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CN115505261A - Polymer film and method for producing same - Google Patents

Polymer film and method for producing same Download PDF

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Publication number
CN115505261A
CN115505261A CN202110632862.6A CN202110632862A CN115505261A CN 115505261 A CN115505261 A CN 115505261A CN 202110632862 A CN202110632862 A CN 202110632862A CN 115505261 A CN115505261 A CN 115505261A
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liquid crystal
crystal polymer
polymer
film
glue
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CN115505261B (en
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何宜学
蔡孟颖
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Taimide Tech Inc
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Taimide Tech Inc
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    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C08J2479/00—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 C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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Abstract

The polymer film comprises a liquid crystal polymer, a liquid crystal polymer film and a liquid crystal film, wherein the liquid crystal polymer comprises a soluble liquid crystal polymer and an insoluble liquid crystal polymer; and a polyimide polymer, which accounts for more than 5wt% of the weight of the high molecular film. The method for manufacturing polymer film comprises providing a liquid crystal polymer fine powder with a particle size of 0.1-20 um; a liquid crystal polymer glue, the solid content of which is more than 3wt%; polyamide acid glue; mixing a liquid crystal polymer micro powder, liquid crystal polymer glue and polyamide acid glue to prepare a mixed solution, and preparing the mixed solution into a gel film; and baking the gel film at the temperature of 300 ℃ to form a polymer film.

Description

Polymer film and method for producing same
Technical Field
The present application relates to a polymer film and a method for manufacturing the same, and more particularly to a polymer film comprising a soluble liquid crystal polymer, an insoluble liquid crystal polymer and a polyimide polymer, which has excellent film processability, temperature resistance and electrical properties, and a low thermal expansion coefficient, and can be applied to high frequency materials.
Background
Although polyimide has better film processability and temperature resistance, it has the disadvantages of poor electrical property and high water absorption, so that it has the problem of poor signal transmission in 5G high frequency applications.
It is known that a film for high frequency applications is made of an insoluble liquid crystal polymer, that is, the liquid crystal polymer is insoluble in a solvent, has good electrical properties and low water absorption rate, but due to its high melting point, when the processing temperature approaches the liquid crystal state temperature (280 to 330 ℃), the mechanical properties of the liquid crystal polymer film are drastically reduced, so that when the film is applied to high frequency applications, the processability of the film by bonding with a copper foil is very difficult, and the liquid crystal polymer film is easily formed by a high temperature bonding process. And the film has high crystallinity and molecular orthotropic property, so the molecular arrangement is easy to be in the same direction with the coating direction in the film preparation process, and finally, the mechanical property difference of the film in the vertical/horizontal direction is too large, and the film is easy to crack in the non-coating direction, thereby having considerable difficulty in manufacturing.
Taiwan patent No. I356834 discloses a method for preparing a soluble liquid crystal polymer, which comprises dissolving a soluble liquid crystal polymer in an organic solution, and coating the solution to form a soluble liquid crystal polymer film, wherein the liquid crystal polymer film prepared by the method has anisotropic and well-balanced mechanical properties in vertical and horizontal directions. However, the liquid crystal polymer film manufactured by the method has poor temperature resistance, high thermal expansion coefficient (the thermal expansion coefficient of 50-150 ℃ is more than 30 ppm/DEG C), and the size of the film can be changed dramatically under the condition that the softening point Tg is about 180 ℃, and the thermal expansion coefficient of 50-200 ℃ in the use temperature range of a general flexible circuit board is more than 100 ppm/DEG C, so the use is limited.
Taiwan patent No. I650358 discloses a method for manufacturing a soluble liquid crystal polymer film, in which a liquid crystal polymer filler is added to a soluble liquid crystal polymer to effectively reduce the thermal expansion coefficient of the soluble liquid crystal polymer film to 12-25 ppm, but the storage elastic modulus of the soluble liquid crystal polymer film at high temperature cannot be improved, so that the film is easily deformed and warped during the subsequent copper foil bonding process.
