CN110818928B - Matte polyimide black film with low thermal shrinkage and preparation method thereof - Google Patents
Matte polyimide black film with low thermal shrinkage and preparation method thereof Download PDFInfo
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- 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
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a preparation method of a matte polyimide black film with low thermal shrinkage, which comprises the following steps: s1, preparing a polyamic acid resin solution: adding a flatting agent into an aromatic diamine solution in an inert gas atmosphere, uniformly mixing, adding aromatic dianhydride, and stirring to react to obtain a polyamic acid resin solution, wherein the aromatic diamine contains rigid aromatic diamine, and the rigid aromatic diamine is at least one of p-phenylenediamine, 2, 5-diaminotoluene, 1, 5-naphthalene diamine, 2, 5-naphthalene diamine and 2, 6-naphthalene diamine; s2, preparing black slurry; s3, preparing the matte polyimide black film with low thermal shrinkage. The invention also discloses the low-thermal-shrinkage matte polyimide black film, which is prepared by the preparation method of the low-thermal-shrinkage matte polyimide black film. The invention has low shrinkage, matte effect, good dimensional stability, low visible light transmittance and low surface gloss while maintaining mechanical property and electrical property.
Description
Technical Field
The invention relates to the technical field of polyimide films, in particular to a low-thermal-shrinkage matte polyimide black film and a preparation method thereof.
Background
Polyimide films are widely used in the fields of electricians, electronics, aerospace and the like due to excellent mechanical, thermal and electrical properties. The electronic grade polyimide cover film is mainly used for protecting a flexible printed circuit board, and has higher requirement on the dimensional stability of the cover film due to the requirements of various processing processes such as downstream gluing compounding, etching and the like.
The black PI film is opaque, so that the black PI film can cover electronic materials such as flexible circuits, electronic elements, lead frames of integrated circuit packages and the like, can prevent visual inspection, tampering and plagiarism, and has high market demand. The traditional bright polyimide black film surface has glare or astigmatism generated by light reflection, which causes visual discomfort and easily causes eye fatigue when being watched for a long time, so in recent years, a matte polyimide black film with better shielding effect and more excellent appearance gradually becomes the focus of the covering film market, and the black film with the glossiness range of 25-60GU is generally called as the matte polyimide black film.
At present, the thermal shrinkage rate range of the black film for the conventional covering film in the market is less than or equal to 0.15 percent, and the black film cannot be well applied to customers with higher requirements. In the traditional preparation process of the black polyimide black film, the preparation method of the carbon black slurry is mainly prepared by matching a solvent with a coupling agent for ultrasonic dispersion or high-speed dispersion, and the slurry has poor storage stability and low solid content.
In addition, aiming at matte black films, the adding method of the flatting agent mainly comprises the steps of mixing the flatting agent with a solvent through high-speed dispersion, and then dispersing the mixture with the synthesized resin in the form of dispersion liquid.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the matte polyimide black film with low thermal shrinkage and the preparation method thereof.
The invention provides a preparation method of a matte polyimide black film with low thermal shrinkage, which comprises the following steps:
s1, preparing a polyamic acid resin solution: adding a flatting agent into an aromatic diamine solution in an inert gas atmosphere, uniformly mixing, adding aromatic dianhydride, and stirring for reaction to obtain a polyamic acid resin solution, wherein the aromatic diamine contains rigid aromatic diamine, and the rigid aromatic diamine is at least one of p-phenylenediamine, 2, 5-diaminotoluene, 1, 5-naphthalene diamine, 2, 5-naphthalene diamine and 2, 6-naphthalene diamine;
s2, preparing black slurry: diluting the polyamic acid resin solution obtained in the step S1 to obtain a solution A, adding a dispersing agent to mix uniformly under the stirring state, adding a black pigment to mix uniformly, and grinding until the particle size of the black pigment is less than or equal to 2 microns to obtain black slurry;
s3, preparing the matte polyimide black film with low thermal shrinkage: stirring and uniformly mixing the polyamic acid resin solution obtained in the step S1 and the black slurry obtained in the step S2, defoaming, coating on the surface of a substrate, drying, and stripping to obtain a polyamic acid casting gel film; and longitudinally stretching the polyamic acid casting gel film, transversely stretching, imidizing and shaping to obtain the matte polyimide black film with low heat shrinkage.
