CN117659697A - Black matt polyimide film - Google Patents
Black matt polyimide film Download PDFInfo
- Publication number
- CN117659697A CN117659697A CN202211031651.8A CN202211031651A CN117659697A CN 117659697 A CN117659697 A CN 117659697A CN 202211031651 A CN202211031651 A CN 202211031651A CN 117659697 A CN117659697 A CN 117659697A
- Authority
- CN
- China
- Prior art keywords
- polyimide film
- polyimide
- film
- black
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000006229 carbon black Substances 0.000 claims abstract description 38
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 description 51
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 50
- 239000000243 solution Substances 0.000 description 40
- 239000000758 substrate Substances 0.000 description 34
- 239000011521 glass Substances 0.000 description 33
- 230000008033 biological extinction Effects 0.000 description 30
- 238000003756 stirring Methods 0.000 description 30
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 25
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 20
- 239000003085 diluting agent Substances 0.000 description 18
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 16
- 229920005575 poly(amic acid) Polymers 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 206010052143 Ocular discomfort Diseases 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application is a black matt polyimide film, comprising: polyimide accounting for 87-97 wt% of the film, wherein the polyimide is prepared by polymerizing aromatic dianhydride and aromatic diamine to form polyimide precursor, and chemically cyclizing the polyimide precursor to obtain polyimide, wherein the aromatic dianhydride at least comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the content of the aromatic dianhydride accounts for more than 20mol% of the total aromatic dianhydride; the aromatic diamine at least comprises one p-phenylenediamine, and the content of the aromatic diamine accounts for 5-40 mol% of the total aromatic diamine; carbon black, which accounts for 2 to 8wt% of the film; silica powder having a particle size of between1-10 mu m, density less than 1g/cm 3 Which accounts for 1 to 5wt% of the film; and the film has a 60 degree gloss of less than 60 and a dielectric dissipation factor of less than 0.045 at 10 GHz.
Description
Technical Field
A black extinction polyimide film, especially a polyimide film with an addition density less than 1g/cm 3 Silica powder providing the black matted polyimide film with a gloss of less than 60 and a dielectric of less than 0.045 at 10GHzAn electrical loss factor.
Background
Polyimide films are commonly used as coverlays for flexible circuit boards, where black matt polyimide films are commonly used for special flexible board applications due to their special optical properties.
In recent years, with the high performance and high functionality of electronic devices, there is still a need for a cover layer that maintains electrical insulation properties, especially at high frequencies, while also maintaining acceptable structural and optical properties to provide protection of the electronic components from unnecessary visual inspection and destruction.
However, the conventional black extinction polyimide film mainly uses carbon black as pigment, colorant and the like to reduce the transmittance, thereby achieving the functions of covering and protecting; in addition, the colored polyimide film can lead a large amount of reflected light generated on the surface of the film to be colored, so that a matting agent is added to reduce the visual discomfort caused by film reflection.
However, the electrical characteristics of carbon black tend to increase the dielectric loss factor (Df) value of the film, which can cause noise or delay in electronic communication transmission, and increase the difficulty of realizing a low dielectric black matt polyimide film.
US840315B2 proposes a black matt polyimide film using silica as a matting agent. Because silicon dioxide is an inorganic compound, the dielectric coefficient (Dk) and the dielectric loss factor (Df) of the silicon dioxide are high, the density is high, the volume of the silicon dioxide is small under the same weight adding proportion, the silicon dioxide can achieve the effect of low glossiness only by adding the silicon dioxide to a certain amount, the defects such as holes and the like can be caused on the film, and the mechanical property of the film can be influenced.
US10336045B2 proposes a substrate formulation using pyromellitic dianhydride, 4' -diaminodiphenyl ether and p-phenylenediamine, which has a low thermal expansion coefficient, but when the proportion of pyromellitic dianhydride is high, moisture in the air is easily absorbed, so that the electrical characteristics are affected, and the substrate formulation cannot be applied to high-frequency communication.
In order to improve the above problems, the present application proposes a black matt polyimide film having excellent electrical characteristics and maintaining a low gloss.
