CN109021566A - A kind of high insulation black matt polyimide film and multilayer film - Google Patents

Abstract

The invention discloses a high-insulation black matt polyimide film and a multilayer film. The high-insulation black matt polyimide film contains polyimide polymer and inorganic filler; The total amount of imine polymer and inorganic filler is 100%, and inorganic filler accounts for 4.35～21.88%; Polyimide polymer is synthesized according to routine, and inorganic filler comprises the component of following parts by weight: low-conductivity carbon black 1.0 parts , 0.4-2.0 parts of matting powder, 0.1-1.2 parts of titanium dioxide; the present invention adds different kinds of inorganic particles to the polyamic acid resin, and the prepared black polyimide film and multilayer film not only have good light-shielding properties , also has high electrical insulation, the electrical strength reaches 134.7 Kv/mm, and the electrical strength of the three-layer film can be as high as 180Kv/mm.

Description

A high insulation black matt polyimide film and multilayer film

technical field

The invention belongs to the technical field of preparation of electronic thin film insulating materials, and in particular relates to a high-insulation black matt polyimide film, a preparation method thereof and a multilayer film.

Background technique

With the rapid development of optoelectronic products in the market, higher requirements are put forward for the comprehensive performance of the black polyimide film as the cover film of optoelectronic products, that is, the glossiness of the black polyimide film is required to be reduced to below 30GU, and it can Maintain good electrical insulation performance, that is, the electrical strength is ≥ 80kV/mm. Since the main factors affecting the electrical insulation of the black matt polyimide film are the amount of added low-conductivity carbon black and the uniformity of dispersion, if the amount of carbon black added will directly affect the transmittance of the film, the shielding effect will not be satisfactory. According to the requirements of product use, the electrical properties can only be improved from the dispersion uniformity of carbon black in the film.

Black matt polyimide film needs to add light-shielding fillers, matting powder, black pigments, etc. during the preparation, and carbon black is the first choice for black film products as an important black pigment, but because of its certain conductivity, the electrical conductivity of the final product The insulation is affected, and other black pigments or titanium dioxide are used instead of carbon black to reduce light transmittance, but black pigments have problems of low blackness and poor heat resistance, which cannot achieve the effect of carbon black, nor can it meet the requirements of polycarbonate. Process requirements for the preparation of imide black film.

According to the report of Zeng Chenghua et al. [Analysis of Factors Affecting Hiding Power of Titanium Dioxide, Mineral Rock, No. 34, No. 2, 2014, pp. 18-21], an important indicator of titanium dioxide is hiding power. Titanium dioxide has the characteristics of stable physical and chemical properties, excellent tinting strength, hiding power and heat resistance, and is widely used in plastic films, coatings and other fields. Combined with the above problems of black polyimide film, many researchers in the industry use titanium oxide to replace part of carbon black, and use its high hiding power as a shielding agent for black polyimide film. For example, the patent of Scolon PI Company: CN _104169330 A reports that _{TiO 2} with a volume average particle size of 0.1-1 μm is used as a shielding agent. The amount is 0.5% to 1.5% based on the total weight of the black polyimide film. When the amount is small, the shielding effect will not be satisfactory. If the amount is more than 1.5%, the mechanical properties, especially the elongation at break, will deteriorate , the incidence of pinholes on the surface of the membrane is high, resulting in reduced yield and poor appearance of the membrane. It can be seen that solving the dispersion uniformity and stability of carbon black and light-shielding fillers is the core problem of preparing black matte polyimide films and multilayer films with high insulation properties, and it is also a problem that has always existed in the industry.

Contents of the invention

According to the existing problems of black matte polyimide film, the object of the present invention is to propose a method of mixing carbon black, matting powder and titanium dioxide according to a certain ratio to prepare a stable filler dispersion, and disperse the filler Add liquid to polyamic acid resin to prepare high-insulation black matt polyimide film and multilayer film; use the synergy between different particles of titanium dioxide, matting powder and carbon black to weaken the surface polarity of matting powder , which inhibits the formation of a network structure between particles, solves the problem of matting powder sedimentation and agglomeration, and improves the stability of filler dispersion; adding the filler dispersion to polyamic acid resin, using the electrical insulation properties of titanium dioxide and strong covering Strength, surface roughness, and weather resistance to improve the electrical insulation and weather resistance of black polyimide film, while reducing light transmittance and specular gloss.

The purpose of the present invention is achieved like this:

A high-insulation black matt polyimide film, comprising polyimide polymer and inorganic filler, the inorganic filler includes the following components in parts by weight: 1.0 parts of low-conductivity carbon black, 0.4-2.0 parts of matting powder, titanium White powder 0.1～1.2 parts.

Calculated by weight percentage, the total amount of the polyimide polymer and the inorganic filler is 100%, and the inorganic filler accounts for 4.35-21.88%.

The inorganic filler dispersion is specifically composed of the following components in grams by weight: 1.0 parts of low-conductivity carbon black, 0.4-2.0 parts of matting powder, 0.1-1.2 parts of titanium dioxide, and 18.0-53.2 parts of polar organic solvent.

The low-conductivity carbon black is a nanometer low-conductivity nano-carbon black with an original ecological particle size of ^10-500nm and a surface resistance ≥ 108; the matting powder is any silicon dioxide produced by a gas-phase method or a precipitation method, preferably gas-phase Silica, whose particle size is 1-8um, is micron-scale silica; the polar organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl One or a combination of two or more of sulfoxide, N-methylpyrrolidone and γ-butyrolactone in any ratio.

The titanium dioxide is any one of rutile type, anatase type and mixed crystal type, preferably rutile type. The rutile type titanium dioxide has a compact crystal structure, a higher refractive index, and stronger covering ability, and the rutile type is preferred.

The particle size of titanium dioxide has a great influence on its own dispersion stability. The larger the particle size, the faster the sedimentation, and the poorer the stability of the dispersion. The smaller the particle size, the easier it is for the particles to form agglomerates due to van der Waals force, which is not conducive to uniform dispersion. , comprehensively considered, the particle size of titanium dioxide is selected to be 0.1-3.0 μm, which is submicron titanium dioxide.