Preferably, in S1, the aromatic diamine includes: 3,3-4, 4-diaminodiphenyl ether and rigid aromatic diamines.
Preferably, in S1, the molar amount of the rigid aromatic diamine is 23.3 to 38.1% of the total molar amount of the aromatic diamine.
Preferably, in S1, the aromatic dianhydride is at least one of pyromellitic dianhydride, 3 '-4, 4' -biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, and 1,2,5, 6-naphthalenetetracarboxylic dianhydride.
Preferably, in S1, the matting agent comprises 4 to 12 wt% of the sum of the masses of the aromatic diamine and the aromatic dianhydride.
Preferably, in S1, the matting agent is micron-sized silica or micron-sized alumina.
Preferably, in S1, the particle size of the matting agent is 4 to 6 μm.
Preferably, in S1, the matting agent is modified with a silane coupling agent.
Preferably, in S1, the reaction temperature is 40-50 ℃ and the reaction time is 4-6 h.
Preferably, in S1, the polyamic acid resin solution has a solid content of 15 to 18 wt%.
Preferably, in S1, the solvent of the aromatic diamine solution is an aprotic solvent.
Preferably, the aprotic solvent is at least one of N, N ' -dimethylacetamide, N ' -dimethylformamide, dimethylsulfoxide, and N, N ' -dialkylcarboxyamide.
Preferably, in S1, the molar ratio of aromatic dianhydride to aromatic diamine is 0.98-1: 1.
preferably, in S1, the aromatic dianhydride is added in portions.
Preferably, in S2, solution A has a solids content of 5 to 8% by weight.
Preferably, in S2, the dispersant is a polyurethane-based polymeric dispersant, the solvating chain of which is a polyether or polyester segment, and the anchoring group is a benzene ring or benzene ring-like structure.
Preferably, in S2, the black pigment is carbon black.
Preferably, the carbon black is a nanoscale carbon black.
Preferably, the primary particle size of the carbon black is 40 to 50 nm.
In the above-mentioned S2, "grinding to a black pigment particle size of 2 μm or less gives a black slurry", the particle size here is different from the primary particle size, which is a larger particle obtained by aggregating the primary black pigment particles.
Preferably, in S2, the weight ratio of the solution A, the black pigment and the dispersant is 152.3-499.2: 2.7-5.2: 1-1.56.
Preferably, in S2, the grinding media are zirconia beads having a particle size of 1 to 2 mm.
Preferably, in S2, the grinding temperature is 30-40 ℃ and the grinding time is 4-6 h.
Preferably, in S3, the weight ratio of the polyamic acid resin solution to the black paste is 9.77-11.48: 1-1.12.
Preferably, in S3, the stirring speed is 2000-3000rpm, and the stirring time is 2-4 h.
Preferably, in S3, the coating thickness is 160-180 μm.
Preferably, in S3, the drying temperature is 125-180 ℃.
Preferably, in S3, drying is performed in a drying tunnel.
Preferably, the drying tunnel is divided into 6 zones, wherein there are three zones from the entrance of the drying tunnel to the middle of the drying tunnel, the temperature of each zone is gradually increased, and there are three zones from the middle of the drying tunnel to the exit of the drying tunnel, the temperature of each zone is gradually decreased.
Preferably, in S3, the polyamic acid cast gel film has a solid content of 70 to 78 wt%.
Preferably, in S3, the polyamic acid casting gel film has a thickness of 30 to 45 μm.
Preferably, in S3, the stretching ratio of the longitudinal stretching is 1.03 to 1.05.
Preferably, in S3, the longitudinal stretching includes three steps of preheating, stretching and setting, wherein the preheating temperature is 78-85 ℃, the stretching temperature is 86-90 ℃, and the setting temperature is 70-80 ℃.
Preferably, in S3, the transverse stretching comprises three steps of preheating, stretching and transition, wherein the preheating temperature is 110-140 ℃, the stretching temperature is 155-185 ℃, and the transition temperature is 250-260 ℃.
Preferably, in S3, the stretching ratio in the transverse direction is 1.05 to 1.07.
Preferably, in S3, the imidization temperature is 400-440 ℃ and the time is 2.5-3.5 min.