Taiwan patent I383021 discloses a soluble liquid crystal polymer film, which is prepared by adding polyimide to a soluble liquid crystal polymer, and the prepared soluble liquid crystal polymer film can also effectively reduce the thermal expansion coefficient of the film and improve the mechanical properties at high temperature. However, the addition of polyimide increases the water absorption and dielectric loss tangent, which is not suitable for the application of 5G high frequency flexible printed circuit board.
Disclosure of Invention
The application provides a high molecular film, which contains a liquid crystal polymer and a polyimide polymer, wherein the liquid crystal polymer comprises a soluble liquid crystal polymer and an insoluble liquid crystal polymer, and the polyimide polymer accounts for more than 5wt% of the high molecular film.
The application provides a method for manufacturing a polymer film, which comprises the following steps: a liquid crystal polymer micro powder, wherein the particle size of the liquid crystal polymer micro powder is 0.1 um-20 um; a liquid crystal polymer glue, the solid content of which is more than 3wt%; polyamide acid glue; mixing a liquid crystal polymer micro powder, a liquid crystal polymer glue and a polyamide acid glue to prepare a mixed solution, preparing the mixed solution into a gel film, and baking the gel film at high temperature to form the high polymer film.
Drawings
FIG. 1 is a flow chart of a method for producing a polymer film according to the present invention.
[ notation ] to show
Providing a liquid crystal polymer micro powder S1
Providing a liquid crystal polymer glue S2
Providing a polyamic acid glue S3
Forming a mixed solution S4
Formation of gel film S5
Forming a polymer film S6
Detailed Description
The polymer film comprises a liquid crystal polymer and a polyimide polymer, wherein the liquid crystal polymer comprises a soluble liquid crystal polymer and an insoluble liquid crystal polymer.
The soluble liquid crystal polymer is soluble in organic solvent, wherein the organic solvent can be dimethyl acetamide (DMAc), N-methyl pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), gamma-butyrolactone (GBL) and N, N-dimethyl formamide (DMF), the solubility of the soluble liquid crystal polymer reaches more than 3wt%, preferably more than 5wt%, 8wt% is used in the application, and the higher solid content is better for the operability of coating and film making.
The soluble liquid crystal polymer accounts for 30-80 wt% of the high molecular film;
wherein the insoluble liquid crystal polymer accounts for 10wt% -60 wt% of the polymer film.
Wherein the polyimide polymer accounts for more than 5wt% of the weight of the high molecular film and is obtained by using a composition containing a dianhydride component and a diamine component, wherein the dianhydride or diamine structure contains an ester functional group.
Referring to fig. 1, the method for manufacturing a polymer film of the present application includes providing a liquid crystal polymer micro powder (S1) with a preferred particle size range of 0.1-20 um, and more preferably 0.1-10 um.
Providing a liquid crystal polymer glue (S2) having a solids content of more than 3wt%.
A polyamic acid glue (S3) is provided, which is obtained by polymerizing dianhydride and diamine, wherein the dianhydride or the diamine must contain ester functional group. The dianhydride or diamine structure containing the ester functional group can increase the compatibility of the polyimide with liquid crystal polymers.
The ester functional group-containing dianhydride or diamine monomer is preferably present in a molar ratio of 20% or more based on the polyimide, more preferably in a molar ratio of 50% or more based on the polyimide, and in the present application the ester functional group-containing dianhydride or diamine is present in a molar ratio of 100% based on the polyimide.
In this application, the dianhydride or diamine must contain an ester functional group, in the case of the dianhydride, such as: p-phenylene-ditrimellitate dianhydride (TAHQ), cyclohexane-1,4-diylbis (methyl) bis (1, 3-dioxo-1, 3-dihydro-benzofuron-5-carboxylate) (TA-CHDM), ethylene glycol bis (trimetallic anhydride) (TMEG), and (4-phthalic anhydride) formyloxy-4-phthalate (8 CI), p-phenylene-ditrimellitate dianhydride (TAHQ) was used as the ester-functional group-containing dianhydride in the examples of the present application.
