pyridazine and 0.8g Pyridine, stirred at a constant speed for 5 minutes, then rapidly degassed in high vacuum, and coated on glass substrate and carbon nanofiber copper foil by casting method (film thickness was controlled at about 20 ⁇ m), and after chemical imidization, oxygen-free vacuum at 250 °C was used. The oven removes acetic anhydride and solvent. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is checked after one month.
  • the water bath was heated to 80°C, and 0.00375mol p-phenylenediamine and 0.00250mol 4,4'-diphenyletherdiamine were weighed and dissolved in 4g N,N-dimethylformamide under nitrogen atmosphere.
  • the difference method is used to add more first and then less. Add 40% at 30°C-35°C, 25% at 45°C-50°C, 20% at 65°C-70°C, and 10% at 75°C-80°C. %, the remaining part is added at a temperature of 80 °C and stirred for 1 hour, depending on the viscosity.
  • the stirring rate is 15rad/min.
  • Fluoromethyl)aniline fully reacted for 60min, cooled to room temperature, weighed 127.25g N,N-dimethylformamide to gradually dilute the resin viscosity to 50000cP, took 100g of the diluted resin, added 0.2g pyridazine and 0.8g Pyridine, stirred at a constant speed for 5 minutes, then rapidly degassed in high vacuum, and coated on glass substrate and carbon nanofiber copper foil by casting method (film thickness was controlled at about 20 ⁇ m), and after chemical imidization, oxygen-free vacuum at 250 °C was used. The oven removes acetic anhydride and solvent. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the film is coated on the glass substrate (the thickness of the film is controlled at about 20 ⁇ m), and the film is formed by imidization in an oxygen-free vacuum oven at 500 °C. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the film is coated on the glass substrate (the thickness of the film is controlled at about 20 ⁇ m), and the film is formed by imidization in an oxygen-free vacuum oven at 500 °C. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the film is coated on the glass substrate (the thickness of the film is controlled at about 20 ⁇ m), and the film is formed by imidization in an oxygen-free vacuum oven at 500 °C. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the film is coated on the glass substrate (the thickness of the film is controlled at about 20 ⁇ m), and the film is formed by imidization in an oxygen-free vacuum oven at 500 °C. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the film is coated on the glass substrate (the thickness of the film is controlled at about 20 ⁇ m), and the film is formed by imidization in an oxygen-free vacuum oven at 500 °C. Test the film tensile strength, thermal expansion coefficient, water absorption, dielectric constant, edge curl. The remaining resin is sealed and stored under normal temperature and pressure, and the viscosity is tested after one month.
  • the films prepared in Comparative Examples 1-5 have low tensile strength, large difference in thermal expansion coefficient and copper foil, high water absorption, high dielectric constant, and obvious curling phenomenon of the film, which cannot meet the requirements of industrial production.
  • the tensile strength was greater than 120MPa
  • the thermal expansion coefficient was close to that of copper foil (18 ⁇ 10-6k-1)
  • the water absorption rate was low, all less than 2%
  • the dielectric constant is less than 3
  • the film does not produce curling phenomenon, indicating that the performance is good
  • the graphene copper foil is used as the base film
  • the tensile strength of the prepared film is greatly increased by more than 320MPa
  • the thermal expansion coefficient is close to that of copper foil ( 18 ⁇ 10-6k-1)
  • the water absorption rate is low, less than 2%
  • the dielectric constant is less than 3
  • the outer side of the film has a very small curling phenomenon, indicating that the performance is good and
  • the present disclosure provides a method for preparing polyimide resin and a film thereof.
  • the polyimide prepared in the present disclosure has the characteristics of long-term storage performance and stable viscosity, and the polyimide resin prepared in the present disclosure is coated on
  • the formed polyimide coating has strong thermal stability, and the thermal expansion coefficient is close to the base film, which solves the problem that the edge of the film is easily curled due to the large difference in the thermal expansion coefficient. Therefore, the polyimide prepared by the present disclosure and the film prepared therefrom have excellent industrial practical properties and good market prospects.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne le domaine du polyimide, et en particulier un procédé de préparation d'une résine de polyimide et un film mince de celle-ci. Le procédé comprend les étapes suivantes : S1, après dissolution d'un premier lot de polydiamine dans un solvant sous une atmosphère de gaz inerte, ajout de polydianhydride dans un environnement à basse température de 30 °C ou moins pour polymérisation préliminaire afin de former une solution de résine, le polydianhydride étant de 105 à 110 % de la quantité molaire totale du premier lot de polydiamine et la viscosité de la solution de résine étant régulée de façon à être de 50 000 à 70 000 cps ; S2, surveillance de la viscosité de la solution de résine et augmentation progressive de la température de la solution de résine dans 30 à 80 °C, et ajout progressif d'un deuxième lot de polyamine par lots dans l'ordre de quantités décroissantes jusqu'à ce que la viscosité de la solution de résine soit de 180 000 à 200 000 cps ; et S3, ajout d'un agent de coiffage contenant du fluor, conduite d'un mélange uniforme, et conduite d'un démoussage sous vide poussé pour obtenir une solution de résine de polyimide. Lorsque la résine de polyimide préparée dans la présente invention est couchée sur un film de base pour préparer un film mince, un revêtement de polyimide formé présente une stabilité thermique élevée et un coefficient de dilatation thermique proche de celui du film de base, et le problème selon lequel le bord du film mince généré dans le cas d'une différence relativement élevée des coefficients de dilatation thermique est sujet à un roulage et un retrait est résolu.
PCT/CN2022/089436 2021-04-29 2022-04-27 Procédé de préparation de résine de polyimide et film mince de celle-ci WO2022228449A1 (fr)

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