Considering that the filler particles gather in the solvent, the shearing machine used in the present invention is equipped with a shearing disc that is made of stainless steel or polytetrafluoroethylene, preferably a stainless steel shearing disc, and the edge of the shearing disc is serrated. . Considering the dispersing efficiency of filler, the unit size of the supporting shear disc, reactor and liquid level height of the shearing machine that the present invention adopts follows following ratio, and promptly reactor diameter: shear disc diameter: liquid level height is 100:( 25~75): (50~100). Considering the energy-efficiency ratio of filler dispersion, the shear rate of the present invention is based on the shear disk at the center of the vortex caused by stirring the dispersion liquid in the shear vessel that can be observed with the naked eye, specifically 500~5000 rpm. Considering that the impact and friction between filler particles can depolymerize filler particle aggregates, that is, low filler content in the system is not conducive to friction and impact between particles and affects the dispersion effect, and high filler content will directly affect the viscosity of the system. In the present invention, the filler content in the filler dispersion is 5-12%.

The polyimide polymer is prepared from 150 parts of polyamic acid resin, and the solid content of the polyamic acid resin is 10%-22%.

The polyamic acid resin is prepared from aromatic diamines, aromatic dianhydrides and polar organic solvents, wherein the aromatic diamines are 4,4'-diaminodiphenyl ether, 3,4'-di Aminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, biphenylenediamine, any one or a mixture of two; aromatic dianhydrides are pyromellitic dianhydride, 3,3', 4,4' - any one of biphenyl tetra-acid dianhydride, 3,3',4,4'-diphenylmethyl ether tetra-acid dianhydride, 3,3',4,4'-benzophenone tetra-acid dianhydride Or a mixture of two or more in any ratio; the polar organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and γ- A combination of one or two or more of butyrolactones in any ratio. The synthesis of the polyimide adopts the conventional synthesis method in the industry, adopts any one of in-situ polymerization, solution polycondensation, random copolymerization and block polymerization, and the molar ratio of the aromatic dianhydride to the aromatic diamine is 0.9～1.1:1, according to the mass percentage, the solid content of the polyamic acid resin is guaranteed to be 10～22%. Viscosity is controlled at 1000mpa·s~150,000mpa·s by rotational viscometer.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1), at a temperature of 0-40°C, according to the conventional polyamic acid synthesis method, dissolve aromatic diamine in a polar organic solvent, then add aromatic dianhydride, and the reaction time is between 3-12 hours Between, obtain polyamic acid resin, and guarantee its solid content is 10～22% according to mass percentage, viscosity is controlled at 1000mpa·s～150,000mpa·s; Wherein the molar ratio of aromatic dianhydride and aromatic diamine 0.9～1.1:1;

Step 2), take 19.5 to 57.4 parts of filler dispersion according to the parts by weight and mix and stir with 150 parts of polyamic acid resin in the above step 1) to prepare black polyamic acid resin. According to the conventional two-way stretching method, the black polyamide Acid resin defoaming, cast into film, and then biaxially stretched, high temperature imidization to obtain high insulation black matte polyimide film.

The filler dispersion is prepared according to the following steps:

Step 2.1), at 10-40°C, mix 1.0 parts of low-conductivity carbon black with a particle size of 10-500nm and 9.0 parts of polar organic solvent according to parts by weight, and transfer it to a shearing machine. Disperse at 500-5000 rpm for 1-10 hours, then transfer to grinding equipment, and disperse for 0-4 hours at a grinding speed of 500-5000 rpm to obtain a black dispersion;

Step 2.2), at 10-40°C, mix 0.4-2.0 parts of matting powder with a particle size of 1-8 μm, 0.1-1.2 parts of titanium dioxide with a particle size of 0.1-3.0 μm and 9.0-35.2 parts of polar organic Mix the solvents, transfer them to any one of shearing, ultrasonic, emulsifying, homogeneous dispersion, and magnetic dispersion equipment, and disperse for 1 to 5 hours at a rate of 500 to 5,000 revolutions/min to obtain a white dispersion;

Step 2.3), at 10-40°C, mix the black dispersion obtained in the above step 2.1) with the white dispersion obtained in step 2.2), and transfer to a shearing machine at a shear speed of 500-5000 rpm Under the condition of shearing and dispersing for 0.5~10h, the filler dispersion liquid was obtained.

The grinding equipment in the step 2.1) is any one of bead mill, sand mill, planetary ball mill or three-roll mill, wherein the bead mill, sand mill, and planetary ball mill are equipped with a grinding medium of zirconia Any one of beads, zirconium beads, ceramic beads, glass beads and stainless steel beads, the particle size of the grinding medium is 0.1-5 mm.

The shearing machine involved in the step 2.1) to step 2.3) is equipped with a shearing disc made of stainless steel or polytetrafluoroethylene, preferably a stainless steel shearing disc, and the edge of the shearing disc is serrated , the unit size of the shearing plate, reactor and liquid level height of the shearing machine involved follows the following ratio: reactor diameter: shearing plate diameter: liquid level height is 100: (25~75): (50~100 ).

A kind of high insulation black matt polyimide multi-layer film is carried out according to the following method:

Step 1), at a temperature of 0-40°C, according to the conventional polyamic acid synthesis method, dissolve aromatic diamine in a polar organic solvent, then add aromatic dianhydride, and the reaction time is between 3-12 hours Between, obtain polyamic acid resin, and guarantee its solid content is 10～22% according to mass percentage, viscosity is controlled at 1000mpa·s～150,000mpa·s; Wherein the molar ratio of aromatic dianhydride and aromatic diamine 0.9～1.1:1;

Step 2), take 19.5-48.4 parts of the filler dispersion according to the parts by weight, mix and stir with 150 parts of the polyamic acid resin in the above step 1), and defoam to obtain a high-insulation black matte polyimide resin;

Step 3), the polyamic acid resin prepared in step 1) is defoamed and cast into a film to obtain a polyimide cast film, and the high-insulation black matt polyamic acid prepared in step 2) is The resin is coated on the top and/or bottom of the polyimide cast film, and after high-temperature imidization, a high-insulation black matt polyimide multilayer film is obtained, wherein the thickness of the polyimide is 8 μm to 50 μm, The thickness of high insulation black matt polyimide coating is 2μm～50μm,

Considering that the casting film and the high-insulation and low-gloss polyamic acid resin layer coated on it are not easy to delaminate during subsequent use, the imidization temperature of the casting film in the above steps (3) is controlled at 140~180°C , to increase the adhesion between the cast film and the high insulation low matt polyamic acid resin layer.