The ester group-containing diamine may be p-aminobenzoate (APAB), p-aminobenzoate (BPTPA), [4- (4-aminobenzoyl) oxyphenyl ] 4-Aminobenzoate (ABHQ), etc., and p-aminobenzoate (APAB) is used as the ester group-functional diamine in the examples of the present application.
In addition to the dianhydride or diamine component containing ester functional group, other kinds of monomers can be selected to match with the ester group-containing monomer to adjust the required characteristics, wherein the ester group-free dianhydride component can be selected from 1,2,4, 5-pyromellitic anhydride (PMDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), 4-hexafluoroisopropylphthalic anhydride (6 FDA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride (BPADA), 2, 3',4' -biphenyl tetracarboxylic dianhydride (. Alpha. -BPDA), and the like.
<xnotran> (PDA), 4,4'- (ODA), 3,4' - (34 ODA), (mPDA), 4,4'- (44 DDS), 3,3' - (33 DDS), 4,4'- -2,2' - -1,1'- (mTB), 2,2' - ( ) (TFMB), 2,2- [4- (4- ) ] -1,1,1,3,3,3- (HFBAPP), 2,2'- ( ) -4,4' - (6 FODA), 2,2'- [4- (4- ) ] (BAPP), 1,3- (3- ) (APB-N), 4,4' - (4- ) (BAPB), 1,3- (4 '- ) (TPER), 1,4- (4- ) (TPEQ), 1,3- (3- ) (APB-N), 4,4' - (44 DABA), 2- (4- ) -5- (5 BPOA), </xnotran> N, N '- (2, 2' -bis (trifluoromethylphenyl) - [1,1'-biphenyl ] -4,4' -diyl) bis (4-aminobenzamide) (AB-TFMB).
Mixing and stirring the polyamic acid glue, the liquid crystal polymer glue and the liquid crystal polymer micro powder uniformly to form a mixed solution (S4), and adjusting the solid content of the mixed solution by using an additional organic solvent so as to adjust the thickness and viscosity of the film. The organic solvent which can be mixed may be dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), gamma-butyrolactone (GBL) and N, N-Dimethylformamide (DMF). Wherein the organic solvent may be used alone or in combination of two or more thereof. In the present application, the preferred solvents are dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP), with N-methylpyrrolidone (NMP) being the more preferred solvent.
The polyamic acid is converted into a gel film through chemical cyclization by adding a dehydrating agent and a catalyst to the mixed solution (S5). Wherein the dehydrating agent can be acetic anhydride or benzoic anhydride, and the acetic anhydride is selected as the dehydrating agent in the application; the catalyst can be pyridine, 3-methylpyridine, 2-methylpyridine, 4-methylpyridine, isoquinoline, quinoline and triethylamine, wherein the preferred choice is pyridine, 3-methylpyridine, 2-methylpyridine and 4-methylpyridine, the preferred choice in the application is 3-methylpyridine, the catalyst and the dehydrating agent can be mixed with a solvent for dilution and then added into the mixed solution, the final mixed solution is subjected to centrifugal defoaming to remove air bubbles in the solution, and the mixed solution after defoaming is coated on a glass substrate by using a scraper with a proper gap. And after the coating is finished, placing the glass substrate coated with the mixed solution in an oven at 60-80 ℃ for baking for 60-120 minutes, taking out the glass substrate, taking the semi-dry film off the glass substrate to obtain a gel film, fixing the gel film on a metal frame, placing the metal frame in the oven at 250 ℃ for baking for 10 minutes, and heating to more than 300 ℃ for baking for 60 minutes to finish the preparation of the polymer film (S6). Wherein, the baking temperature is preferably more than 300 ℃, and more preferably more than 320 ℃.