Disclosure of Invention
The application relates to a black extinction polyimide film, which comprises polyimide, wherein the polyimide accounts for 87-97 wt% of the film, the polyimide is a polyimide precursor formed by polymerizing aromatic dianhydride and aromatic diamine, and the polyimide precursor is chemically cyclized to obtain polyimide, wherein the aromatic dianhydride at least comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the content of the aromatic dianhydride accounts for more than 20mol% of the total aromatic dianhydride; the aromatic diamine at least comprises one p-phenylenediamine, and the content of the aromatic diamine accounts for 5-40 mol% of the total aromatic diamine; carbon black, which accounts for 2 to 8wt% of the film; silica powder having a particle size of 1 to 10 mu m and a density of less than 1g/cm 3 It comprises 1 to 5wt% of the film; and the film has a 60 degree gloss of less than 60, a dielectric dissipation factor of less than 0.045 at 10GHz, and a coefficient of thermal expansion of less than 35ppm/°C.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the embodiments of the present application, and it is apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
It is particularly pointed out that similar substitutions and modifications made in relation to the present application will be apparent to a person skilled in the art and are all considered to be included in the present application. It will be apparent to those skilled in the relevant art that modifications and variations can be made in the methods and applications described herein, or in the appropriate variations and combinations, without departing from the spirit and scope of the application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application.
The application is carried out according to the conventional conditions or the conditions suggested by manufacturers if the specific conditions are not noted, and the raw materials or auxiliary materials and the reagents or the equipment are conventional products which can be obtained commercially if the manufacturers are not noted.
The black matt polyimide film is produced by using polyimide precursor (polyamic acid), silica powder and carbon black. Wherein the silicon dioxide powder and the carbon black are respectively prepared into extinction sizing agent and carbon black sizing agent, and then are mixed with polyimide precursor, and the polyimide precursor is cyclized into polyimide through a chemical cyclizing process.
Preparation of polyimide precursor
The polyimide precursor is composed of aromatic dianhydride and aromatic diamine.
At least one of the aromatic dianhydrides is 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA), and the addition amount of the 3,3', 4' -biphenyltetracarboxylic dianhydride is at least 20mol% to the total mole number of the dianhydride.
At least one of the aromatic diamines is p-Phenylenediamine (PDA), and the addition amount of the p-phenylenediamine is 5 to 40mol% of the total mole number of the diamine.
As the solvent, dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ -butyrolactone (GBL), N-Dimethylformamide (DMF) may be used for the preparation of the polyimide precursor, and dimethylacetamide is used as the solvent in the present application.
Preparation of black slurry
Carbon black and dimethylacetamide are mixed according to the weight ratio of 1:7, preparing a solution according to the proportion, stirring uniformly, and vibrating for 1 hour by using an ultrasonic vibrator to finish black slurry.
The carbon black of the black slurry is insulating carbon black.
The weight ratio of the carbon black and the dimethylacetamide in the black slurry can be adjusted according to the requirement, wherein the weight ratio of the carbon black is related to the penetrability and the dielectric loss factor, and if the ratio of the carbon black is excessive, the dielectric loss factor can be increased, and the carbon black addition amount of the black polyimide film accounts for 2-8wt% of the black polyimide film
Preparation of matting slurry
Silica powder, a dispersing agent and dimethylacetamide in a weight ratio of 1:0.05:19 is prepared into a solution, and the solution is stirred uniformly and then is oscillated for 2 hours by an ultrasonic oscillator to finish the extinction sizing agent.
The silica powder of the matting slurry is hollow and has a density of less than 1g/cm 3 。
The silica powder of the matting slurry has a particle size of 1 to 10. Mu.m.
The weight ratio of the silica powder, the dispersing agent and the dimethylacetamide of the extinction slurry can be adjusted according to requirements, wherein the weight ratio of the silica powder is related to the glossiness and the dielectric loss factor, and if the proportion of the silica powder is too small, the glossiness and the dielectric loss factor of the black extinction polyimide film are increased, so that the difficulty of visual inspection, the increase of transmission loss and the like of a finished product are caused.
Preparation of black extinction polyimide film
Mixing the black slurry, the extinction slurry and the polyimide precursor, uniformly stirring, and then adding a catalyst and a dehydrating agent for chemical cyclization, wherein the dehydrating agent can be acetic anhydride or benzoic anhydride, and acetic anhydride is selected as the dehydrating agent in the application; wherein the catalyst may be pyridine, 3-picoline, 2-picoline, 4-picoline, isoquinoline, quinoline, triethylamine, and preferably selected from pyridine, 3-picoline, 2-picoline, 4-picoline, and 3-picoline is used as the catalyst in the present application.
