CN108892792B - Black polyimide film and preparation method thereof - Google Patents
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Abstract
The black polyimide film and the preparation method thereof are provided, and the method comprises the following steps: (1) reacting aromatic tetracarboxylic dianhydride and an aromatic diamine compound in a predetermined molar ratio in a first solvent under an inert atmosphere and at a certain temperature to obtain a PAA solution; (2) adding the non-carbon black pigment into the second solvent, uniformly stirring, and dispersing to obtain non-carbon black pigment slurry; (3) mixing the third solvent and the fumed silica powder and dispersing to prepare fumed silica slurry; (4) fully stirring and mixing the PAA solution, the non-carbon black pigment slurry and the fumed silica slurry to obtain a PAA composite solution; and mixing the PAA composite solution, a catalyst and an anhydride dehydrating agent to obtain a mixture solution, and carrying out tape casting, coating, drying, stretching and the like to obtain the black polyimide film. The black polyimide film has good physical and chemical properties, and both surfaces of the film have uniformly colored black appearance, so the film has good light-shielding effect and wide product application.
Description
Technical Field
The invention relates to polyimide film materials, in particular to a black polyimide film and a preparation method thereof.
Background
The flexible printed circuit board FPC is widely applied to products such as computers, communication, consumer electronics products, optical lens modules, Liquid Crystal Display (LCD) modules, solar cells and the like, and Polyimide (PI) films are often used as base materials or covering film materials of the PI films. The black PI film has good light shading property, antistatic property, thermal conductivity and other properties, meets the requirements, and is widely applied to the fields of optics, electronics, aerospace and the like.
In the preparation of a black PI film with low gloss, low light transmittance and insulation, a color additive and a matting agent need to be added in the PI film process, and usually the transmittance of the PI film is reduced by the color additive, or the matting agent is added to form a concave-convex microstructure on the surface of the PI film to reduce the gloss of the PI film. In the process of manufacturing the black PI film, the physical properties of the PI film are adversely affected by the particle size of the inorganic particles or the carbon powder material being too large or too small. If the particle size of the inorganic particles or the carbon powder material is larger, the surface of the prepared film is too rough, and the film is not suitable for electronic products; if the particle size of the inorganic particles or carbon powder material is small, aggregation is easily caused, which causes a problem of non-uniform dispersion in the film and is not easy to control in operation. Besides the particle size of the inorganic particles or the carbon powder material can influence the dispersibility of the inorganic particles or the carbon powder material in the PI film, the content of the inorganic particles or the carbon powder material can also influence, and if the content of the inorganic particles or the carbon powder material is larger, the phenomenon of uneven dispersion can also occur; however, if the content is small, the gloss and transmittance of the film are too high, and the haze effect and the light transmittance are poor.
Disclosure of Invention
The invention aims to provide a black polyimide film and a preparation method thereof, and the prepared black PI film has good physical and chemical properties, and simultaneously has uniformly colored black appearance on two sides, good light-shielding effect, simple synthesis process, high yield and wide product application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a black polyimide film comprises the following steps:
(1) preparation of polyamic acid (PAA) solution: reacting aromatic tetracarboxylic dianhydride and an aromatic diamine compound in a predetermined molar ratio in a first solvent under an inert atmosphere and at a certain temperature to obtain a PAA solution;
(2) preparation of non-carbon black pigment slurry: adding the non-carbon black pigment into the second solvent, uniformly stirring, and dispersing to obtain non-carbon black pigment slurry;
(3) preparing gas-phase white carbon black slurry: mixing the third solvent and the fumed silica powder and dispersing to prepare fumed silica slurry;
(4) chemical imidization: fully stirring and mixing the PAA solution, the non-carbon black pigment slurry and the fumed silica slurry to obtain a PAA composite solution; mixing the PAA composite solution, a catalyst and an anhydride dehydrating agent to obtain a mixture solution, coating the mixture solution by tape casting, stretching a gel film formed after drying at room temperature, heating under the action of tension to remove the solvent, defoaming, continuously heating and drying the film in an oxygen-free heat imine furnace protected by inert gas in drying areas at different temperatures, and obtaining the black polyimide film by tape casting-biaxial stretching.
Preferably, the aromatic diamine compound in the step (1) is at least one of 2,2 '-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), p-phenylenediamine and 4, 4' -diaminodiphenyl ether.