The polymer film of the present application can also be added with other types of inorganic fillers or organic fillers to enhance the desired effect. For example, organic fluorinated polymer such as Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), etc. is added to reduce the dielectric constant of the polymer film; or, inorganic fillers such as silicon dioxide, aluminum oxide, etc. can be added to further increase the temperature resistance of the polymer film.
The flexible circuit substrate can be used for a flexible circuit substrate and comprises an insulating base material and a covering film, and particularly the insulating base material is better.
Therefore, the present application can be used for a laminate laminated with a metal laminate, which comprises at least a metal layer and the polymer film, and can also comprise an adhesive layer between the metal layer and the polymer film.
The structure of the metal layer is not particularly limited, and a simple substance or an alloy of copper, nickel, aluminum, silver, or the like can be used. Of these, copper is preferred.
The metal layer can be prepared by electroplating or hot pressing.
Examples
< detection method >
The properties of the polymer films obtained in the following examples were measured by the following methods.
Coefficient of thermal expansion (50 ℃ to 200 ℃): measured according to ASTM D696 specifications using a model Q400 TMA instrument from TA Instruments. The thermal expansion coefficient of the polyimide film at 50 ℃ to 200 ℃ was measured, and the temperature rise rate was set to 10 ℃/min. In order to remove the stress caused by the heat treatment, the residual stress is removed by the first measurement, and then the second measurement result is used as the actual value.
Water absorption: the film was baked at 120 ℃ for 30 minutes, then allowed to stand in distilled water for 24 hours, and the weight loss rate at 120 ℃ for 30 minutes was measured using a model Discovery TGA 550 thermogravimetric analyzer from TA Instruments.
Dielectric loss tangent Df (10 GHz): measured using a Keysight Technologies Inc. model No. E5071C ENA Network Analyzer instrument. The measurement method of the present application is: and baking the polymer film in an oven at 120 ℃ for 30 minutes, taking out, standing in an environment with the humidity of 65%, standing for 48 hours, and measuring.
Dielectric constant Dk (10 GHz): measured using a Keysight Technologies Inc. model E5071C ENA Network Analyzer instrument. The measurement method of the present application is: and baking the polymer film in an oven at 120 ℃ for 30 minutes, taking out, standing in an environment with the humidity of 65%, standing for 48 hours, and measuring.
The storage modulus of elasticity at 310 ℃ was measured using a DMA25 instrument manufactured by Metravib:
sample assay range: the width is 15mm, and the length between the clamps is 20mm
Temperature measurement range: 30 ℃ to 400 DEG C
Temperature increase rate: 10 deg.C/min
·Dynamic force：100mN
Frequency: 5Hz
·Static force：1N
[ example 1 ]
Polyimide polymer (B): the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared by dissolving 45.711 g of APAB in 412.5 g of dimethylacetamide, slowly adding 90.871 g of TAHQ after complete dissolution, stirring for 48 hours, and adjusting the viscosity of the solution to 185,000cps with a small amount of TAHQ to obtain the polyamic acid glue with 25wt% of solid content.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, a liquid crystal polymer fine powder with a particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue having a solids content of 8wt% dissolved in NMP was used.
Production of polymer film
Weighing 56.25 g of 8wt% of liquid crystal polymer glue (soluble liquid crystal polymer), adding 7.6 g of 25wt% of polyamic acid glue, stirring uniformly, adding 2.7 g of liquid crystal polymer micro powder (insoluble liquid crystal polymer), stirring uniformly, adding 1.13 g of acetic anhydride and 0.53 g of 3-methylpyridine, carrying out centrifugal defoaming on the solution to remove bubbles in the solution, coating the solution on a glass substrate after defoaming, and using a scraper with a gap of 900 um. And after the coating is finished, placing the glass substrate coated with the mixed solution in an oven at 80 ℃ for baking for 60 minutes, taking out the glass substrate, taking the semi-dry film off the glass substrate to finish the gel film, fixing the gel film on a metal frame, placing the metal frame in the oven at 250 ℃ for baking for 10 minutes, and heating to 340 ℃ for baking for 60 minutes to finish the preparation of the polymer film.