Preferably, in S3, the setting temperature is 200-280 ℃.
The invention also provides a low-thermal-shrinkage matte polyimide black film prepared by the preparation method of the low-thermal-shrinkage matte polyimide black film.
According to the invention, the shrinkage rate of the black film is further reduced by introducing a rigid diamine monomer into a molecular chain of the polyamide acid resin and adjusting the longitudinal and transverse stretching ratios and the setting temperature in the film making process; selecting a proper dispersant, and performing dispersion grinding by using a resin solution with certain viscosity, so that the particle size of the black pigment is controlled within a certain range, and the stability of the black slurry is improved by the viscosity of the resin solution and the entropy repulsion of the dispersant; adding the measured modified delustering agent into the aromatic diamine solution, and continuously stirring and dispersing in the whole synthesis process to avoid the conditions of dispersion unevenness and particle size agglomeration; according to the invention, through a proper formula and process, the black pigment and the flatting agent are added into the polyamic acid solution, so that the prepared film is black and has a certain matte effect; the preparation method is simple in process, and the polyimide black film prepared by casting and biaxial stretching has good dimensional stability, low visible light transmittance and low surface gloss on the premise of maintaining certain mechanical properties and electrical properties, and has an excellent confidentiality keeping function on flexible circuit design.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a matte polyimide black film with low thermal shrinkage comprises the following steps:
s1, preparing a polyamic acid resin solution: in nitrogen atmosphere, adding 2.47kg of 3,3-4, 4-diaminodiphenyl ether and 0.82kg of p-phenylenediamine into 40kg of N, N' -dimethylacetamide and dissolving to obtain an aromatic diamine solution; adding 0.56kg of coupling agent modified silicon dioxide with the average particle size of 4 mu m into an aromatic diamine solution, uniformly mixing, then adding 3.78kg of pyromellitic dianhydride at constant speed for 10 times, and stirring and reacting at 40 ℃ for 4 hours to obtain a polyamic acid resin solution, wherein the solid content of the polyamic acid resin solution is 15 wt%;
s2, preparing black slurry: diluting 1.44kg of polyamic acid resin solution obtained in S1 with N, N' -dimethylacetamide until the solid content is 5 wt% to obtain solution A, adding 0.09kg of polyurethane dispersant under the high-speed stirring state, uniformly mixing, slowly adding 0.30kg of carbon black with the primary particle size of 40nm, dispersing at the high shear of 2000rpm, uniformly mixing, grinding for 4 hours at 30 ℃ by using zirconia beads with the particle size of 1mm as grinding media through a sand mill until the particle size of the carbon black is less than or equal to 2 mu m to obtain black slurry, wherein the solvation chain of the polyurethane dispersant is a polyether chain segment, and the anchoring group is a benzene ring;
s3, preparing the matte polyimide black film with low thermal shrinkage: 42.36kg of polyamic acid resin solution obtained in S1 and 4.71kg of black slurry obtained in S2 are mixed and stirred for 2 hours at 2000rpm, are defoamed, are coated on the surface of an annular steel strip through a casting die head, the coating thickness is controlled to be 180 mu m, then part of solvent is removed through drying in a drying tunnel, the temperatures of the drying tunnel from an inlet to an outlet are respectively set to be 128 ℃, 151 ℃, 179 ℃, 170 ℃, 158 ℃ and 149 ℃, and a self-supporting polyamic acid gel film with the solid content of 70 wt% and the thickness of 42-45 mu m is obtained through stripping;
conveying the polyamic acid casting gel film to a longitudinal stretcher, preheating at 78 ℃, longitudinally stretching at 86 ℃, and shaping at 70 ℃, wherein the longitudinal stretching ratio is 1.03; preheating at 110 ℃ by a chain clamp type transverse stretcher, transversely stretching at 155 ℃, enabling the transverse stretching ratio to be 1.07, transiting at 250 ℃, carrying out imidization at 400 ℃ and keeping the temperature for 3min, shaping at 220 ℃ to obtain a matte polyimide black film with the thickness of 25 mu m and low shrinkage rate, and finally rolling.