Preferably, the aromatic tetracarboxylic dianhydride in step (1) is one or a combination of 3,3 ', 4, 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and pyromellitic dianhydride.
Preferably, the molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine compound in the step (1) is 1-1.01: 1; the content of PAA in the prepared PAA solution is 18-28 wt%; the reaction temperature is 0-50 ℃, and the reaction time is 2-6 hours.
Preferably, the non-carbon black pigment in the step (2) is at least one of cobalt oxide, black iron oxide, ferrochrome oxide and aniline black, and the particle size is 0.1-10 μm; in the black polyimide film, the content of the non-carbon black pigment is 10-30 wt%.
Preferably, the dispersion in the step (2) is ultrasonic dispersion, the dispersion time is 10-30 minutes, and the dispersion temperature is 0-50 ℃; the dispersion in the step (3) is shear dispersion, the rotation speed of the shear dispersion is 2500r/min, the processing time is 1-3h, and the dispersion temperature is 0-50 ℃.
Preferably, the fumed silica powder in the step (3) has a median particle diameter of 3.2-3.5 μm and a density of 3-5g/cm3(ii) a In the black polyimide film, the content of fumed silica powder is 1.5 wt% -10 wt%.
Preferably, the first solvent in step (1), the second solvent in step (2), and the third solvent in step (3) are each independently at least one of N, N-dimethylformamide, N-Dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, sulfolane, tetramethylurea, dimethylsulfone.
Preferably, the catalyst in the step (4) is at least one of pyridine, alpha-picoline, beta-picoline, 3, 4-lutidine, 3, 5-lutidine, 4-picoline, 4-isopropylpyridine, N-dimethylbenzylamine, isoquinoline, 4-benzylpyridine, N-dimethyldodecylamine and triethylamine; the catalyst is used in an amount of 0.1 to 0.5 mole relative to 1 mole of the amount of PAA in the PAA solution prepared in the step (1).
Preferably, the anhydride dehydrating agent in the step (4) is at least one of benzoic anhydride, acetic anhydride, propionic anhydride and butyric anhydride; the amount of the acid anhydride dehydrating agent to be used is 0.2 to 0.6 mole relative to 1 mole of the amount of PAA in the PAA solution prepared in the step (1).
The catalyst in the step (4) is prepared by mixing at least two of pyridine, alpha-picoline, beta-picoline, 3, 4-lutidine, 3, 5-lutidine, 4-picoline, 4-isopropylpyridine, N-dimethylbenzylamine, isoquinoline, 4-benzylpyridine, N-dimethyldodecylamine and triethylamine; the anhydride dehydrating agent in the step (4) is formed by mixing at least one of acetic anhydride, propionic anhydride and butyric anhydride with benzoic anhydride.
Preferably, the temperature for continuously heating and drying the membrane in the drying zones with different temperatures in the step (4) is 80-300 ℃, the temperature for continuously heating and drying the membrane is divided into 4 drying zones with different temperatures, the temperature of the first zone is (80 ℃ and 120 ℃), the temperature of the second zone is (120 ℃ and 185 ℃), the temperature of the third zone is (185 ℃ and 260 ℃), and the temperature of the fourth zone is (260 ℃ and 300℃)]Each drying area can be controlled to be +/-2, and the cleanness of the hot temperature and the amount of hot air on the upper side of the drying tunnel can be ensured to be not less than 10m3The amount of hot air at the lower side cannot be less than 20 m/min3Per minute, each zone is of the same length and the total drying time is 25-60 minutes.
The black polyimide film consists of polyimide, non-carbon black pigment in 10-30 wt% and fumed silica in 1.5-10 wt%, except polyimide.