The high molecular film contains insoluble liquid crystal polymer 30wt%, soluble liquid crystal polymer 50wt% and polyimide 20wt%.
[ example 2 ]
Polyimide polymer: the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared in the same manner as in example 1.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, liquid crystal polymer micro powder with particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue with a solids content of 8 wt.% dissolved in NMP was used.
Production of polymer film
Weighing 6.84 g of a polyamic acid solution with a solid content of 25wt%, adding 40.5 g of liquid crystal polymer glue (soluble liquid crystal polymer) with a solid content of 8wt%, stirring uniformly, adding 3.24 g of liquid crystal polymer micro powder (insoluble liquid crystal polymer), continuously stirring until the solution is uniform, adding 1.02 g of acetic anhydride and 0.46 g of 3-methylpyridine, performing centrifugal defoaming on the solution to remove bubbles in the solution, coating the solution on a glass substrate after defoaming is completed, and coating the glass substrate by using a scraper with a gap of 600 um. And after the coating is finished, placing the glass substrate coated with the mixed solution in an oven at 80 ℃ for baking for 60 minutes, taking out the glass substrate, taking the semi-dry film off the glass substrate, fixing the gel film on a metal frame after the gel film is finished, placing the metal frame in the oven at 250 ℃ for baking for 10 minutes, and heating to 340 ℃ for baking for 60 minutes to finish the preparation of the polymer film.
The polymer film contains insoluble liquid crystal polymer 40wt%, solvent soluble liquid crystal polymer 40wt% and polyimide 20wt%.
[ example 3 ] A method for producing a polycarbonate
Polyimide polymer (B): the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared in the same manner as in example 1.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, a liquid crystal polymer fine powder with a particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue having a solids content of 8wt% dissolved in NMP was used.
Production of polymer film
11.4 g of a polyamic acid solution with a solid content of 25wt% is weighed, 2.85 g of dimethylacetamide is added, after uniform stirring, 33.75 g of 8wt% of liquid crystal polymer glue (soluble liquid crystal polymer) is added, after uniform stirring, 3.6 g of liquid crystal polymer micropowder (insoluble liquid crystal polymer) is added, after continuous stirring is carried out until the solution is uniform, 1.70 g of acetic anhydride and 0.77 g of 3-methylpyridine are added, the solution is subjected to centrifugal defoaming to remove bubbles in the solution, after defoaming is completed, the solution is coated on a glass substrate, and a scraper with a gap of 600 micrometers is used. After the coating is finished, the glass substrate coated with the mixed solution is placed in an oven at 80 ℃ for baking for 60 minutes and then taken out, the semi-dry film is taken off from the glass substrate, after the gel film is finished, the gel film is fixed on a metal frame and is placed in the oven at 250 ℃ for baking for 10 minutes, and then the temperature is raised to 340 ℃ for baking for 60 minutes, thus finishing the manufacture of the polymer film.
The polymer film contains insoluble liquid crystal polymer 40wt%, soluble liquid crystal polymer 30wt% and polyimide 30wt%.
[ example 4 ] A method for producing a polycarbonate
Polyimide polymer (B): the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared in the same manner as in example 1.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, a liquid crystal polymer fine powder with a particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue with a solids content of 8 wt.% dissolved in NMP was used.