The catalyst and the dehydrating agent can be used independently, or can be mixed with a solvent for dilution and then added into the mixed solution, the mixed solution mixed with the dehydrating agent and the catalyst is uniformly stirred and then defoamed by using a centrifugal defoamer, and the defoamed solution is coated on a glass substrate and then is coated by using a scraper with a gap of 900 mu m. And (3) placing the coated sample in an oven at 80 ℃ for baking for 20 minutes, heating to 170 ℃ for baking for 20 minutes, heating to 350 ℃ for baking for 20 minutes as final treatment, placing glass in water after baking, and taking off the film to obtain the black extinction polyimide film.
The substrate in the film-making process can be a metal plate besides glass, when the black extinction polyimide film is made of the metal plate, the metal plate is required to be taken down after baking and drying in an oven at 80 ℃, the taken-down semi-dried film is fixed on a metal frame, and the black extinction polyimide film can be obtained after the baking at 170 ℃ for 20 minutes and the baking at 350 ℃ for 20 minutes as final treatment.
The black matt polyimide film may have a film thickness of 5 μm to 100. Mu.m.
The black extinction polyimide film can be used as a covering film, and the covering film is provided with a glue layer and a base layer film.
Examples
Hereinafter, the present application will be specifically described with reference to examples, but the present application is not limited thereto. Further, details of the raw materials indicated in shorthand are presented in the following examples.
Raw materials of polyimide:
PMDA: pyromellitic dianhydride
BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride
PDA: para-phenylenediamine
ODA:4,4' -diaminodiphenyl ether
Raw materials of the extinction sizing agent:
high density silica powder: SFP-30MHE with a density of 2.2g/cm 3 Manufactured by Denka Co
Low density silica powder: cell Spheres-NF, density of 0.63g/cm 3 Pacific Cement Co Ltd
Raw materials of carbon black slurry:
carbon black: specific BLACK 4A (SB 4A), manufactured by Evonik Co
Dispersing agent:
dispersing agent: BYK-180 manufactured by Pick chemical Co
Solvent:
DMAc: dimethylacetamide
AA: acetic anhydride
AP: 3-methylpyridine
< detection method >
The properties of the composite films obtained in the following examples were measured using the following methods.
Coefficient of thermal expansion (100 ℃ C. To 200 ℃ C.). Measured in accordance with ASTM D696 using a model Q400 TMA instrument from TA Instruments. The thermal expansion coefficient of the polyimide film at 100-200 ℃ is measured, and the heating rate is set to 10 ℃/min. In order to remove the stress caused by the heat treatment, the residual stress is removed by the first measurement and then the second measurement is used as the actual value.
Optical penetration: measured according to ISO 14782 using an instrument model NDH-2000N from Nippon Denshoku Co.
Gloss level: gloss at 60 degrees was measured using a BYK brand, model micro-TRI-gloss meter.
[ example 1 ]
Preparation of carbon black slurry
1g of carbon black and 7 g of DMAc are prepared into a solution, and after being uniformly stirred, the solution is vibrated for 1 hour by an ultrasonic vibrator to complete black slurry.
Preparation of low-density extinction sizing agent
0.5 g of low-density silicon dioxide powder, 0.025 g of dispersing agent and 9.5 g of DMAc are prepared into a solution, and after being uniformly stirred, the solution is vibrated for 2 hours by an ultrasonic vibrator, so that the extinction sizing agent is finished.