Compared with the prior art, the invention has the following advantages:
according to the invention, the black polyimide film prepared by adding the non-carbon black pigment and the fumed silica (the flatting agent) into the polyimide resin through a chemical imidization method has high surface black uniformity, consistent glossiness of two surfaces, low glossiness, optical density value larger than 2.5 and good shading effect; the preparation process of research and development is simple to operate and high in yield. The black film prepared by chemical imidization has higher dielectric strength and better physical and chemical properties than the black film prepared by the thermal imidization method. Even if the black polyimide film prepared by chemical imidization is cast on a smooth surface, both surfaces of the black polyimide film are matt (matte effect), which is beneficial to applying any additional layer to any side of the black polyimide film, and the practical range is expanded. When the polyimide precursor film prepared by the hot imine method is thermally converted and cast on a smooth surface, only the air surface has good matte effect. The film prepared by the chemical imine has higher insulating strength than the film prepared by the thermal imidization method, and the dielectric strength is more than 144 kv/mm. In general, dielectric strength decreases with increasing dose of the extinction agent. Therefore, although the gloss of 60 degrees can be reduced by the thermal imidization treatment, the dielectric strength is lowered by increasing the amount of the matting agent.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
A preparation method of a black polyimide film comprises the following steps:
(1) preparation of polyamic acid (PAA) solution: reacting aromatic tetracarboxylic dianhydride and an aromatic diamine compound in a predetermined molar ratio in a first solvent under an inert atmosphere and at a certain temperature to obtain a PAA solution;
(2) preparation of non-carbon black pigment slurry: adding the non-carbon black pigment into the second solvent, uniformly stirring, and dispersing to obtain non-carbon black pigment slurry;
(3) preparing gas-phase white carbon black slurry: mixing the third solvent and the fumed silica powder and dispersing to prepare fumed silica slurry;
(4) chemical imidization: fully stirring and mixing the PAA solution, the non-carbon black pigment slurry and the fumed silica slurry to obtain a PAA composite solution; mixing the PAA composite solution, a catalyst and an anhydride dehydrating agent to obtain a mixture solution, coating the mixture solution by tape casting, stretching a gel film formed after drying at room temperature, heating under the action of tension to remove the solvent, defoaming, continuously heating and drying the film in an oxygen-free heat imine furnace protected by inert gas in drying areas at different temperatures, and obtaining the black polyimide film by tape casting-biaxial stretching.
In some preferred embodiments, one or any combination of the following preferences may be selected, without conflict:
the aromatic diamine compound in the step (1) is at least one of 2,2 '-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), p-phenylenediamine and 4, 4' -diaminodiphenyl ether.
The aromatic tetracarboxylic dianhydride in the step (1) is one or a combination of 3,3 ', 4, 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and pyromellitic dianhydride.
The molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine compound in the step (1) is 1-1.01: 1. Further, in the reaction process, the following operations may be employed: firstly, dissolving aromatic tetracarboxylic dianhydride and an aromatic diamine compound in an amount less than that of an aromatic diamine compound in a first solvent for reaction, after reacting for a period of time, additionally adding the aromatic tetracarboxylic dianhydride (the molar ratio of the total added aromatic tetracarboxylic dianhydride to the aromatic diamine compound is 1-1.01:1), simultaneously monitoring the solution viscosity, and stopping adding the aromatic tetracarboxylic dianhydride when the viscosity reaches 2000-3000 poise to obtain a PAA solution. The temperature of the PAA solution may be maintained at 20-30 ℃ for use. For example, 40 to 60 parts by volume of the aromatic diamine and 35 to 55 parts by volume of the aromatic tetracarboxylic dianhydride (and the parts by volume of the aromatic tetracarboxylic dianhydride added at this time is less than the parts by volume of the aromatic diamine) may be reacted in the first solvent, and after a certain period of time, 6 to 8 parts by volume of the aromatic tetracarboxylic dianhydride may be additionally added.
The PAA content of the prepared PAA solution is 18-28 wt%. The reaction temperature of the step (1) is 0-50 ℃, and the reaction time is 2-6 hours.
The non-carbon black pigment in the step (2) is at least one of cobalt oxide, black iron oxide, ferrochrome oxide and aniline black, and the particle size is 0.1-10 mu m. In the black polyimide film, the content of the non-carbon black pigment is 10-30 wt%.
The dispersion in the step (2) is ultrasonic dispersion, the dispersion time is 10-30 minutes, and the dispersion temperature is 0-50 ℃.
The dispersion in the step (3) is shear dispersion, the rotation speed of the shear dispersion is 2500r/min, the processing time is 1-3h, and the dispersion temperature is 0-50 ℃.
The fumed silica powder in the step (3) has a median particle diameter of 3.2-3.5 μm and a density of 3-5g/cm3(ii) a In the black polyimide film, the content of fumed silica powder is 1.5 wt% -10 wt%.