Production of polymer film
11.82 g of a polyamic acid solution with a solid content of 25wt% is weighed, 2.95 g of dimethylacetamide is added and stirred uniformly, then 46.67 g of 8wt% liquid crystal polymer glue (soluble liquid crystal polymer) is added, 2.8 g of liquid crystal polymer micro powder (insoluble liquid crystal polymer) is added after stirring uniformly, 1.75 g of acetic anhydride and 0.80 g of 3-methylpyridine are added after the solution is continuously stirred uniformly, the solution is subjected to centrifugal defoaming to remove air bubbles in the solution, the solution is coated on a glass substrate after defoaming, and a scraper with a gap of 900um is used. And after the coating is finished, placing the glass substrate coated with the mixed solution in an oven at 80 ℃ for baking for 60 minutes, taking out the glass substrate, taking the semi-dry film off the glass substrate, fixing the gel film on a metal frame after the gel film is finished, placing the metal frame in the oven at 250 ℃ for baking for 10 minutes, and heating to 340 ℃ for baking for 60 minutes to finish the preparation of the polymer film.
The polymer film contains insoluble liquid crystal polymer 30wt%, solvent soluble liquid crystal polymer 40wt% and polyimide 30wt%.
[ example 5 ]
Polyimide polymer: the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared in the same manner as in example 1.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, liquid crystal polymer micro powder with particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue having a solids content of 8wt% dissolved in NMP was used.
Production of polymer film
Weighing 9.5 g of polyamide acid solution with the solid content of 25wt%, adding 2.37 g of dimethylacetamide, uniformly stirring, adding 42.19 g of liquid crystal polymer glue (soluble liquid crystal polymer) with the solid content of 8wt%, uniformly stirring, adding 5.63 g of liquid crystal polymer micropowder (insoluble liquid crystal polymer), continuously stirring until the solution is uniform, adding 1.41 g of acetic anhydride and 0.64 g of 3-methylpyridine, performing centrifugal defoaming on the solution to remove bubbles in the solution, coating the solution on a glass substrate after defoaming is completed, and using a scraper with the gap of 600 um. And after the coating is finished, placing the glass substrate coated with the mixed solution in an oven at 80 ℃ for baking for 60 minutes, taking out the glass substrate, taking the semi-dry film off the glass substrate, fixing the gel film on a metal frame after the gel film is finished, placing the metal frame in the oven at 250 ℃ for baking for 10 minutes, and heating to 340 ℃ for baking for 60 minutes to finish the preparation of the polymer film.
The high molecular film comprises 50wt% of insoluble liquid crystal polymer, 30wt% of soluble liquid crystal polymer and 20wt% of polyimide.
[ example 6 ]
Polyimide polymer: the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared in the same manner as in example 1.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, a liquid crystal polymer fine powder with a particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue with a solids content of 8 wt.% dissolved in NMP was used.
Production of polymer film
Weighing 2.64 g of a polyamic acid solution with a solid content of 25wt%, adding 62.5 g of liquid crystal polymer glue (soluble liquid crystal polymer) with a solid content of 8wt%, stirring uniformly, adding 0.63 g of liquid crystal polymer micropowder (insoluble liquid crystal polymer), continuously stirring until the solution is uniform, adding 0.39 g of acetic anhydride and 0.18 g of 3-methylpyridine, carrying out centrifugal deaeration on the solution to remove bubbles in the solution, coating the solution on a glass substrate after deaeration is finished, and using a scraper with a gap of 1200 um. After the coating is finished, the glass substrate coated with the mixed solution is placed in a 60-DEG C oven to be baked for 30 minutes, then the temperature is raised to 80 ℃ to be baked for 60 minutes, then the glass substrate is taken out, the semi-dry film is taken off from the glass substrate, after the gel film is finished, the gel film is fixed on a metal frame, the glass substrate is placed in a 250-DEG C oven to be baked for 10 minutes, and then the glass substrate is heated to 340 ℃ to be baked for 60 minutes, so that the polymer film is manufactured.
The high molecular film comprises 10wt% of insoluble liquid crystal polymer, 80wt% of soluble liquid crystal polymer and 10wt% of polyimide.