The beneficial effects of the present invention are as follows: the present invention adopts the high-insulation black matt polyimide film obtained by the above-mentioned preparation method, compared with the prior art, the high-insulation black matt polyimide film and the multilayer The film has high electrical insulation, the electric strength reaches 134.7 Kv/mm, the electric strength of the three-layer film can be as high as 180Kv/mm, and it has good light-shielding properties.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments.

Example 1:

A high-insulation black matt polyimide film: according to the percentage by weight, it is composed of 95.65% polyimide polymer and 4.35% inorganic filler, specifically 150 kilograms of polyamic acid resin, inorganic filler dispersion 19.5 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 10 nm, 0.4 kg of matting powder with a particle size of 3 μm produced by the gas phase method, and a mixture of 0.1 μm particle size 0.1 kg of crystalline titanium dioxide, and 18.0 kg of N,N-dimethylformamide as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 15.8 kg of 4,4-diaminodiphenyl ether in 117 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 17.2 kilograms of pyromellitic dianhydride were reacted for 5 hours to obtain 150 kilograms of polyamic acid resin; its solid content was 22%, and its viscosity was 12000mpa s;

Step 2), take 19.5 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 10°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 500 rpm , shear and disperse for 10 hours, then transfer to a planetary ball mill, grind and disperse for 0.5 hours under the conditions that the rotating speed is 5000 rpm, the grinding medium is zirconia beads, and the particle size is 1 mm, to obtain a black dispersion;

Step 2.2), at 10°C, mix 0.4 kg of matting powder and 0.1 kg of titanium dioxide with 9.0 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 500 rpm Under the condition of 1 min, the shear dispersion was carried out for 5 hours to obtain a white dispersion liquid;

Step 2.3), at 10°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer to a shearing machine equipped with a serrated shearing disc (reaction kettle diameter: shear Disc diameter: liquid level height (100:25:50), shear dispersion at 3000 rpm for 0.5h to obtain a stable filler dispersion with a solid content of 7.7%.

Example 2:

A high-insulation black matte polyimide film: according to the percentage by weight, it is composed of 78.12% polyimide polymer and 21.88% inorganic filler, specifically 150 kg of polyamic acid resin, inorganic filler dispersion It is 57.4 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 10 nm, 2.0 kg of matting powder with a particle size of 3 μm produced by the gas phase method, and a mixture of 0.1 μm particle size 1.2 kg of crystalline titanium dioxide, and 53.2 kg of N,N-dimethylformamide as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 4.0 kg of 4,4-diaminodiphenyl ether and 2.2 kg of p-phenylenediamine in 135 kg of N,N-dimethyl In acetamide, add 8.8 kilograms of pyromellitic dianhydride, and react for 5 hours to obtain a polyamic acid resin; its solid content is 10%, and its viscosity is 1000mpa·s;

Step 2) Take 57.4 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 10°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 500 rpm , shear and disperse for 10 hours, then transfer to a planetary ball mill, grind and disperse for 0.5 hours under the conditions that the rotating speed is 5000 rpm, the grinding medium is zirconia beads, and the particle size is 1 mm, to obtain a black dispersion;

Step 2.2), at 10°C, mix 2.0 kg of matting powder and 1.2 kg of titanium dioxide with 44.2 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 500 rpm Under the condition of 1 min, the shear dispersion was carried out for 5 hours to obtain a white dispersion liquid;

Step 2.3), at 10°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer to a shearing machine equipped with a serrated shearing disc (reaction kettle diameter: shear Disc diameter: liquid level height (100:70:125), shear dispersion at 3000 rpm for 0.5h to obtain a stable filler dispersion with a solid content of 7.3%.

Example 3:

A high-insulation black matt polyimide film is composed of 93.46% polyimide polymer and 6.54% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion 21 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 10 nm, 1.0 kg of silica with a particle size of 3 μm produced by the gas phase method as a matting powder, and a mixture of 0.1 μm particle size 0.1 kg of crystalline titanium dioxide, and 18.9 kg of N,N-dimethylformamide as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4'-diaminodiphenyl ether in 120 kg of N,N-dimethylformamide according to the conventional polyamic acid synthesis method at a temperature of 0°C, and then 15.6 kg of pyromellitic dianhydride was added, and the reaction time was 3 hours to obtain a polyamic acid resin with a solid content of 20% and a viscosity of 1000 mpa·s;

Step 2), take 21.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 10°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 500 rpm , shear and disperse for 10 hours, then transfer to a planetary ball mill, grind and disperse for 0.5 hours under the conditions that the rotating speed is 5000 rpm, the grinding medium is zirconia beads, and the particle size is 1 mm, to obtain a black dispersion;

Step 2.2), at 10°C, mix 1.0 kg of matting powder and 0.1 kg of titanium dioxide with 9.9 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 500 rpm Under the condition of 1 min, the shear dispersion was carried out for 5 hours to obtain a white dispersion liquid;

Step 2.3), at 10°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer to a shearing machine equipped with a serrated shearing disc (reaction kettle diameter: shear Disc diameter: liquid surface height (100:50:110), shear dispersion at 3000 rpm for 0.5h to obtain a stable filler dispersion with a solid content of 10%.

A kind of high insulation black matt polyimide multi-layer film is carried out according to the following method:

Step 1) Dissolve 14.4 kg of aromatic diamine in 120 kg of N,N-dimethylformamide at a temperature of 0°C according to the conventional polyamic acid synthesis method, and then add 15.6 kg of aromatic dianhydride kg, and the reaction time is 3h to obtain polyamic acid resin, and ensure that its solid content is 20% according to mass percentage, and its viscosity is 1000mpa s;

Step 2), take 21.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin in the above step 1), defoaming, and obtain high insulating black matt polyamic acid resin;

Step 3), according to the method of step 1), another 150 kg polyamic acid resin was produced, and the polyamic acid resin prepared according to the method of step 1) was defoamed, cast at 140°C to form a film, and the obtained Polyimide cast film. At the same time, the high-insulation black matt polyamic acid resin prepared in step 2) is coated on the upper surface of the polyimide cast film, and after imidization, a high-insulation black matt polyimide two-layer film is obtained. Among them, the thickness of polyimide is 8 μm, and the thickness of high-insulation black matt polyimide coating is 2 μm;

Step 4), re-coat the highly insulating black matt polyamic acid resin prepared in step 2) on the other side of the high insulating black matt polyimide two-layer film prepared in step 3), imidization Finally, a three-layer film of high-insulation black matt polyimide is prepared, and the thickness of the high-insulation black matt polyimide coating is 2 μm.