Example 2
A preparation method of a matte polyimide black film with low thermal shrinkage comprises the following steps:
s1, preparing a polyamic acid resin solution: adding 3.64kg of 3,3-4, 4-diaminodiphenyl ether and 0.85kg of 2, 5-diaminotoluene into 45kg of N, N' -dimethylacetamide in a nitrogen atmosphere to dissolve to obtain an aromatic diamine solution; adding 0.4kg of coupling agent modified aluminum oxide with the average particle size of 4 mu m into the aromatic diamine solution, uniformly mixing, then adding 4.68kg of pyromellitic dianhydride at constant speed for 12 times, and stirring and reacting at 45 ℃ for 6 hours to obtain a polyamic acid resin solution, wherein the solid content of the polyamic acid resin solution is 16.9 wt%;
s2, preparing black slurry: diluting 1.28kg of polyamic acid resin solution obtained in S1 with N, N' -dimethylacetamide until the solid content is 6 wt% to obtain solution A, adding 0.14kg of polyurethane dispersant under the high-speed stirring state, uniformly mixing, slowly adding 0.45kg of carbon black with the primary particle size of 50nm, dispersing at the rotation speed of 2500rpm, uniformly mixing, grinding for 5 hours at 35 ℃ by using zirconia beads with the particle size of 1.5mm as grinding media through a sand mill until the particle size of the carbon black is less than or equal to 2 mu m to obtain black slurry, wherein the solvation chain of the polyurethane dispersant is a polyether chain segment, and the anchoring group is a benzene ring;
s3, preparing the matte polyimide black film with low thermal shrinkage: 49.86kg of polyamic acid resin solution obtained in S1 and 4.34kg of black slurry obtained in S2 are mixed and stirred for 3 hours at 2500rpm, mixed uniformly, defoamed, coated on the surface of an annular steel strip through a casting die head, the coating thickness is controlled to be 160 mu m, and then part of solvent is removed through drying of a drying tunnel, the temperatures of the drying tunnel from an inlet to an outlet are respectively set to be 130 ℃, 155 ℃, 180 ℃, 174 ℃, 162 ℃ and 153 ℃, and the drying tunnel is stripped to obtain a polyamic acid casting gel film with self-supporting property, wherein the solid content is 78wt%, and the thickness is 30-33 mu m;
conveying the polyamic acid casting gel film to a longitudinal stretcher, preheating at 80 ℃, longitudinally stretching at 90 ℃, and shaping at 75 ℃, wherein the longitudinal stretching ratio is 1.04; preheating at 130 ℃ by a chain clip type transverse stretcher, transversely stretching at 165 ℃ with the transverse stretching ratio of 1.06, transiting at 255 ℃, imidizing at 410 ℃ and keeping the temperature for 2.5min, shaping at 250 ℃ to obtain the matte polyimide black film with the thickness of 25 mu m and low heat shrinkage rate, and finally rolling.
Example 3
A preparation method of a matte polyimide black film with low thermal shrinkage comprises the following steps:
s1, preparing a polyamic acid resin solution: in a nitrogen atmosphere, 3.77kg of 3,3-4, 4-diaminodiphenyl ether and 0.62kg of p-phenylenediamine were added to a mixed solvent of 34kg of N, N '-dimethylacetamide and 6kg of N, N' -dimethylformamide to dissolve the mixture to obtain an aromatic diamine solution; adding 0.53kg of coupling agent modified silicon dioxide with the average particle size of 6 mu m into an aromatic diamine solution, uniformly mixing, then adding 0.62kg of 3,3 '-4, 4' -biphenyltetracarboxylic dianhydride and 3.85kg of pyromellitic dianhydride (sequentially adding 3,3 '-4, 4' -biphenyltetracarboxylic dianhydride at constant speed) for 12 times, and stirring and reacting at 50 ℃ for 5 hours to obtain a polyamic acid resin solution, wherein the solid content of the polyamic acid resin solution is 18 wt%;
s2, preparing black slurry: diluting 2.01kg of polyamic acid resin solution obtained in S1 with N, N' -dimethylformamide until the solid content is 8wt% to obtain solution A, adding 0.1kg of polyurethane dispersant under the high-speed stirring state, uniformly mixing, slowly adding 0.27kg of carbon black with the primary particle size of 40nm, dispersing at a high shear of 3000rpm, uniformly mixing, grinding for 6 hours at 40 ℃ by using zirconia beads with the particle size of 2mm as grinding media through a sand mill until the particle size of the carbon black is less than or equal to 2 mu m to obtain black slurry, wherein the solvation chain of the polyurethane dispersant is a polyether chain segment, and the anchoring group is a benzene ring;