[ example 7 ] A method for producing a polycarbonate
Polyimide polymer: the polyimide is obtained by polymerizing diamine and dianhydride to obtain polyamic acid glue, and the polyamic acid glue is subjected to dead circulation in a high-temperature or chemical cyclization mode to obtain the polyimide. The polyamic acid glue is prepared in the same manner as in example 1.
Insoluble type liquid crystal polymer: an insoluble liquid crystal polymer produced by ENEOS, model Lf-31P, a liquid crystal polymer fine powder with a particle size of 5 um.
Soluble type liquid crystal polymer: a liquid crystalline polymer glue having a solids content of 8wt% dissolved in NMP was used.
Production of polymer film
Weighing 5.28 grams of a polyamic acid solution with a solid content of 25wt%, adding 54.67 grams of liquid crystal polymer glue (soluble liquid crystal polymer) with a solid content of 8wt%, stirring uniformly, adding 0.63 gram of liquid crystal polymer micro powder (insoluble liquid crystal polymer), continuously stirring until the solution is uniform, adding 0.79 gram of acetic anhydride and 0.36 gram of 3-methylpyridine, performing centrifugal defoaming on the solution to remove bubbles in the solution, coating the solution on a glass substrate after defoaming is completed, and using a scraper with a gap of 1200 um. After the coating is finished, the glass substrate coated with the mixed solution is placed in a 60-DEG C oven to be baked for 30 minutes, then the temperature is raised to 80 ℃ to be baked for 60 minutes, then the glass substrate is taken out, the semi-dry film is taken off from the glass substrate, after the gel film is finished, the gel film is fixed on a metal frame, the glass substrate is placed in a 250-DEG C oven to be baked for 10 minutes, and then the glass substrate is heated to 340 ℃ to be baked for 60 minutes, so that the polymer film is manufactured.
The high molecular film contains 10wt% of insoluble liquid crystal polymer, 70wt% of soluble liquid crystal polymer and 20wt% of polyimide.
[ COMPARATIVE EXAMPLE 1 ]
Weighing 70 g of liquid crystal polymer glue (soluble liquid crystal polymer) with the solid content of 8wt%, carrying out centrifugal deaeration on the solution to remove air bubbles in the solution, coating the solution on a glass substrate after deaeration is finished, and coating the glass substrate by using a scraper with a gap of 900 micrometers. After coating, placing the glass substrate coated with the mixed solution in a 60-DEG C oven for baking for 30 minutes, heating to 80 ℃, baking for 60 minutes, taking out, taking the semi-dry film off the glass substrate, fixing the gel film on a metal frame after finishing the gel film, placing the metal frame in a 250-DEG C oven for baking for 10 minutes, heating to 320 ℃, and baking for 60 minutes to finish the manufacture of the polymer film.
[ COMPARATIVE EXAMPLE 2 ]
60 g of liquid crystal polymer glue (soluble liquid crystal polymer) with the solid content of 8wt% is weighed, 2.06 g of liquid crystal polymer micro powder (insoluble liquid crystal polymer) is added, the solution is continuously stirred until the solution is uniform, the solution is subjected to centrifugal defoaming to remove bubbles in the solution, the solution is coated on a glass substrate after defoaming, and a scraper with a gap of 900 micrometers is used for coating. After coating, placing the glass substrate coated with the mixed solution in a 60-DEG C oven for baking for 30 minutes, heating to 80 ℃, baking for 60 minutes, taking out, taking the semi-dry film off the glass substrate, fixing the gel film on a metal frame after finishing the gel film, placing the metal frame in a 250-DEG C oven for baking for 10 minutes, heating to 340-DEG C, and baking for 60 minutes to finish the manufacture of the polymer film.
[ COMPARATIVE EXAMPLE 3 ]
A solvent-insoluble liquid crystal polymer manufactured by Kuraray, inc. under the trademark Vecstar, model CTQ-50 was used.
[ COMPARATIVE EXAMPLE 4 ]
Weighing 40.18 g of liquid crystal polymer glue (soluble liquid crystal polymer) with the solid content of 8wt%, adding 31.66 g of polyamide acid glue with the solid content of 25wt%, stirring until the solution is uniform, performing centrifugal defoaming on the solution to remove bubbles in the solution, coating the solution on a glass substrate after defoaming is completed, and coating the glass substrate by using a scraper with a gap of 900 micrometers. After the coating is finished, the glass substrate coated with the mixed solution is placed in an 80-DEG C oven to be baked for 60 minutes, the semi-dry film is taken down from the glass substrate, the gel film is fixed on a metal frame after the gel film is finished, the glass substrate is placed in a 250-DEG C oven to be baked for 10 minutes, and then the temperature is raised to 340 ℃ to be baked for 60 minutes, so that the polymer film is manufactured.
[ COMPARATIVE EXAMPLE 5 ]
Weighing 38 g of 25wt% polyamide acid glue, adding 9.5 g of dimethyl to uniformly stir with amide, adding 3.86 g of liquid crystal polymer micro powder (insoluble liquid crystal polymer) to stir until the solution is uniform, performing centrifugal defoaming on the solution to remove bubbles in the solution, coating the solution on a glass substrate after defoaming is completed, and coating the glass substrate by using a scraper with a gap of 600 um. After the coating is finished, the glass substrate coated with the mixed solution is placed in an 80-DEG C oven to be baked for 60 minutes, the semi-dry film is taken down from the glass substrate, the gel film is fixed on a metal frame after the gel film is finished, the glass substrate is placed in a 250-DEG C oven to be baked for 10 minutes, and then the temperature is raised to 340 ℃ to be baked for 60 minutes, so that the polymer film is manufactured.
The examples are compared to the comparative examples table as follows:
Figure BDA0003104383270000141
the foregoing description of specific embodiments is provided for the purpose of illustrating the present application, which is by way of illustration only and is not intended to be limiting of the present application. It will be appreciated by those skilled in the art that the present application is directed to this application without departing from the scope of the invention as defined by the appended claims. Variations or modifications may be made which fall within the scope of the present application.

Claims (9)

1. A polymeric film, comprising:
a liquid crystal polymer, which comprises a soluble liquid crystal polymer and an insoluble liquid crystal polymer; and
and the polyimide polymer accounts for more than 5wt% of the weight of the high molecular film.
2. The polymer film according to claim 1, wherein the soluble liquid crystal polymer is a liquid crystal polymer soluble in an organic solvent and having a solubility of 3wt% or more.
3. The polymer thin film according to claim 2, wherein the organic solvent is selected from the group consisting of dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), gamma-butyrolactone (GBL) and N, N-Dimethylformamide (DMF).
4. The polymer film according to claim 1, wherein the soluble liquid crystal polymer is 30wt% to 80wt% of the polymer film.
5. The polymer film according to claim 1, wherein the insoluble liquid crystal polymer is 10wt% to 60wt% of the polymer film.
6. The polymer film according to claim 1, wherein the polyimide polymer is obtained by using a composition comprising a dianhydride component and a diamine component, and the dianhydride or diamine structure contains an ester functional group.
7. A method for producing a polymer film, comprising:
providing liquid crystal polymer micro powder with the particle size of 0.1-20 um;
providing liquid crystal polymer glue, wherein the solid content of the liquid crystal polymer glue is more than 3wt%;
providing polyamide acid glue;
mixing the liquid crystal polymer micro powder, the liquid crystal polymer glue and the polyamide acid glue to prepare a mixed solution, and preparing the mixed solution into a gel film; and baking the gel film at a temperature of more than 300 ℃ to form the polymer film.
8. The method of claim 7, wherein the polyamic acid glue is obtained by using a composition comprising a dianhydride component and a diamine component.
9. The method for producing a polymer film according to claim 7, wherein the mixed solution is formed into a gel film by a chemical cyclization method.
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