Preparation of polyimide precursor
Adding 8.909 g of PDA into 467.5 g of DMAc, stirring and mixing, adding 15.15 g of BPDA after PDA dissolution is completed, adding 24.746 g of ODA after stirring and reacting for 60 minutes, slowly adding 32.021 g of PMDA after the PDA dissolution is completed, controlling the temperature at 25 ℃, stirring and reacting for two hours, and using trace amount of PMDA to carry out viscosity adjustment, thus finally obtaining the polyamic acid solution with the solid content of 15% and the viscosity of 255,600 cps.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.553 g of low-density matting slurry, 40 g of polyamic acid solution and 20 g of DMAc are uniformly stirred, AA and DMAc are diluted in a weight ratio of 5 to 1, and 5.21 ml of AA diluent and 3.54 ml of AP diluent are respectively added after AP and DMAc are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ example 2 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
Preparation of polyimide film precursor the same as in example 1
Preparation of black extinction polyimide film
2.087 g of carbon black slurry, 5.2174 g of low-density extinction slurry, 40 g of polyamic acid solution and 20 g of DMAc are uniformly stirred, AA and DMAc are diluted in a weight ratio of 5 to 1, and 5.21 ml of AA diluent and 3.54 ml of AP diluent are respectively added after AP and DMAc are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ example 3 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
Preparation of polyimide precursor
6.532 g of PDA is added into 467.5 g of DMAc, stirred and mixed, 14.810 g of BPDA is added after PDA dissolution is completed, 28.221 g of ODA is added after stirring and reacting for 60 minutes, 32.278 g of PMDA is slowly added after the PDA dissolution is completed, the temperature is controlled at 25 ℃, and after stirring and reacting for two hours, micro PMDA is used for viscosity adjustment, and finally a polyamic acid solution with 15% of solid content and 223,400cps of viscosity is obtained.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.5532 g of low-density matting slurry, 40 g of polyamic acid solution and 20 g of DMAc are uniformly stirred, AA and DMAc are diluted in a weight ratio of 5 to 1, and 5.10 ml of AA diluent and 3.46 ml of AP diluent are respectively added after AP and DMAc are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ example 4 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
Preparation of polyimide precursor
8.067 g of PDA is added into 467.5 g of DMAc, stirred and mixed, 43.894 g of BPDA is added after PDA dissolution is completed, 22.405 g of ODA is added after stirring and reacting for 60 minutes, 7.525 g of PMDA is slowly added after the PDA dissolution is completed, the temperature is controlled at 25 ℃, and after stirring and reacting for two hours, a trace amount of PMDA is used for viscosity adjustment, so that a polyamic acid solution with 15% of solid content and 233,000cps of viscosity is finally obtained.
Preparation of black matt polyimide film
2.043 g of carbon black slurry, 2.5532 g of low-density matting slurry, 40 g of polyamic acid solution and 20 g of DMAc are uniformly stirred, AA and DMAc are diluted in a weight ratio of 5 to 1, and 4.72 ml of AA diluent and 3.20 ml of AP diluent are respectively added after AP and DMAc are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ example 5 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
Preparation of polyimide precursor
Adding 3.748 g of PDA into 467.5 g of DMAc, stirring and mixing, adding 6.374 g of BPDA after PDA dissolution is completed, adding 27.762 g of ODA after stirring and reacting for 60 minutes, slowly adding 43.851 g of BPDA after the PDA dissolution is completed, controlling the temperature at 25 ℃, stirring and reacting for two hours, and using trace amount of BPDA to carry out viscosity adjustment, thus finally obtaining the polyamic acid solution with the solid content of 15% and the viscosity of 242,000 cps.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.5532 g of low-density matting slurry, 40 g of polyamic acid solution and 20 g of DMAc were uniformly stirred, and then AA and DMAc were diluted in a weight ratio of 5 to 1, and then AP and DMAc were diluted in a weight ratio of 1 to 1, and 4.39 ml of AA diluted solution and 2.97 ml of AP diluted solution were added respectively. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ comparative example 1 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
Preparation of polyimide precursor
39.487 g of ODA is added into 467.5 g of DMAc, stirred and mixed, 42.368 g of PMDA is added after the ODA is dissolved, the temperature is controlled at 25 ℃, the stirring reaction is carried out for two hours, and then a trace amount of PMDA is used for viscosity adjustment, so that a polyamic acid solution with the solid content of 15% and the viscosity of 246,000cps is finally obtained.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.5532 g of low-density extinction slurry, 40 g of polyamide acid solution and 20 g of dimethylacetamide are uniformly stirred, acetic anhydride and dimethylacetamide are diluted in a weight ratio of 5 to 1, and 4.99 ml of acetic anhydride diluent and 3.38 ml of 3-methylpyridine diluent are respectively added after 3-methylpyridine and dimethylacetamide are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was applied to a glass substrate and then applied using a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ comparative example 2 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
And (3) preparing a polyimide precursor.
8.087 g of PDA is added into 467.5 g of DMAc, stirred and mixed, 13.049 g of PMDA is added after PDA dissolution is completed, 27.809 g of ODA is added after stirring and reacting for 60 minutes, 32.856 g of PMDA is slowly added after the PDA dissolution is completed, the temperature is controlled at 25 ℃, and after stirring and reacting for two hours, micro PMDA is used for viscosity adjustment, so that a polyamic acid solution with 15% of solid content and 240,000cps of viscosity is finally obtained.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.5532 g of low-density extinction slurry, 40 g of polyamide acid solution and 20 g of dimethylacetamide are uniformly stirred, acetic anhydride and dimethylacetamide are diluted in a weight ratio of 5 to 1, and 5.41 ml of acetic anhydride diluent and 3.67 ml of 3-methylpyridine diluent are respectively added after 3-methylpyridine and dimethylacetamide are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was applied to a glass substrate and then applied using a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ comparative example 3 ]
The carbon black slurry was prepared as in example 1.