Example 4:

A high-insulation black matte polyimide film is composed of 91.46% polyimide polymer and 8.54% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion For 28 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 50 nm, 1.0 kg of silica produced by precipitation with a particle size of 5 μm and used as a matting powder, and rutile with a particle size of 2.0 μm 0.8 kg of titanium dioxide, 25.2 kg of N,N-dimethylacetamide used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 20°C, and then add 15.6 kilograms of pyromellitic dianhydride, and the reaction time is 5 hours to obtain a polyamic acid resin, and ensure that its solid content is 20% according to mass percentage, and its viscosity is 1000mpa s;

Step 2), take 28.0 grams of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), step 1), at 20°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc at 1200 rpm Under the condition of shearing and dispersing for 6 hours under the condition of 1 mm, it is transferred to a planetary ball mill, and the rotating speed is 4000 rpm, the grinding medium is zirconia beads, and the particle size is 1 mm, and it is ground and dispersed for 2 hours to obtain a black dispersion;

Step 2.2), at 20°C, mix 1.0 kg of matting powder and 0.8 kg of titanium dioxide with 16.2 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 800 rpm Under the condition of 1 min, shear and disperse for 4 hours to obtain a white dispersion;

Step 2.3), at 20°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:100), shear dispersion at 2500 rpm for 2 hours to obtain a stable filler dispersion with a solid content of 10%.

A kind of high insulation black matt polyimide multi-layer film is carried out according to the following method:

Step 1) Dissolve 14.4 kg of aromatic diamine in 120 kg of N,N-dimethylformamide at a temperature of 0°C according to the conventional polyamic acid synthesis method, and then add 15.6 kg of aromatic dianhydride kg, and the reaction time was 3 hours to obtain a polyamic acid resin, and ensure that its solid content was 20% according to the mass percentage, and its viscosity was 100,000 mpa s;

Step 2), take 28 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin in the above step 1), and defoam to obtain a high-insulation black matte polyamic acid resin;

Step 3), according to the method of step 1), another 150 kg polyamic acid resin was produced, and the polyamic acid resin prepared according to the method of step 1) was defoamed, cast at 180°C to form a film, and the obtained Polyimide cast film, its thickness is. At the same time, the high-insulation black matt polyamic acid resin prepared in step 2) is coated on the upper surface of the polyimide cast film, and after imidization, a high-insulation black matt polyimide two-layer film is obtained. Among them, the thickness of polyimide is 50 μm, and the thickness of high-insulation black matte polyimide coating is 50 μm;

Step 4), apply the highly insulating black matte polyamic acid resin prepared in step 2) on the other side of the highly insulating black matt polyimide two-layer film prepared in step 3), imidization Finally, a three-layer film of high-insulation black matt polyimide was prepared, wherein the thickness of the high-insulation black matt polyimide coating was 50 μm.

Example 5:

A high-insulation black matt polyimide film is composed of 90.36% polyimide polymer and 9.64% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion for 40 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 100 nm, 1.0 kg of silicon dioxide with a particle size of 8 μm produced by a gas phase method, and rutile with a particle size of 3.0 μm 1.2 kilograms of titanium dioxide, 36.8 kilograms of dimethyl sulfoxide used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of dimethyl sulfoxide according to the conventional polyamic acid synthesis method at a temperature of 15°C, and then add pyromellitic acid 15.6 kilograms of dianhydride, the reaction time is 8h, obtain polyamic acid resin, and guarantee its solid content is 20% according to mass percentage, viscosity 9000mpa s;

Step 2), take 32.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain black polyamic acid resin, defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), step 1), at 30°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc at a speed of 3000 rpm /min, shear dispersion for 4 hours to obtain a black dispersion;

Step 2.2), at 30°C, mix 1.0 kg of matting powder and 1.2 kg of titanium dioxide with 27.8 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 1200 rpm Under the condition of 1 min, shear and disperse for 3 hours to obtain a white dispersion;

Step 2.3), at 30°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer to a shearing machine equipped with a serrated shearing disk (reactor diameter: shear Disc diameter: liquid level height (100:50:100), shear dispersion at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 8.0%.

A kind of high insulation black matt polyimide multi-layer film is carried out according to the following method:

Step 1) Dissolve 14.4 kg of aromatic diamine in 120 kg of N,N-dimethylformamide at a temperature of 0°C according to the conventional polyamic acid synthesis method, and then add 15.6 kg of aromatic dianhydride kg, the reaction time is 3h, to obtain polyamic acid resin, and ensure that its solid content is 20% according to the mass percentage, and the viscosity is 9000mpa s;

Step 2), take 40.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin in the above step 1), and defoam to obtain a high-insulation black matt polyamic acid resin;

Step 3), according to the method of step 1), another 150 kg polyamic acid resin was produced, and the polyamic acid resin prepared according to the method of step 1) was defoamed, cast at 160°C to form a film, and the obtained Polyimide cast film. At the same time, the high-insulation black matt polyamic acid resin prepared in step 2) is coated on the upper surface of the polyimide cast film, and after imidization, a high-insulation black matt polyimide two-layer film is obtained. Among them, the thickness of polyimide is 12.5 μm, and the thickness of high-insulation black matt polyimide coating is 10 μm;

Step 4), apply the highly insulating black matte polyamic acid resin prepared in step 2) on the other side of the highly insulating black matt polyimide two-layer film prepared in step 3), imidization Finally, a three-layer film of high-insulation black matt polyimide was prepared, and the thickness of the high-insulation black matt polyimide coating was 10 μm.

Other embodiments of a high-insulation black matt polyimide multilayer film are the same as the method of this embodiment, the difference is that the content characteristics change with different implementations, and it is the same as a high-insulation black matt polyimide The film proportioning is the same and will not be described again.

Embodiment 6:

A high-insulation black matte polyimide film is composed of 93.75% polyimide polymer and 6.25% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion for 20 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 300 nm, 0.4 kg of silicon dioxide with a particle size of 2 μm produced by a gas phase method, and rutile with a particle size of 2.0 μm 0.6 kg of titanium dioxide, 18.0 kg of N-methylpyrrolidone used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of N-methylpyrrolidone according to the conventional polyamic acid synthesis method at a temperature of 40°C, and then add pyromellitic acid 15.6 kilograms of dianhydride, the reaction time is 8h, obtain polyamic acid resin, and its solid content is 20% according to mass percentage, viscosity 9000mpa·s;

Step 2), take 20.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 40°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 4000 rpm , shear and disperse for 2 hours, then transfer to a three-roll mill, and grind and disperse for 1 hour at a speed of 2000 rpm to obtain a black dispersion;

Step 2.2), at 40°C, mix 0.4 kg of matting powder and 0.6 kg of titanium dioxide with 9.0 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 2000 rpm Under the condition of 1 min, shear and disperse for 2 hours to obtain a white dispersion;

Step 2.3), at 40°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer to a shearing machine equipped with a serrated shearing disc (reaction kettle diameter: shear Disc diameter: liquid level height (100:50:75), shear dispersion at 1200 rpm for 8 hours to obtain a stable filler dispersion with a solid content of 10%.

Embodiment 7:

A high-insulation black matte polyimide film is composed of 92.59% polyimide polymer and 7.41% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion For 24 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 500nm, 0.8 kg of silicon dioxide produced by a gas phase method with a particle size of 1 μm and used as a matting powder, and rutile with a particle size of 0.1 μm Type titanium dioxide 0.6 kg, 21.6 kg of gamma-butyrolactone used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of γ-butyrolactone according to the conventional polyamic acid synthesis method at a temperature of 40°C, and then add pyromellitic acid 15.6 kilograms of dianhydride, the reaction time is 10h, obtain polyamic acid resin, and guarantee its solid content is 20% according to mass percentage, viscosity 15000mpa s;

Step 2), take 24.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), step 1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc at a speed of 5000 rpm Under the condition of shearing and dispersing for 1 hour, transfer it to a planetary ball mill, grind and disperse for 4 hours under the condition that the rotating speed is 500 rpm, the grinding medium is zirconia beads, and the particle size is 1 mm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 0.8 kg of matting powder and 0.6 kg of titanium dioxide with 12.6 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 3000 rpm Under the condition of 1 min, shear and disperse for 1 h to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear dispersion at 500 rpm for 10 hours to obtain a stable filler dispersion with a solid content of 10%.

Embodiment 8:

A high-insulation black matte polyimide film is composed of 90.03% polyimide polymer and 9.97% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion is 33 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 25 nm, 1.3 kg of silicon dioxide produced by a gas phase method with a particle size of 5 μm and used as a matting powder, and rutile with a particle size of 0.4 μm 1.0 kg of titanium dioxide, 14.8 kg of N,N-dimethylacetamide and 14.9 kg of N-methylpyrrolidone mixture used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 60 kg of N,N-dimethylacetamide and 60 kg of N - Add 15.6 kg of pyromellitic dianhydride to methylpyrrolidone, and the reaction time is 10 hours to obtain a polyamic acid resin, and its solid content is 20% according to the mass percentage, and its viscosity is 18000mpa·s;

Step 2), take 33.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 15 °C, mix 1.0 kg of low-conductivity carbon black, 4.5 kg of N,N-dimethylacetamide and 4.5 kg of N-methylpyrrolidone mixture, and transfer to a In the shearing machine, under the condition of the shearing speed of 3000 rpm, shear and disperse for 2 hours, and then transfer to the planetary ball mill, at the rotational speed of 2500 rpm, the grinding medium is zirconia beads, the particle size is 1mm Grinding and dispersing for 4h under the condition of the black dispersion liquid;

Step 2.2), at 15 ° C, mix 1.3 kg of matting powder and 1.0 kg of titanium dioxide with 10.3 kg of N,N-dimethylacetamide and 10.4 kg of N-methylpyrrolidone mixture, and turn it into a sawtooth In a shearing machine with a shear disk, shear and disperse for 1 hour under the condition of 1800 rpm to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear and disperse at 1000 rpm for 5 hours to obtain a stable filler dispersion with a solid content of 10%.

Embodiment 9:

A high-insulation black matte polyimide film is composed of 88.24% polyimide polymer and 11.76% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion It is 33.3 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 30 nm, 2.0 kg of silicon dioxide with a particle size of 5 μm produced by a gas phase method as a matting agent, and rutile titanium with a particle size of 0.4 μm 1.0 kg of white powder, 29.3 kg of N,N-dimethylacetamide used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of γ-butyrolactone according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 15.6 kg of phenylene Tetraformic acid dianhydride, react 5h to obtain 150 kilograms of polyamic acid resins; Its solid content is 20%, viscosity 15000mpa s;

Step 2), take 33.3 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 3000 rpm , shear and disperse for 2 hours, then transfer to a sand mill, grind and disperse for 4 hours under the conditions that the rotating speed is 2500 rpm, the grinding medium is zirconium beads, and the particle size is 0.1 mm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 2.0 kg of matting powder and 1.0 kg of titanium dioxide with 20.3 kg of polar organic solvent, transfer to an ultrasonic dispersion device, and ultrasonically disperse for 2 hours to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear dispersion at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 12%.

Example 10:

A high-insulation black matt polyimide film is composed of 90.91% polyimide polymer and 9.09% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion for 30 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 30 nm, 1.3 kg of silicon dioxide with a particle size of 6 μm produced by a gas phase method as a matting powder, and rutile with a particle size of 1.0 μm 0.7 kg of titanium dioxide, and 27.0 kg of N,N-dimethylacetamide as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 15.6 kilograms of pyromellitic dianhydride were reacted for 5 hours to obtain 150 kilograms of polyamic acid resin; its solid content was 20%, and its viscosity was 15000mpa s;

Step 2), mix and stir 30.0 kg of filler dispersion with 150 kg of polyamic acid resin obtained in step 1) to obtain black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method Stretching into a film, and then biaxially stretching, high-temperature imidization to obtain a high-insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 3000 rpm , shear and disperse for 2 hours, then transfer to a sand mill, grind and disperse for 4 hours under the conditions that the rotating speed is 2500 rpm, the grinding medium is zirconium beads, and the particle size is 0.8 μm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 1.3 kg of matting powder and 0.7 kg of titanium dioxide with 18.0 kg of polar organic solvent, transfer to an emulsifier, and emulsify and disperse at a speed of 2000 rpm for 4 hours to obtain white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear and disperse at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 10%.