The first solvent in step (1), the second solvent in step (2), and the third solvent in step (3) are each independently at least one of N, N-dimethylformamide, N-Dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, sulfolane, tetramethylurea, and dimethylsulfone.
The catalyst in the step (4) is at least one of pyridine, alpha-picoline, beta-picoline, 3, 4-lutidine, 3, 5-lutidine, 4-picoline, 4-isopropylpyridine, N-dimethylbenzylamine, isoquinoline, 4-benzylpyridine, N-dimethyldodecylamine and triethylamine.
The catalyst of the step (4) is used in an amount of 0.1 to 0.5 mole relative to 1 mole of the amount of PAA in the PAA solution prepared in the step (1).
Further, the catalyst in the step (4) is a mixture of at least two of pyridine, α -picoline, β -picoline, 3, 4-lutidine, 3, 5-lutidine, 4-picoline, 4-isopropylpyridine, N-dimethylbenzylamine, isoquinoline, 4-benzylpyridine, N-dimethyldodecylamine, and triethylamine. Preferably, the catalyst is prepared by mixing triethylamine, pyridine and the like in a molar ratio, and the formed catalyst can improve the production efficiency of polyimide and improve the mechanical physical properties, tensile strength and film quality of the polyimide.
The anhydride dehydrating agent in the step (4) is at least one of benzoic anhydride, acetic anhydride, propionic anhydride and butyric anhydride.
The amount of the acid anhydride dehydrating agent in the step (4) is 0.2 to 0.6 mole relative to 1 mole of the amount of PAA in the PAA solution prepared in the step (1).
Further, the anhydride dehydrating agent in the step (4) is formed by mixing at least one of acetic anhydride, propionic anhydride and butyric anhydride with benzoic anhydride. Preferably, the anhydride dehydrating agent is formed by mixing acetic anhydride and benzoic anhydride in equal molar, and the formed mixed dehydrating agent has higher dehydrating rate. The temperature for continuously heating and drying the membrane in the drying zones with different temperatures in the step (4) is 80-300 ℃, the membrane is divided into 4 drying zones with different temperatures for continuously heating and drying, the temperature of the first zone is (80 ℃, 120 ℃), the temperature of the second zone is (120 ℃, 185 ℃), the temperature of the third zone is (185 ℃, 260 ℃), and the temperature of the fourth zone is (260 ℃, 300℃)]Each drying area can be controlled to be +/-2, and the cleanness of the hot temperature and the amount of hot air on the upper side of the drying tunnel can be ensured to be not less than 10m3The amount of hot air at the lower side cannot be less than 20 m/min3Per minute, each zone is of the same length and the total drying time is 25-60 minutes.
Room temperature herein means 20-30 ℃.
Example 1
(1) Dissolving 25 liters of 2,2 ' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP) and 25 liters of 4,4 ' -diaminodiphenyl ether (4,4 ' -ODA) in DMAC at room temperature, adding 30 liters of 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride (BTDA), adding 15 liters of pyromellitic dianhydride (PMDA) after the dissolution and stirring for 2 hours to form a thermoplastic polyimide prepolymer; after a certain reaction time, 6-8 liters (in this case, 6 liters) of BTDA and/or pyromellitic dianhydride were additionally added, the solution viscosity was monitored, the addition was stopped when the viscosity reached 3000 poise (so that eventually the aromatic diamine compound and the aromatic tetracarboxylic dianhydride were approximately equimolar), stirring was carried out for 2 hours to obtain a PAA solution having a PAA content of 20 wt%, and the temperature was maintained at 20 ℃ for future use.
(2) 7.5g of cobalt oxide was dispersed in 38.9 g of DMAC and dispersed ultrasonically with a sonicator for 10 minutes to deagglomerate the pigment.
(3) 75.4g of DMAC and 15.0g of fumed silica powder (the median particle size is 3.2-3.5 mu m) are fully mixed in a high-shear rotor-stator type mixer to prepare fumed silica slurry.
(4) In a mixer, 170.5 grams of the PAA solution, 6.1 grams of fumed silica slurry, and 36.6 grams of non-carbon black pigment slurry were thoroughly mixed to give a PAA mixed solution. Under the protection of nitrogen flow, 10 moles of a mixture of acetic anhydride and benzoic anhydride in equimolar proportion and 20 moles of a mixed catalyst of triethylamine and pyridine in equimolar proportion are added into each 100 moles of PAA obtained, casting is carried out at the width of 600mm, a mixture solution is coated, the thickness is 50 mu m, a gel film formed after drying is stretched at room temperature, then the solvent is removed by heating under the action of tension, defoaming is carried out, the film is dried by continuously raising the temperature in 4 drying zones with different temperatures in an oxygen-free imine furnace protected by inert gas, the temperature in the first zone is 80 ℃, the temperature in the second zone is 120 ℃, the temperature in the third zone is 185 ℃, the temperature in the fourth zone is 260 ℃, the temperature in each drying zone is controlled to be +/-2, and the cleanness of the hot temperature and the amount of hot air on the upper side of a drying channel can not be less than 10m3The amount of hot air at the lower side cannot be less than 20 m/min3Per minute, each zone length was the same and total drying time was 25 minutes, and a black polyimide film of about 50 μm was obtained by cast biaxial stretching.
The finally prepared black polyimide film comprises 2.5 wt% of fumed silica and 15 wt% of black pigment, and the balance is polyimide.
Example 2
Example 2 differs from example 1 in that: the content of the non-carbon black pigment was changed to 10% by weight. The finally prepared black polyimide film contains 2.5 wt% of fumed silica and 10 wt% of black pigment.
Example 3
Example 3 differs from example 1 in that: the content of the non-carbon black pigment was changed to 30%. The finally prepared black polyimide film contains 2.5 wt% of fumed silica and 30 wt% of black pigment.
Example 4
Example 4 differs from example 1 in that: changing the content of the fumed silica to 5 wt%. The finally prepared black polyimide film contains 5 wt% of fumed silica and 15 wt% of black pigment.
Example 5
Example 5 differs from example 1 in that: changing the content of the fumed silica to 10 wt%. The finally prepared black polyimide film contains 10 wt% of fumed silica and 15 wt% of black pigment.
Comparative example
The comparative example was the same as steps (1) to (3) of example 1, and step (4) employed a thermal imidization method.
(4) Thermal imidization: the degassed PAA mixed solution prepared was cast onto a glass plate using a stainless steel casting bar. The glass plate containing the wet cast film was placed on a hot plate at 80-100 ℃ and dried for 30-45 minutes to form a partially dried, partially imidized film. Peeling the black film from the glass, and placing the black film in an oven; the oven temperature was raised to 320 ℃ over 60-75min, held for 10 min, then raised to 400 ℃ for 5min, and then removed from the oven and cooled.
The finally prepared black polyimide film contains 2.5 wt% of fumed silica and 15 wt% of black pigment.
The properties of the films produced in the examples and comparative examples are as follows:
examples 1-5 demonstrate that black polyimide films prepared by chemical imidization have 60 degrees gloss values on both sides of less than 5 (matte appearance) which are much lower than the 60 degrees gloss values of polyimide films without added filler, achieving the typical black polyimide film gloss of less than or equal to 50.
Optical Density (OD) is defined as an indication of the ability of a material to block light. Measured with a transmission mirror, the optical density absorbed by the test object is indicated. Optical density is the logarithm of the ratio of incident light to transmitted light or the logarithm of the reciprocal of the light transmittance. The formula is OD ═ lg (incident light/transmitted light) or OD ═ lg (1/transmittance)
With the increase of the composite filler, the optical density of the film is obviously increased compared with the PI film without the composite filler, which indicates that the light shading capability of the material is enhanced.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (8)
1. The preparation method of the black polyimide film is characterized by comprising the following steps:
(1) preparation of polyamic acid (PAA) solution: reacting aromatic tetracarboxylic dianhydride and an aromatic diamine compound in a predetermined molar ratio in a first solvent under an inert atmosphere and at a certain temperature to obtain a PAA solution;
(2) preparation of non-carbon black pigment slurry: adding the non-carbon black pigment into the second solvent, uniformly stirring, and dispersing to obtain non-carbon black pigment slurry;
(3) preparing gas-phase white carbon black slurry: mixing the third solvent and fumed silica powder, and dispersing to obtain fumed silica slurry, wherein the fumed silica powder has a median particle diameter of 3.2-3.5 μm and a density of 3-5g/cm3；
(4) Chemical imidization: fully stirring and mixing the PAA solution, the non-carbon black pigment slurry and the fumed silica slurry to obtain a PAA composite solution; mixing the PAA composite solution, a catalyst and an anhydride dehydrating agent to obtain a mixture solution, coating the mixture solution by tape casting, stretching a gel film formed after drying at room temperature, heating under the action of tension to remove the solvent, defoaming, continuously heating and drying the film in drying zones with different temperatures in an oxygen-free thermal imine furnace protected by inert gas, and preparing a black polyimide film by tape casting-biaxial stretching, wherein:
the catalyst is formed by mixing triethylamine and pyridine in equal mol, and the dosage of the catalyst is 0.1-0.5 mol relative to the amount of PAA in 1 mol of the PAA solution;
the temperature for continuously heating and drying the membrane in drying zones with different temperatures is 80-300 ℃, the membrane is divided into 4 drying zones with different temperatures for continuously heating and drying, the temperature of the first zone is (80 ℃ and 120 ℃), the temperature of the second zone is (120 ℃ and 185 ℃), the temperature of the third zone is (185 ℃ and 260 ℃), and the temperature of the fourth zone is (260 ℃ and 300℃)]Each drying area can be controlled to be +/-2, and the cleanness of the hot temperature and the amount of hot air on the upper side of the drying tunnel can be ensured to be not less than 10m3The amount of hot air at the lower side cannot be less than 20 m/min3Per minute, each zone is of the same length and the total drying time is 25-60 minutes.
2. The method of claim 1, wherein: the aromatic diamine compound in the step (1) is at least one of 2,2 '-bis [4- (4-aminophenoxy) phenyl ] propane, p-phenylenediamine and 4, 4' -diaminodiphenyl ether; and/or the aromatic tetracarboxylic dianhydride in the step (1) is one or the combination of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride.
3. The method of claim 1, wherein: the molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine compound in the step (1) is 1-1.01: 1; the content of PAA in the prepared PAA solution is 18-28 wt%; the reaction temperature is 0-50 ℃, and the reaction time is 2-6 hours.
4. The method of claim 1, wherein: the non-carbon black pigment in the step (2) is at least one of cobalt oxide, black iron oxide, ferrochrome oxide and aniline black, and the particle size is 0.1-10 mu m; the content of the non-carbon black pigment in the black polyimide film is 10-30 wt%.
5. The method of claim 1, wherein: in the black polyimide film, the content of fumed silica powder is 1.5 wt% -10 wt%.
6. The method of claim 1, wherein: the anhydride dehydrating agent in the step (4) is at least one of benzoic anhydride, acetic anhydride, propionic anhydride and butyric anhydride; the amount of the acid anhydride dehydrating agent to be used is 0.2 to 0.6 mole relative to 1 mole of the amount of PAA in the PAA solution prepared in the step (1).
7. The method of claim 1, wherein: the anhydride dehydrating agent in the step (4) is formed by mixing at least one of acetic anhydride, propionic anhydride and butyric anhydride with benzoic anhydride.
8. The black polyimide film is characterized by comprising polyimide, non-carbon black pigment and fumed silica, wherein the weight content of the non-carbon black pigment is 10-30 wt%, the weight content of the fumed silica is 1.5-10 wt%, and the balance is the polyimide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482436A (en) * | 2009-08-13 | 2012-05-30 | E.I.内穆尔杜邦公司 | Matte finish polyimide films and methods relating thereto |
| KR101156084B1 (en) * | 2011-09-19 | 2012-06-20 | 에스케이씨코오롱피아이 주식회사 | Black polyimide film and method for preparing the same |
| CN105385159A (en) * | 2015-12-25 | 2016-03-09 | 桂林电器科学研究院有限公司 | Black matte polyimide thin film and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482436A (en) * | 2009-08-13 | 2012-05-30 | E.I.内穆尔杜邦公司 | Matte finish polyimide films and methods relating thereto |
| KR101156084B1 (en) * | 2011-09-19 | 2012-06-20 | 에스케이씨코오롱피아이 주식회사 | Black polyimide film and method for preparing the same |
| CN105385159A (en) * | 2015-12-25 | 2016-03-09 | 桂林电器科学研究院有限公司 | Black matte polyimide thin film and preparation method thereof |
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