Preparation of high-density extinction sizing agent
3g of high-density silica powder, 0.5 g of dispersant and 27 g of DMAc were prepared into a solution, and after stirring uniformly, the solution was ground for 2 hours at a zirconium bead filling rate of 0.5mm and a zirconium bead filling rate of 14% by volume, to complete a high-density matting slurry.
Preparation of polyimide precursor the same as in example 1
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 1.2766 g of high-density extinction slurry, 40 g of polyamide acid solution and 20 g of dimethylacetamide are uniformly stirred, acetic anhydride and dimethylacetamide are diluted in a weight ratio of 5 to 1, and 5.21 ml of acetic anhydride diluent and 3.54 ml of 3-methylpyridine diluent are respectively added after 3-methylpyridine and dimethylacetamide are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was applied to a glass substrate and then applied using a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ comparative example 4 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
And (3) preparing a polyimide precursor.
9.171 g of PDA is added into 467.5 g of DMAc, stirred and mixed, 6.238 g of BPDA is added after PDA dissolution is completed, 25.472 g of ODA is added after stirring and reacting for 60 minutes, 40.926 g of PMDA is slowly added after the PDA dissolution is completed, the temperature is controlled at 25 ℃, and after stirring and reacting for two hours, micro PMDA is used for viscosity adjustment, so that a polyamic acid solution with 15% of solid content and 287,200cps of viscosity is finally obtained.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.553 g of low-density matting slurry, 40 g of polyamic acid solution and 20 g of DMAc are uniformly stirred, AA and DMAc are diluted in a weight ratio of 5 to 1, and 5.37 ml of AA diluent and 3.64 ml of AP diluent are respectively added after AP and DMAc are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
[ comparative example 5 ]
The carbon black slurry was prepared as in example 1.
The low density matting slurry was prepared as in example 1.
And (3) preparing a polyimide precursor.
23.404 g of PDA is added into 467.5 g of DMAc, stirred and mixed, 7.075 g of BPDA is added after PDA dissolution is completed, 4.815 g of ODA is added after stirring and reaction is carried out for 60 minutes, 46.419 g of PMDA is slowly added after the PDA dissolution is completed, the temperature is controlled at 25 ℃, and after stirring and reaction is carried out for two hours, a trace amount of PMDA is used for viscosity adjustment, so that a polyamic acid solution with 15% of solid content and 263,000cps of viscosity is finally obtained.
Preparation of black extinction polyimide film
2.043 g of carbon black slurry, 2.553 g of low-density matting slurry, 40 g of polyamic acid solution and 20 g of DMAc are uniformly stirred, AA and DMAc are diluted in a weight ratio of 5 to 1, and 6.09 ml of AA diluent and 4.13 ml of AP diluent are respectively added after AP and DMAc are diluted in a weight ratio of 1 to 1. After uniform stirring, defoaming was performed using a centrifugal deaerator, and the defoamed solution was poured onto a glass substrate and coated with a doctor blade having a gap of 900 μm. The coated sample was placed in an 80 ℃ oven for 20 minutes, then baked for 20 minutes at 170 ℃ at a rate of 1.8 ℃/min, and then baked for 20 minutes at 350 ℃ at a rate of 2.0 ℃/min.
The glass substrate was immersed in water, and a black matt polyimide film having a thickness of 25 μm was peeled off from the glass substrate.
Examples are compared with the comparative example table as follows:
list one
As shown in table 1, it was confirmed that the black matt polyimide film manufactured according to the examples of the present application not only maintained the original optical characteristics, but also exhibited lower dielectric loss factors.
The key to the embodiments being able to exhibit lower dielectric dissipation factors is their lower density of silicon dioxide powder. When the density is small, it means that the proportion of air present in the powder particles is high, and thus the dielectric characteristics of the black matt polyimide film can be reduced.
In addition, the low-density silica powder also affects the gloss of the film, and the number of particles present on the film surface is important in addition to the size and addition ratio of matting particles.
The low density silica powder in the examples exhibits lower gloss than the comparative examples because it has a lower density and the volume of the powder is higher than the total volume of the film at the same weight addition.