s3, preparing the low-thermal shrinkage matte polyimide black film: 43.89kg of polyamic acid resin solution obtained in S1 and 4.87kg of black slurry obtained in S2 are mixed and stirred at 2700rpm for 3.5h, are mixed and stirred uniformly, are defoamed, are coated on the surface of an annular steel strip through a casting die head, the coating thickness is controlled to be 180 mu m, then part of solvent is removed through drying of a drying tunnel, the temperatures of the drying tunnel from an inlet to an outlet are respectively set to be 125 ℃, 150 ℃, 178 ℃, 167 ℃, 160 ℃ and 149 ℃, and the drying tunnel is stripped to obtain a polyamic acid casting gel film with self-supporting property, wherein the solid content is 76 wt%, and the thickness is 33-38 mu m;
conveying the polyamic acid casting gel film to a longitudinal stretcher, preheating at 85 ℃, longitudinally stretching at 90 ℃, and shaping at 80 ℃, wherein the longitudinal stretching ratio is 1.05; preheating at 140 ℃ by a chain clamp type transverse stretcher, transversely stretching at 185 ℃, wherein the transverse stretching ratio is 1.07, transition is carried out at 260 ℃, imidization and heat preservation are carried out at 430 ℃ for 3.5min, shaping is carried out at 280 ℃ to obtain the matte polyimide black film with the thickness of 25 mu m and low heat shrinkage rate, and finally rolling is carried out.
The matte polyimide black films with low heat shrinkage ratios prepared in examples 1-3 were subjected to various property measurements, and a common polyimide black film was used as a comparative example, and the results are shown in the following table:
as shown in the table, the matte polyimide black films with low heat shrinkage ratios prepared in examples 1 to 3 have good mechanical properties and electrical properties, and the heat shrinkage ratio is remarkably reduced compared with that of a common black film while the glossiness and the light transmittance are kept low.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. A preparation method of a matte polyimide black film with low thermal shrinkage is characterized by comprising the following steps:
s1, preparing a polyamic acid resin solution: adding a flatting agent into an aromatic diamine solution in an inert gas atmosphere, uniformly mixing, adding aromatic dianhydride, and stirring to react to obtain a polyamic acid resin solution, wherein the aromatic diamine contains rigid aromatic diamine, and the rigid aromatic diamine is at least one of p-phenylenediamine, 2, 5-diaminotoluene, 1, 5-naphthalene diamine, 2, 5-naphthalene diamine and 2, 6-naphthalene diamine;
s2, preparing black slurry: diluting the polyamic acid resin solution obtained in the step S1 to obtain a solution A, adding a dispersing agent to mix uniformly under the stirring state, adding a black pigment to mix uniformly, and grinding until the particle size of the black pigment is less than or equal to 2 microns to obtain black slurry; the solid content of the solution A is 5-8 wt%; in S2, the dispersant is polyurethane polymer dispersant, the solvating chain is polyether or polyester chain segment, and the anchoring group is benzene ring or benzene ring-like structure; in S2, the black pigment is carbon black; the carbon black is nano-scale carbon black; the primary particle size of the carbon black is 40-50 nm; in S2, the weight ratio of the solution A, the black pigment and the dispersant is 152.3-499.2: 2.7-5.2: 1 to 1.56; in S2, the grinding media are zirconia beads having a particle size of 1-2 mm; in S2, grinding at 30-40 deg.C for 4-6 h;
s3, preparing the matte polyimide black film with low thermal shrinkage: stirring and uniformly mixing the polyamic acid resin solution obtained in the step S1 and the black slurry obtained in the step S2, defoaming, coating on the surface of a substrate, drying, and stripping to obtain a polyamic acid casting gel film; and longitudinally stretching the polyamic acid casting gel film, transversely stretching, imidizing and shaping to obtain the low-heat-shrinkage matte polyimide black film.
2. The method for preparing the matte polyimide black film with low thermal shrinkage rate according to claim 1, wherein in S1, the aromatic diamine comprises: 3,3-4, 4-diaminodiphenyl ether and a rigid aromatic diamine; in S1, the molar amount of the rigid aromatic diamine accounts for 23.3-38.1% of the total molar amount of the aromatic diamine; in S1, the aromatic dianhydride is at least one of pyromellitic dianhydride, 3 '-4, 4' -biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, and 1,2,5, 6-naphthalenetetracarboxylic dianhydride.
3. The method for preparing the matte polyimide black film with low thermal shrinkage rate according to claim 1 or 2, wherein in S1, the flatting agent accounts for 4-12% wt of the total mass of the aromatic diamine and the aromatic dianhydride; in S1, the matting agent is micron-sized silica or micron-sized alumina; in S1, the particle size of the matting agent is 4 to 6 μm; in S1, the matting agent is modified with a silane coupling agent.
4. The preparation method of the matte polyimide black film with low thermal shrinkage rate according to claim 1, wherein in S1, the reaction temperature is 40-50 ℃, and the reaction time is 4-6 h; in S1, the polyamic acid resin solution has a solid content of 15 to 18 wt%; in S1, the solvent of the aromatic diamine solution is an aprotic solvent; the aprotic solvent is at least one of N, N ' -dimethylacetamide, N ' -dimethylformamide, dimethyl sulfoxide and N, N ' -dialkylcarboxyamide; in S1, the molar ratio of aromatic dianhydride to aromatic diamine is 0.98-1: 1; in S1, the aromatic dianhydride was added in portions.
5. The method for preparing the matte polyimide black film with low thermal shrinkage rate according to claim 1, wherein in S3, the weight ratio of the polyamic acid resin solution to the black slurry is 9.77-11.48: 1 to 1.12; in S3, the stirring speed is 2000-3000rpm, and the stirring time is 2-4 h; in S3, the coating thickness was 160-180 μm.
6. The preparation method of the matte polyimide black film with low thermal shrinkage rate as claimed in claim 1, wherein in S3, the drying temperature is 125-180 ℃; drying in a drying tunnel in S3; the drying tunnel is divided into 6 areas, wherein three areas are arranged from the entrance of the drying tunnel to the middle of the drying tunnel, the temperature of each area is gradually increased, and three areas are arranged from the middle of the drying tunnel to the exit of the drying tunnel, and the temperature of each area is gradually decreased.
7. The method for preparing the matte polyimide black film with low thermal shrinkage rate according to claim 1, wherein in S3, the solid content of the polyamic acid casting gel film is 70-78 wt%; in S3, the polyamic acid cast gel film has a thickness of 30 to 45 μm; a draw ratio of the longitudinal drawing in S3 of 1.03 to 1.05; in S3, the longitudinal stretching comprises three steps of preheating, stretching and shaping, wherein the preheating temperature is 78-85 ℃, the stretching temperature is 86-90 ℃, and the shaping temperature is 70-80 ℃.
8. The method for preparing the matte polyimide black film with low thermal shrinkage rate as claimed in claim 1, wherein in S3, the transverse stretching comprises three steps of preheating, stretching and transition, wherein the preheating temperature is 110-; a draw ratio of 1.05 to 1.07 in the transverse direction in S3; in S3, the imidization temperature is 400-440 ℃, and the time is 2.5-3.5 min; in S3, the setting temperature was 200 ℃ and 280 ℃.
9. A matte polyimide black film with low thermal shrinkage is characterized by being prepared according to the preparation method of the matte polyimide black film with low thermal shrinkage of any one of claims 1-8.
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| CN111793360A (en) * | 2020-07-09 | 2020-10-20 | 安徽国风塑业股份有限公司 | Black polyimide film with high electrical strength and high shielding property and preparation process thereof |
| CN112759763B (en) * | 2021-01-20 | 2022-05-17 | 株洲时代新材料科技股份有限公司 | Polyimide composite glue solution, black matte polyimide material, preparation and application |
| CN116253880B (en) * | 2023-05-15 | 2023-08-29 | 天津市嘉诺缘电子科技有限公司 | Polyamic acid resin and preparation method thereof, black polyimide film and preparation method thereof |
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