Example 11:

A high-insulation black matte polyimide film is composed of 91.46% polyimide polymer and 8.54% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion For 28 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 30 nm, 1.3 kg of silica with a particle size of 6 μm produced by the precipitation method as a matting agent, and rutile titanium with a particle size of 0.4 μm 0.5 kg of white powder, 25.2 kg of N,N-dimethylacetamide used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 15.6 kilograms of pyromellitic dianhydride were reacted for 5 hours to obtain 150 kilograms of polyamic acid resin; its solid content was 20%, and its viscosity was 12000mpa s;

Step 2), take 28.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 3000 rpm , shear and disperse for 2 hours, then transfer to a sand mill, grind and disperse for 4 hours under the conditions that the rotating speed is 2500 rpm, the grinding medium is zirconium beads, and the particle size is 1.2 mm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 1.3 kg of matting powder and 0.5 kg of titanium dioxide with 16.2 kg of polar organic solvent, transfer to a homogenizer, and emulsify and disperse at a speed of 1200 rpm for 4 hours. A white dispersion is obtained;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear and disperse at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 10%.

Embodiment 12:

A high-insulation black matt polyimide film is composed of 84.27% polyimide polymer and 15.73% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion is 56 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 20 nm, 1.3 kg of silicon dioxide with a particle size of 6 μm produced by the gas phase method, and rutile with a particle size of 0.6 μm 0.5 kg of titanium dioxide, 53.2 kg of N,N-dimethylacetamide used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 4.0 kg of 4,4-diaminodiphenyl ether and 2.2 kg of p-phenylenediamine in 135 kg of N,N-dimethyl In the base acetamide, add 8.8 kilograms of pyromellitic dianhydride, react for 5 hours to obtain polyamic acid resin; its solid content is 10%, viscosity 15000mpa·s;

Step 2), take 56 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain black polyamic acid resin, defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), step 1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc at a speed of 3000 rpm Under the condition of 1/min, shear and disperse for 2 hours, then transfer to a sand mill, and grind and disperse for 4 hours under the condition that the rotating speed is 2500 rpm, the grinding medium is zirconium beads, and the particle size is 3 mm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 1.3 kg of matting powder and 0.5 kg of titanium dioxide with 44.2 kg of polar organic solvent, transfer to a magnetic stirrer, stir and disperse at a speed of 1200 rpm for 4 hours , to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear and disperse at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 5%.

Example 13:

A high-insulation black matt polyimide film is composed of 88.93% polyimide polymer and 11.07% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion for 35 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 20nm, 1.3 kg of silica produced by the precipitation method with a particle size of 6 μm and used as a matting powder, and rutile with a particle size of 1.0 μm 0.5 kg of titanium dioxide, 32.2 kg of N,N-dimethylacetamide used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 9.9 kg of 4,4-diaminodiphenyl ether in 127.5 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 5.4 kg of pyromellitic dianhydride and 7.2 kg of biphenyl dianhydride were reacted for 5 hours to obtain 150 kg of polyamic acid resin; its solid content was 15%, and its viscosity was 15000mpa s;

Step 2), take 35.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc, at a speed of 3000 rpm Under the conditions of shearing and dispersing for 2 hours, then transfer to a bead mill, and grind and disperse for 4 hours under the conditions that the rotating speed is 2500 rpm, the grinding medium is zirconium beads, and the particle size is 4 mm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 1.3 kg of matting powder and 0.5 kg of titanium dioxide with 23.2 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 1800 rpm Under the condition of 1 min, shear and disperse for 1 h to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear and disperse at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 8%.

Example 14:

A high-insulation black matt polyimide film is composed of 91.72% polyimide polymer and 8.28% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion 23.3 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 20nm, 1.3 kg of silica produced by the precipitation method with a particle size of 6 μm and used as a matting powder, and rutile with a particle size of 3.0 μm 0.5 kg of titanium dioxide, 20.5 kg of gamma-butyrolactone used as a polar organic solvent.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 15.8 kg of 4,4-diaminodiphenyl ether in 117 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 17.2 kilograms of pyromellitic dianhydride were reacted for 5 hours to obtain 150 kilograms of polyamic acid resin; its solid content was 22%, and its viscosity was 12000mpa s;

Step 2), take 23.3 kg of filler dispersion and mix and stir with the polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, defoam the black polyamic acid resin according to the conventional biaxial stretching method, and cast Film formation, biaxial stretching, and high-temperature imidization to obtain a high-insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc at a shearing speed of 5000 rpm Disperse for 1h under the condition of the grinding medium, then transfer to the grinding equipment containing the grinding medium, and disperse for 4h under the condition of 500 rpm at the grinding speed to obtain a black dispersion liquid; the grinding equipment is a planetary ball mill, and the grinding medium is zirconia beads. The particle size of the grinding media is 1mm.

Step 2.2), at 15°C, mix 1.3 kg of matting powder and 0.5 kg of titanium dioxide with 11.5 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc, at 1800 rpm Under the condition of 1 min, shear and disperse for 1 h to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear dispersion at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 12%.

Comparative example 1:

A high-insulation black matt polyimide film is composed of 88.93% polyimide polymer and 11.07% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion 28.8 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 20nm, 1.3 kg of silicon dioxide used as a matting powder with a particle size of 6 μm produced by the precipitation method, and used as a polar organic solvent 26.5 kg of N,N-dimethylacetamide.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 4.0 kg of 4,4-diaminodiphenyl ether and 2.2 kg of p-phenylenediamine in 135 kg of N,N-dimethyl In acetamide, add 8.8 kilograms of pyromellitic dianhydride, and react for 5 hours to obtain a polyamic acid resin; its solid content is 15%, and its viscosity is 15000mpa·s;

Step 2), take 28.8 kg of filler dispersion and mix and stir with the polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, defoam the black polyamic acid resin according to the conventional biaxial stretching method, and cast Film formation, biaxial stretching, and high-temperature imidization to obtain a high-insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), step 1), at 15°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer it to a shearing machine equipped with a serrated shearing disc at a speed of 3000 rpm Under the condition of 1/min, shear and disperse for 2 hours, then transfer to the bead mill, grind and disperse for 4 hours under the condition that the rotating speed is 2500 rpm, the grinding medium is zirconium beads, and the particle size is 4 mm, to obtain a black dispersion;

Step 2.2), at 15°C, mix 1.3 kg of matting powder with 17.5 kg of polar organic solvent, transfer to a shearing machine equipped with a serrated shearing disc, and shear at 1800 rpm Disperse for 1 hour to obtain a white dispersion;

Step 2.3), at 15°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer it to a shearing machine equipped with a serrated shearing disc (diameter of the reactor: shear Disc diameter: liquid level height (100:50:75), shear and disperse at 2000 rpm for 4 hours to obtain a stable filler dispersion with a solid content of 8%.

A kind of high insulation black matt polyimide multi-layer film is carried out according to the following method:

Step 1) Dissolve 14.4 kg of aromatic diamine in 120 kg of N,N-dimethylformamide at a temperature of 0°C according to the conventional polyamic acid synthesis method, and then add 15.6 kg of aromatic dianhydride kg, and the reaction time is 3h to obtain polyamic acid resin, and ensure that its solid content is 20% according to mass percentage, and its viscosity is 1000mpa s;

Step 2), take 28.8 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin in the above step 1), and defoam to obtain a high-insulation black matte polyamic acid resin;

Step 3), according to the method of step 1), another 150 kg polyamic acid resin was produced, and the polyamic acid resin prepared according to the method of step 1) was defoamed, cast at 160°C to form a film, and the obtained Polyimide cast film. At the same time, the high-insulation black matt polyamic acid resin prepared in step 2) is coated on the upper surface of the polyimide cast film, and after imidization, a high-insulation black matt polyimide two-layer film is obtained. Among them, the thickness of polyimide is 12.5 μm, and the thickness of high-insulation black matt polyimide coating is 10 μm;

Step 4), apply the highly insulating black matte polyamic acid resin prepared in step 2) on the other side of the highly insulating black matt polyimide two-layer film prepared in step 3), imidization Finally, a three-layer film of high-insulation black matt polyimide was prepared, and the thickness of the high-insulation black matt polyimide coating was 10 μm.

Comparative example 2:

A high-insulation black matte polyimide film is composed of 93.75% polyimide polymer and 6.25% inorganic filler according to the percentage by weight, specifically, 150 kg of polyamic acid resin, inorganic filler dispersion for 20 kg. The inorganic filler dispersion is composed of the following components in grams by weight: 1.0 kg of low-conductivity carbon black with a particle size of 50 nm, 1.0 kg of silicon dioxide produced by a precipitation method with a particle size of 5 μm used as a matting powder, and used as a polar organic solvent 18 kg of N,N-dimethylacetamide.

A kind of preparation method of high insulation black matte polyimide film, is prepared by following method:

Step 1) Dissolve 14.4 kg of 4,4-diaminodiphenyl ether in 120 kg of N,N-dimethylacetamide according to the conventional polyamic acid synthesis method at a temperature of 25°C, and then add 15.6 kilograms of pyromellitic dianhydride were reacted for 5 hours to obtain a polyamic acid resin; the polyamic acid resin had a solid content of 20% and a viscosity of 15000 mpa s;

Step 2), take 20.0 kg of filler dispersion and mix and stir with 150 kg of polyamic acid resin obtained in the above step 1) to obtain a black polyamic acid resin, and defoam the black polyamic acid resin according to the conventional biaxial stretching method, Cast film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film.

Wherein, the filler dispersion is prepared according to the following steps:

Step 2.1), step 1), at 20°C, mix 1.0 kg of low-conductivity carbon black with 9.0 kg of polar organic solvent, and transfer to a shearing machine equipped with a serrated shearing disc at 1200 rpm Under the condition of shearing and dispersing for 6 hours under the condition of 1 mm, it is transferred to a planetary ball mill, and the rotating speed is 4000 rpm, the grinding medium is zirconia beads, and the particle size is 1 mm, and it is ground and dispersed for 2 hours to obtain a black dispersion;

Step 2), at 20°C, mix 1.0 kg of matting powder with 9.0 kg of polar organic solvent, transfer to a shearing machine equipped with a serrated shearing disc, and shear at 800 rpm Disperse for 4 hours to obtain a white dispersion;

Step 3), at 20°C, mix the black dispersion obtained in the above step 1) with the white dispersion obtained in step 2), and transfer to a shearing machine equipped with a serrated shearing disc (reactor diameter: shear Disc diameter: liquid level height (100:50:100), shear dispersion at 2500 rpm for 2 hours to obtain a stable filler dispersion with a solid content of 10%.

The properties of the high-insulation black matt polyimide film prepared by Examples 1-14 and Comparative Examples 1-2 are shown in Table 1. Comparative Examples and Comparative Examples, when the amount of carbon black added is the same, after adding titanium dioxide The shading effect is relatively good. When the particle size of titanium dioxide is increased, the shading rate decreases and the electrical properties decrease relatively. The particle size of titanium dioxide in the black polyimide film is preferably 0.1-0.6 μm. After adding titanium dioxide to the black polyimide film, the electric strength is greatly increased, up to 134kv/mm. The properties of the high-insulation black matt polyimide three-layer film prepared in Example 1 are shown in Table 2, and the electrical properties are as high as 180kv/mm.

Table 1 High insulation black matt polyimide monolayer film

Claims (9)

1. a high insulation black matt polyimide film, comprising polyimide polymer and inorganic filler, is characterized in that, inorganic filler comprises the component of following parts by weight: 1.0 parts of low-conductivity carbon black, matting powder 0.4-2.0 parts, titanium dioxide 0.1-1.2 parts. 2. the high insulation black matte polyimide film according to claim 1, is characterized in that, calculates according to weight percentage, is 100% with the total amount of polyimide polymer and inorganic filler, and inorganic filler accounts for 4.35% ~21.88%. 3. high insulation black matt polyimide film according to claim 1, is characterized in that, the raw material of preparing polyimide polymer comprises aromatic diamine, aromatic dianhydride and polar organic solvent, wherein Aromatic diamine is any one or a mixture of 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, and biphenylenediamine ; Aromatic dianhydride is pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl ether tetracarboxylic dianhydride, 3 , any one of 3',4,4'-benzophenone tetraacid dianhydride or a mixture of two or more in any ratio; the polar organic solvent is N,N-dimethylformamide, N,N- Dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and γ-butyrolactone or a combination of two or more in any ratio; the synthesis of polyimide polymers adopts the conventional synthesis method in the industry , using any one of in-situ polymerization, solution polycondensation, random copolymerization and block polymerization, the molar ratio of the aromatic dianhydride to the aromatic diamine is 0.9 to 1.1:1, and the synthesized poly The solid content of the amic acid resin is 10-22%, the synthesis temperature is controlled at 0-40°C, the reaction time is 3-10 hours after the dianhydride is added, and the viscosity of the polyamic acid resin is controlled at 1000mpa s~15 by rotational viscosity measurement. 10,000 mpa·s. 4. The high-insulation black matt polyimide film according to claim 1, characterized in that, the low-conductivity carbon black is a nanometer low-conductivity nano-carbon with a surface resistance of 10～500nm in the original ecology particle size ≥ 10 ⁸ black; the matting powder is any kind of silica produced by gas phase method and precipitation method, preferably fumed silica, whose particle size is 1-8um, and is micron-sized silica; the titanium dioxide is rutile type , any one of anatase type and mixed crystal type, preferably rutile type, and its particle size is 0.1-3.0 μm. 5. a kind of preparation method of high insulation black matt polyimide film is characterized in that, prepares according to the following steps: Step 1), at a temperature of 0-40°C, according to the conventional polyimide synthesis method, dissolve aromatic diamine in a polar organic solvent, then add aromatic dianhydride, and the reaction time is 3-12h Between, obtain polyamic acid resin, and guarantee its solid content is 10～22% according to mass percentage, viscosity is controlled at 1000mpa·s～150,000mpa·s; Wherein the mole of aromatic dianhydride and aromatic diamine The ratio is 0.9～1.1:1; Step 2), take 19.5 to 57.4 parts of filler dispersion according to the parts by weight and mix and stir with 150 parts of polyamic acid resin in the above step 1) to prepare black polyamic acid resin. According to the conventional two-way stretching method, the black polyamide Acid resin defoaming, cast into film, and then biaxially stretched, high temperature imidization to obtain high insulation black matt polyimide film. 6. according to the preparation method of a kind of high insulation black matte polyimide film described in claim 5, it is characterized in that, described filler dispersion is prepared according to the following steps: Step 2.1), at 10-40°C, mix 1.0 parts of low-conductivity carbon black with 9.0 parts of polar organic solvent according to parts by weight, and transfer to a shearing machine, at a shear rate of 500-5000 rpm Disperse for 1-10 hours under the same conditions, then transfer to the grinding equipment containing grinding media, and disperse for 0-4 hours under the condition of grinding speed of 500-5000 rpm to obtain a black dispersion; Step 2.2), at 10-40°C, mix 0.4-2.0 parts of matting powder with a particle size of 1-8 μm, 0.1-1.2 parts of titanium dioxide with a particle size of 0.1-3.0 μm and 9.0-44.2 parts of polar organic Mix the solvents, transfer to any one of shearing, ultrasonic, emulsifying, homogeneous dispersion, and magnetic dispersion equipment, and disperse for 1 to 5 hours at a rate of 500 to 5000 rpm to obtain a white dispersion; Step 2.3), at 10-40°C, mix the white dispersion liquid obtained in the above step 2.1) with the white dispersion liquid obtained in step 2.2), and transfer to a shearing machine at a shear speed of 500-5000 rpm Under the condition of shearing and dispersing for 0.5~10h, the filler dispersion liquid was obtained. 7. A method for preparing a high-insulation black matt polyimide film according to claim 6, wherein the grinding equipment in step 2.1) is a bead mill, a sand mill, a planetary ball mill or a three-roller Any of the grinding machines, wherein the bead mill, sand mill, and planetary ball mill are equipped with grinding media that are any of zirconia beads, zirconium beads, ceramic beads, glass beads and stainless steel beads, and the grinding media particles The diameter is 0.1-5mm. 8. A method for preparing a high-insulation black matte polyimide film according to claim 6, wherein the shearing machine involved in the above step 2.1) to step 2.3) is equipped with a shear disc made of Any one of stainless steel and polytetrafluoroethylene, preferably a stainless steel shearing disc, the edge of the shearing disc is serrated, and the unit dimensions of the shearing disc, reactor and liquid level height of the shearing machine involved are as follows Ratio: diameter of reactor: diameter of shearing disc: height of liquid level is 100: (25~75): (50~100). 9. A high insulation black matt polyimide multilayer film is characterized in that it is prepared according to the following method: Step 1), at a temperature of 0-40°C, according to the conventional polyamic acid synthesis method, dissolve aromatic diamine in a polar organic solvent, then add aromatic dianhydride, and the reaction time is between 3-12 hours Between, obtain polyamic acid resin, and guarantee its solid content is 10～22% according to mass percentage, viscosity is controlled at 1000mpa·s～150,000mpa·s; Wherein the molar ratio of aromatic dianhydride and aromatic diamine 0.9～1.1:1; Step 2), mix 19.5-57.4 parts of the filler dispersion with 150 parts of the polyamic acid resin in the above step 1), and defoam to obtain a high-insulation black matte polyamic acid resin; the filler dispersion is obtained according to the rights Prepared according to requirement 6; Step 3), the polyamic acid resin prepared in step 1) is defoamed and cast into a film to obtain a polyimide cast film, and the high-insulation black matt polyamic acid prepared in step 2) is The resin is coated on the top and/or bottom of the polyimide casting film, and after imidization, a high-insulation black matt polyimide multilayer film is obtained, wherein the thickness of the polyimide film is 8 μm to 50 μm, high The thickness of the insulating black matt polyimide coating is 2 μm to 50 μm.