The above description of embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it would be obvious to those skilled in the art that various improvements and modifications can be made to the present application without departing from the principles of the present application, and such improvements and modifications fall within the scope of the claims of the present application.
Claims (4)
1. A black matt polyimide film, comprising:
polyimide accounting for 87-97 wt% of the polyimide film, wherein the polyimide is obtained by polymerizing aromatic dianhydride and aromatic diamine to form polyimide precursor and then chemically cyclizing, the aromatic dianhydride at least comprises 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the content of the 3,3', 4' -biphenyl tetracarboxylic dianhydride accounts for more than 20mol% of the total content of the aromatic dianhydride; the aromatic diamine at least comprises one p-phenylenediamine, and the total content of the one p-phenylenediamine accounts for 5-40 mol% of the total content of the aromatic diamine;
carbon black accounting for 2 to 8 weight percent of the polyimide film; and
silica powder with particle size of 1-10 μm and density less than 1g/cm 3 1 to 5 weight percent of the polyimide film;
wherein the polyimide film has a 60 degree gloss of less than 60 and a dielectric dissipation factor of less than 0.045 at 10 GHz.
2. The polyimide film of claim 1, wherein the polyimide film has a coefficient of thermal expansion of less than 35ppm/°c.
3. The polyimide film according to claim 1, wherein the polyimide film has a thickness of 5 to 100 μm.
4. The polyimide film according to claim 1, wherein the silica powder is hollow and has a density of less than 1g/cm 3 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211031651.8A CN117659697A (en) | 2022-08-26 | 2022-08-26 | Black matt polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211031651.8A CN117659697A (en) | 2022-08-26 | 2022-08-26 | Black matt polyimide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117659697A true CN117659697A (en) | 2024-03-08 |
Family
ID=90084910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211031651.8A Pending CN117659697A (en) | 2022-08-26 | 2022-08-26 | Black matt polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117659697A (en) |
-
2022
- 2022-08-26 CN CN202211031651.8A patent/CN117659697A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109734910B (en) | Polyimide, and preparation method and application thereof | |
| EP3106487B1 (en) | Polyamide acid composition and polyimide composition | |
| TW201930403A (en) | Polyimide film and preparation method thereof for preparing flexible copper clad laminate, and flexible copper clad laminate and electronic device comprising the same | |
| KR20200030268A (en) | Polyimide Film with Improved Surface Property and Method for Preparing the Same | |
| CN112823181A (en) | Polyimide film, method for preparing same, and flexible metal-clad laminate including same | |
| CN112409621B (en) | High-strength low-dielectric-property polyimide multilayer film and preparation method thereof | |
| JP7405560B2 (en) | Resin compositions, resin films, and metal-clad laminates | |
| KR19980079256A (en) | Polyimide precursor solution, preparation method thereof, film or film obtained from such solution and preparation method of film | |
| KR20210084279A (en) | Resin composition, resin film and metal clad laminate | |
| JP2021070592A (en) | Silica particle, resin composition, resin film, and metal-clad laminate | |
| CN112480405A (en) | Intrinsic polyimide film with low dielectric loss factor and preparation method thereof | |
| US11597880B2 (en) | Polymer film and method for manufacturing the same | |
| CN117659697A (en) | Black matt polyimide film | |
| JP6858693B2 (en) | Polyamide acid for high-frequency substrate materials, polyimide for high-frequency substrate materials, polyimide film for high-frequency substrate materials, polyimide molded products for high-frequency substrate materials, and high-frequency substrates | |
| TWI822297B (en) | Black matt polyimide film | |
| JP6789186B2 (en) | Polyamic acid, polyimide, electronic substrate, high frequency substrate and coverlay film | |
| JPH02202950A (en) | Silicon polyimide precursor composition | |
| KR102472528B1 (en) | Polyamic acid composition and polyimide comprising the same | |
| JP2007169392A (en) | Polyamic acid varnish composition and metal polyimide composite | |
| CN113501985A (en) | Preparation method of polyimide film with low dielectric constant | |
| CN116715850B (en) | High-temperature-resistant polyimide composite material composition and construction method thereof | |
| CN115505261B (en) | Polymer film and method for producing same | |
| JP7319950B2 (en) | Polyamic acid, polyimide, polyimide film, materials for electronic substrates and electronic substrates | |
| WO2014115827A1 (en) | Black polyimide film | |
| CN115505262B (en) | Polymer film and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |