CN109021566A - A kind of high insulation black matt polyimide film and multilayer film - Google Patents
A kind of high insulation black matt polyimide film and multilayer film Download PDFInfo
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- CN109021566A CN109021566A CN201810674009.9A CN201810674009A CN109021566A CN 109021566 A CN109021566 A CN 109021566A CN 201810674009 A CN201810674009 A CN 201810674009A CN 109021566 A CN109021566 A CN 109021566A
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- dispersion liquid
- polyamic acid
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 150
- 238000009413 insulation Methods 0.000 title claims abstract description 117
- 239000011347 resin Substances 0.000 claims abstract description 138
- 229920005989 resin Polymers 0.000 claims abstract description 138
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 133
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000004642 Polyimide Substances 0.000 claims abstract description 77
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 63
- 239000010408 film Substances 0.000 claims abstract description 51
- 239000011256 inorganic filler Substances 0.000 claims abstract description 49
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 49
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 36
- 239000004952 Polyamide Substances 0.000 claims abstract description 33
- 229920002647 polyamide Polymers 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims description 239
- 239000007788 liquid Substances 0.000 claims description 209
- 238000010008 shearing Methods 0.000 claims description 124
- 239000000945 filler Substances 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 67
- 239000007787 solid Substances 0.000 claims description 43
- 239000003495 polar organic solvent Substances 0.000 claims description 40
- 238000005266 casting Methods 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000010189 synthetic method Methods 0.000 claims description 26
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 25
- 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 description 25
- 238000000227 grinding Methods 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 150000004984 aromatic diamines Chemical class 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- 239000011324 bead Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 12
- 239000012808 vapor phase Substances 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 44
- 238000009740 moulding (composite fabrication) Methods 0.000 description 22
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 16
- 238000009826 distribution Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229940113088 dimethylacetamide Drugs 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- -1 4,4 '-diaminodiphenyl ethers Chemical class 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of high insulation black matt polyimide film and multilayer film, height insulation black matt polyimide film includes polyimide polymer and inorganic filler；It calculates in percentage by weight, with polyimide polymer and the total amount of inorganic filler for 100%, inorganic filler accounts for 4.35 ~ 21.88%；Polyimide polymer is routinely to synthesize, and inorganic filler includes the component of following parts by weight: 1.0 parts of low conductive black, 0.4~2.0 part of flatting silica, 0.1~1.2 part of titanium dioxide；The present invention in polyamic acid resin by adding different types of inorganic particulate, prepared black polyamide thin film and multilayer film not only has good light-proofness, also there are high electrical insulating properties, electrical strength has reached 134.7 Kv/mm, and the electrical strength of trilamellar membrane may be up to 180Kv/mm.
Description
Technical field
The invention belongs to electric thin insulating materials preparation technical fields, and in particular to a kind of high insulation black matt polyamides
Imines film and preparation method thereof and multilayer film.
Background technique
With the fast development of photovoltaic in the market, to the black polyamide thin film as photovoltaic cover film
Comprehensive performance is put forward higher requirements, that is, requires black polyamide thin film glossiness being reduced to 30GU hereinafter, and being able to maintain
Preferable electrical insulation capability, i.e. electrical strength >=80kV/mm.Due to influencing the electrical insulating property master of black matt polyimide film
Wanting factor is the additive amount and dispersing uniformity of the low conductive black of addition, if reducing carbon black additive amount directly affects film
Transmitance, screening effect is not able to satisfy product requirement, is only capable of the dispersing uniformity of the carbon black from film to improve electrical property
Energy.
Black matt polyimide film needs to be added in the preparation opacifying fillers, flatting silica, mineral black etc., and carbon black is made
It is the first choice of black film product for important black pigment, but because it is with certain electric conductivity, so that the electrical insulating property of final products
It is affected, admittedly carbon black is replaced using other black pigments or titanium dioxide to reduce light transmittance, but there are black for black pigment
Problem relatively low, that heat resistance is bad is spent, carbon black effect cannot be reached, polyimides black film preparation process requirement can not be met.
According to Zeng Chenghua et al. [titanium dioxide covering power analysis of Influential Factors, Minerals And Rocks, the 2nd phase of the 34th phase in 2014,18-
Page 21] report, an important indicator of titanium dioxide is covering power.Titanium dioxide has stable physics, chemical property and excellent
The features such as color power, covering power and heat resistance, is widely used in the fields such as plastic film, coating.In conjunction with the above black polyamides
There are problems for imines film, and many researchers replace part carbon black using titanium oxide in the industry, using its high covering power as black
The screener of color Kapton.Cologne PI Corp. patent like that: 104169330 A of CN report, using volume average particle size
For 0.1~1 μm of TiO2For screener, dispersing method is by carbon black and TiO2Pipeline mixing is supplied respectively to after being uniformly dispersed
Device, TiO2Additive amount is that 0.5%~1.5% of the total weight based on black polyamide film is not achieved when additive amount is few and makes us full
The shield effectiveness of meaning, additive amount are more than 1.5%, and mechanical performance especially elongation at break deteriorates, and film surface pin hole incidence is more,
The yield of film is caused to reduce, poor appearance.As it can be seen that the dispersing uniformity and stability that solve carbon black and opacifying fillers are to prepare to have
The key problem of high-insulativity black matt polyimide film and multilayer film, and the problem of always exist in the industry.
Summary of the invention
According to current black matt polyimide film there are the problem of, it is a kind of by charcoal it is an object of the invention to propose
Black, flatting silica and titanium dioxide are used in mixed way according to a certain percentage, are prepared into stable filler dispersion liquid, and by the filler dispersion liquid
It is added in polyamic acid resin, is prepared into high insulation black matt polyimide film and multilayer film；Utilize titanium dioxide, delustring
The powder synergistic effect mutual with carbon black difference particle, slackens flatting silica surface polarity, it is suppressed that network knot is formed between particle
Structure solves the problems, such as that flatting silica sedimentation and agglomeration, filler dispersion stabilization improve；The filler dispersion liquid is added to polyamic acid
It is thin to improve black polyamide using the electrical insulation capability of titanium dioxide, strong covering power, the rough property in surface, weatherability in resin
The electrical insulating property and weatherability of film, while light transmission rate and mirror surface luster can be reduced.
The object of the present invention is achieved like this:
A kind of high insulation black matt polyimide film, includes polyimide polymer and inorganic filler, and inorganic filler includes
The component of following parts by weight: 1.0 parts of low conductive black, 0.4~2.0 part of flatting silica, 0.1~1.2 part of titanium dioxide.
It calculates in percentage by weight, with polyimide polymer and the total amount of inorganic filler for 100%, inorganic filler is accounted for
4.35~21.88%。
Inorganic filler dispersion liquid is specifically the component by following weight grams: 1.0 parts of low conductive black, flatting silica 0.4~
2.0 parts, 0.1~1.2 part of titanium dioxide, 18.0~53.2 parts of polar organic solvent.
The low conductive black is sheet resistance >=10 that ecosystem partial size is 10~500nm8The low electrical-conductive nanometer of nanometer
Carbon black；The flatting silica is vapor phase method and any one silica that the precipitation method produce, preferably fumed silica, grain
Diameter is 1~8um, is micron silica；The polar organic solvent is n,N-Dimethylformamide, N, N- dimethylacetamide
The combination of any ratio of one or more of amine, dimethyl sulfoxide, N- methyl pyrrolidone and gamma-butyrolacton.
The titanium dioxide is any one of rutile-type, Detitanium-ore-type and mixed crystal type, preferably rutile-type, rutile
Type titanium dioxide crystal structure is fine and close, and refractive index is higher, and covering power is stronger, Gu preferred rutile-type.
The partial size of titanium dioxide has large effect, faster, the dispersion stable of the bigger sedimentation of partial size to itself dispersion stabilization
Property it is poor, partial size is smaller, due to Van der Waals force aggregate more easy to form between particle, is unfavorable for being uniformly dispersed, comprehensively consider, select
The partial size for selecting titanium dioxide is 0.1~3.0 μm, is submicron order titanium dioxide.
In view of filler grain is assembled in a solvent, cutter that the present invention uses equipped with shearing disk for stainless steel,
Any one of polytetrafluoro material, preferably stainless steel shearing disk, the edge of the shearing disk are zigzags.In view of point of filler
Efficiency is dissipated, the unit sizes of the matched shearing disk of the cutter that the present invention uses, reactor and liquid level follow following ratio,
That is reaction kettle diameter: shearing disk diameter: liquid level is 100:(25 ~ 75): (50 ~ 100).In view of the efficiency of filler dispersion
Than shear rate of the present invention is can with the naked eye observe in shearing container due to being dispersed with stirring at swirl center caused by liquid
Subject to shearing disk, specially 500 ~ 5000 turns/min.In view of between filler grain shock and friction can be with depolymerization filler grain
Aggregation, i.e., in system filer content it is relatively low be unfavorable for occur particle between friction and shock and influence dispersion effect, filler
The higher viscosity that can directly influence system of content, filer content is 5~12% in filler dispersion liquid in the present invention.
The polyimide polymer is prepared by 150 parts of polyamic acid resins, and polyamic acid resin solid content is
10%~22%。
The polyamic acid resin be by being prepared for aromatic diamine, aromatic dianhydride and polar organic solvent,
Middle aromatic diamine is 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), biphenyl two
Any one in amine or two kinds of mixtures；Aromatic dianhydride is pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracids two
Acid anhydride, any one in 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracid dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides or two kinds
The mixture of any of the above ratio；The polar organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl
The combination of any ratio of one or more of sulfoxide, N- methyl pyrrolidone and gamma-butyrolacton.The polyimides
Synthesis is using conventional synthetic methods in industry, using any one in in-situ polymerization, solution polycondensation, random copolymerization and block polymerization,
The aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1, guarantee polyamic acid resin according to mass percent
Solid content is 10~22%, and synthesis temperature is controlled at 0~40 DEG C, and the reaction time is 3~12h after aromatic dianhydride adds, and is gathered
Amic acid resin viscosity is with rotational viscometer observing and controlling system in the mpas of 1000mpas ~ 150,000.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 0~40 DEG C under conditions of, according to conventional polyamide acid synthetic method, aromatic diamine is dissolved
In polar organic solvent, aromatic dianhydride is added, the reaction time between 3~12h, obtains polyamic acid resin, and
Guarantee that its solid content is 10~22% according to mass percent, viscosity is controlled in the mpas of 1000mpas ~ 150,000；It is wherein described
Aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1；
Step 2, the filler dispersion liquid for taking 19.5~57.4 parts according to parts by weight and above-mentioned steps 1) 150 parts of polyamic acids
Resin is mixed obtained black polyamic acid resin and defoams black polyamic acid resin according to conventional biaxial tension method, flows
Prolong film forming, then through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
The filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 10~40 DEG C, according to parts by weight by 1.0 parts of partial sizes be 10~500nm low conductive black and 9.0
The mixing of part polar organic solvent, is transferred in cutter, under conditions of shear velocity is 500~5000 turns/min dispersion 1~
10h, after be transferred in milling apparatus, grinding rate be 500~5000 turns/min under the conditions of disperse 0~4h, obtain black dispersion
Liquid；
Step 2.2), at 10~40 DEG C, according to parts by weight by 0.4~2.0 part of partial size be 1~8 μm of flatting silica and 0.1~
1.2 parts of partial sizes are that 0.1~3.0 μm of titanium dioxide is mixed with 9.0~35.2 parts of polar organic solvents, be transferred to shearing, ultrasound, emulsification,
Homogeneous dissipates, magnetic force divides in any one in dispersing apparatus, and 1~5h is dispersed under conditions of rate is 500~5000 turns/min,
Obtain white dispersion liquid；
Step 2.3), at 10~40 DEG C, by above-mentioned steps 2.1) the obtained white of obtained black dispersion liquid and step 2.2)
Dispersion liquid mixing, is transferred in cutter, 0.5~10h of shearing dispersion under conditions of shear velocity is 500~5000 turns/min,
Obtain filler dispersion liquid.
Milling apparatus is appointing in ball mill, sand mill, planetary ball mill or three-roll grinder in the step 2.1)
It anticipates one kind, wherein ball mill, sand mill, planetary ball mill are zirconium oxide bead, zirconium pearl, ceramic bead, glass equipped with abrasive media
Any one in pearl and stainless shot, the abrasive media particle size are 0.1~5mm.
Material of the cutter involved in the step 2.1) to step 2.3) equipped with shearing disk is stainless steel, polytetrafluoro material
Any one of matter, preferably stainless steel shearing disk, the edge of the shearing disk are zigzags, the matched shearing of the cutter being related to
The unit sizes of disk, reactor and liquid level follow following ratio: reaction kettle diameter: shearing disk diameter: liquid level is
100:(25 ~ 75): (50 ~ 100).
A kind of high insulation black matt polyimide multilayer film carries out as follows:
Step 1), temperature be 0~40 DEG C under conditions of, according to conventional polyamide acid synthetic method, aromatic diamine is dissolved
In polar organic solvent, aromatic dianhydride is added, the reaction time between 3~12h, obtains polyamic acid resin, and
Guarantee that its solid content is 10~22% according to mass percent, viscosity is controlled in the mpas of 1000mpas ~ 150,000；It is wherein described
Aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1；
Step 2, the filler dispersion liquid for taking 19.5~48.4 parts according to parts by weight and above-mentioned steps 1) 150 parts of polyamic acids
Resin is mixed, defoaming, obtains high insulation black matt polyimide resin;
Step 3), by polyamic acid resin made from step 1) through defoaming, casting film-forming, be made polyimides casting films, and will
The high insulation black matt polyamic acid resin prepared in step 2 be coated in the upper surface of polyimides casting films and/or in the following,
High insulation black matt polyimide plural layers are made after high temperature imidization, wherein polyimides with a thickness of 8 μm~50 μm,
Height insulation black matt polyimide coating layer thickness is 2 μm~50 μm,
In view of the height of casting films and the face that is coated on insulate low matt polyamic acid resin layer in subsequent use process not
Easily layering, (the casting films imidization temperature in 3 is controlled at 140 ~ 180 DEG C above-mentioned steps, increases casting films and the high low matt that insulate
Cementability between polyamic acid resin layer.
Beneficial effects of the present invention are as follows: the present invention is sub- using the high insulation black matt polyamides that above-mentioned preparation method obtains
Amine film, compared with prior art, high insulation black matt polyimide film and multilayer film of the present invention have high electricity
Insulating properties, electrical strength have reached 134.7 Kv/mm, and the electrical strength of trilamellar membrane may be up to 180Kv/mm, and have good hide
Photosensitiveness.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
Embodiment 1:
A kind of high insulation black matt polyimide film: according to weight percent hundred be by 95.65% polyimide polymer and
4.35% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 19.5 kilograms.It is inorganic
Filler dispersion liquid is the component according to following weight grams: partial size produces for 1.0 kilograms of the low conductive black of 10nm, with vapor phase method
3 μm of partial size of silica be that 0.4 kilogram of flatting silica, 0.1 kilogram of the mixed-crystal titanium pigment of 0.1 μm of partial size, polarity are organic molten
Agent is 18.0 kilograms of n,N-Dimethylformamide.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 15.8 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 117 kilograms of n,N-dimethylacetamide, adds 17.2 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
150 kilograms of polyamic acid resins；Its solid content is 22%, viscosity 12000mpas；
Step 2 takes 19.5 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in revolving speed in machine, abrasive media is zirconium oxide bead, and partial size is grinding distribution 0.5h under conditions of 1mm, is obtained
Black dispersion liquid；
Step 2.2), at 10 DEG C, 0.4 kilogram of flatting silica and 0.1 kilogram of titanium dioxide and 9.0 kilograms of polarity is organic molten
Agent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 5h, obtains white under conditions of 500 turns/min
Dispersion liquid；
Step 2.3), at 10 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:25:50),
Shearing dispersion 0.5h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid content under conditions of 3000 turns/min
It is 7.7%.
Embodiment 2:
A kind of high insulation black matt polyimide film: according to weight percent hundred be by 78.12% polyimide polymer and
21.88% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 57.4 kilograms.Nothing
Machine filler dispersion liquid is the component according to following weight grams: partial size is given birth to for 1.0 kilograms of the low conductive black of 10nm, with vapor phase method
3 μm of partial size of silica of production is that 2.0 kilograms of flatting silica, 1.2 kilograms of the mixed-crystal titanium pigment of 0.1 μm of partial size, polarity are organic
Solvent is 53.2 kilograms of n,N-Dimethylformamide.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 4.0 kilograms of 4,4- diamino
Diphenyl ether and 2.2 kilograms of p-phenylenediamine are dissolved in 135 kilograms of n,N-dimethylacetamide, add 8.8 kilograms of equal benzene tetramethyls
Acid dianhydride, reaction 5h obtain polyamic acid resin；Its solid content is 10%, viscosity 1000mpas；
Step 2 takes 57.4 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in revolving speed in machine, abrasive media is zirconium oxide bead, and partial size is grinding distribution 0.5h under conditions of 1mm, is obtained
Black dispersion liquid；
Step 2.2), at 10 DEG C, 2.0 kilograms of flatting silica and 1.2 kilograms of titanium dioxide and 44.2 kilograms of polarity is organic
Solvent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 5h, obtains white under conditions of 500 turns/min
Color dispersion liquid；
Step 2.3), at 10 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred to the cutter (reaction kettle diameter: shearing disk diameter: liquid level 100:70:125) equipped with zigzag shearing disk
In, shearing dispersion 0.5h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid contains under conditions of 3000 turns/min
Amount is 7.3%.
Embodiment 3:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 93.46% polyimide polymer and
6.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 21 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: partial size produces for 1.0 kilograms of the low conductive black of 10nm, with vapor phase method
The silica that 3 μm of partial size is 0.1 kilogram of mixed-crystal titanium pigment, the polar organic solvent of 1.0 kilograms of flatting silica, 0.1 μm of partial size
It is 18.9 kilograms of n,N-Dimethylformamide.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), under conditions of temperature is 0 DEG C, according to conventional polyamide acid synthetic method, by 14.4 kilogram 4,4 '-diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time
In 3h, polyamic acid resin, solid content 20%, viscosity 1000mpas are obtained；
Step 2 takes 21.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in revolving speed in machine, abrasive media is zirconium oxide bead, and partial size is grinding distribution 0.5h under conditions of 1mm, is obtained
Black dispersion liquid；
Step 2.2), at 10 DEG C, 1.0 kilograms of flatting silica and 0.1 kilogram of titanium dioxide and 9.9 kilograms of polarity is organic molten
Agent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 5h, obtains white under conditions of 500 turns/min
Dispersion liquid；
Step 2.3), at 10 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred to the cutter (reaction kettle diameter: shearing disk diameter: liquid level 100:50:110) equipped with zigzag shearing disk
In, shearing dispersion 0.5h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid contains under conditions of 3000 turns/min
Amount is 10%.
A kind of high insulation black matt polyimide multilayer film carries out as follows:
Step 1), temperature be 0 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of aromatic diamines
It is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of aromatic dianhydride, the reaction time in 3h, is gathered
Amide acid resin, and guarantee that its solid content is 20% according to mass percent, viscosity 1000mpas；
Step 2, the filler dispersion liquid for taking 21.0 kilograms and above-mentioned steps 1) 150 kilograms of polyamic acid resins be mixed, disappear
Bubble obtains high insulation black matt polyamic acid resin；
Step 3) makes to obtain in addition a 150 kilograms of polyamic acid resins again according to the method for step 1), and will be according to
Polyamic acid resin made from step 1) method is through defoaming, 140 DEG C of casting film-formings, and polyimides casting films are made.It simultaneously will step
Rapid 2) the middle high insulation black matt polyamic acid resin prepared is coated in the upper surface of polyimides casting films, makes after imidization
High insulation black matt polyimide double-layer films are obtained, wherein polyimide thickness is 8 μm, height insulation black matt polyimide
Coating layer thickness is 2 μm；
The insulation black matt polyamic acid resin of height made from step 2) is coated in the height of step 3) preparation absolutely by step 4) again
High three layers of black matt polyimide of insulation is made on another side in edge black matt polyimide double-layer films, after imidization
Film, height insulation black matt polyimide coating layer thickness is 2 μm,.
Embodiment 4:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 91.46% polyimide polymer and
8.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 28 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 50nm, the grain produced with the precipitation method
0.8 kilogram of the rutile type titanium white of 5 μm of diameter 2.0 μm of .0 kilograms of silica 1, the partial sizes used as flatting silica, as pole
Use 25.2 kilograms of n,N-dimethylacetamide of property organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 20 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time exists
5h obtains polyamic acid resin, and guarantees that its solid content is 20% according to mass percent, viscosity 1000mpas；
Step 2, the filler dispersion liquid for taking 28.0 grams and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins are mixed
Black polyamic acid resin is made to defoam black polyamic acid resin, casting film-forming, then pass through according to conventional biaxial tension method
Biaxial tension, high temperature imidization obtain high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), step 1), at 20 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of revolving speed is 1200 turns/min, shearing dispersion 6h, after be transferred to row
It is 4000 turns/min in revolving speed, abrasive media is zirconium oxide bead, and partial size is grinding distribution under conditions of 1mm in planetary ball mill
2h obtains black dispersion liquid；
Step 2.2), at 20 DEG C, 1.0 kilograms of flatting silica and 0.8 kilogram of titanium dioxide and 16.2 kilograms of polarity is organic
Solvent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 4h, obtains white under conditions of 800 turns/min
Color dispersion liquid；
Step 2.3), at 20 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred to the cutter (reaction kettle diameter: shearing disk diameter: liquid level 100:50:100) equipped with zigzag shearing disk
In, shearing dispersion 2h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid content under conditions of 2500 turns/min
It is 10%.
A kind of high insulation black matt polyimide multilayer film carries out as follows:
Step 1), temperature be 0 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of aromatic diamines
It is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of aromatic dianhydride, the reaction time in 3h, is gathered
Amide acid resin, and guarantee that its solid content is 20% according to mass percent, 100,000 mpas of viscosity；
Step 2, the filler dispersion liquid for taking 28 kilograms and above-mentioned steps 1) 150 kilograms of polyamic acid resins be mixed, disappear
Bubble obtains high insulation black matt polyamic acid resin；
Step 3) makes to obtain in addition a 150 kilograms of polyamic acid resins again according to the method for step 1), and will be according to
Polyamic acid resin made from step 1) method is through defoaming, casting film-forming at 180 DEG C, and polyimides casting films, thickness is made
For.The high insulation black matt polyamic acid resin prepared in step 2 is coated in the upper table of polyimides casting films simultaneously
High insulation black matt polyimide double-layer films are made in face after imidization, wherein polyimide thickness is 50 μm, and height insulation is black
Color matt polyimide coating layer thickness is 50 μm；
Step 4), the height that the insulation black matt polyamic acid resin of height made from step 2) is coated in step 3) preparation again
High insulation black matt polyimide three is made on another side in insulation black matt polyimide double-layer films, after imidization
Tunic, wherein high insulation black matt polyimide coating layer thickness is 50 μm.
Embodiment 5:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 90.36% polyimide polymer and
9.64% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 40 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 100nm is produced with vapor phase method
1.2 kilograms of the rutile type titanium white of 8 μm of partial size 3.0 μm of .0 kilograms of silica 1, the partial sizes used as flatting silica, conduct
Use 36.8 kilograms of dimethyl sulfoxide of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 15 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of dimethyl sulfoxides, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time in 8h, obtains
Guarantee that its solid content is 20% to polyamic acid resin, and according to mass percent, viscosity 9000mpas；
Step 2 takes 32.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), step 1), at 30 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
It is transferred in the cutter equipped with zigzag shearing disk, under conditions of revolving speed is 3000 turns/min, shearing dispersion 4h obtains black
Dispersion liquid；
Step 2.2), at 30 DEG C, 1.0 kilograms of flatting silica and 1.2 kilograms of titanium dioxide and 27.8 kilograms of polarity is organic
Solvent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 3h, obtains white under conditions of 1200 turns/min
Color dispersion liquid；
Step 2.3), at 30 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred to the cutter (reaction kettle diameter: shearing disk diameter: liquid level 100:50:100) equipped with zigzag shearing disk
In, shearing dispersion 4h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid content under conditions of 2000 turns/min
It is 8.0%.
A kind of high insulation black matt polyimide multilayer film carries out as follows:
Step 1), temperature be 0 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of aromatic diamines
It is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of aromatic dianhydride, the reaction time in 3h, is gathered
Amide acid resin, and guarantee that its solid content is 20% according to mass percent, viscosity 9000mpas；
Step 2, the filler dispersion liquid for taking 40.0 kilograms and above-mentioned steps 1) 150 kilograms of polyamic acid resins be mixed, disappear
Bubble obtains high insulation black matt polyamic acid resin；
Step 3) makes to obtain in addition a 150 kilograms of polyamic acid resins again according to the method for step 1), and will be according to
Polyamic acid resin made from step 1) method is through defoaming, casting film-forming at 160 DEG C, and polyimides casting films are made.Simultaneously will
The high insulation black matt polyamic acid resin prepared in step 2 is coated in the upper surface of polyimides casting films, after imidization
High insulation black matt polyimide double-layer films are made, wherein polyimide thickness is 12.5 μm, and height insulation black matt is poly-
Acid imide coating layer thickness is 10 μm；
Step 4), the height that the insulation black matt polyamic acid resin of height made from step 2) is coated in step 3) preparation again
High insulation black matt polyimide three is made on another side in insulation black matt polyimide double-layer films, after imidization
Tunic, height insulation black matt polyimide coating layer thickness is 10 μm.
A kind of other embodiments of high insulation black matt polyimide multilayer film are identical with the method for the present embodiment, difference
It is that content characteristics change with different implementation, and identical with a kind of high insulation black matt polyimide film proportion,
No longer describe.
Embodiment 6:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 93.75% polyimide polymer and
6.25% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 20 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 300nm is produced with vapor phase method
0.6 kilogram of the rutile type titanium white for 2.0 μm of 0.4 kilogram of silica, the partial size that 2 μm of partial size is used as flatting silica, conduct
Use 18.0 kilograms of N- methyl pyrrolidone of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 40 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of N- methyl pyrrolidones, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time exists
8h obtains polyamic acid resin, and is 20% according to its solid content of mass percent, viscosity 9000mpas；
Step 2 takes 20.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 40 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 4000 turns/min under conditions of, shearing dispersion 2h, after be transferred to three-roll grinder
In, grinding distribution 1h under conditions of revolving speed is 2000 turns/min obtains black dispersion liquid；
Step 2.2), at 40 DEG C, 0.4 kilogram of flatting silica and 0.6 kilogram of titanium dioxide and 9.0 kilograms of polarity is organic molten
Agent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 2h, obtains white under conditions of 2000 turns/min
Dispersion liquid；
Step 2.3), at 40 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 8h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid content under conditions of 1200 turns/min
10%。
Embodiment 7:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 92.59% polyimide polymer and
7.41% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 24 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 500nm is produced with vapor phase method
0.6 kilogram of the rutile type titanium white for 0.1 μm of 0.8 kilogram of silica, the partial size that 1 μm of partial size is used as flatting silica, conduct
Use 21.6 kilograms of gamma-butyrolacton of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 40 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of gamma-butyrolactons, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time in 10h, obtains
Guarantee that its solid content is 20% to polyamic acid resin, and according to mass percent, viscosity 15000mpas；
Step 2 takes 24.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), step 1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of revolving speed is 5000 turns/min, shearing dispersion 1h, after be transferred to row
It is 500 turns/min in revolving speed, abrasive media is zirconium oxide bead, and partial size is grinding distribution under conditions of 1mm in planetary ball mill
4h obtains black dispersion liquid；
Step 2.2), at 15 DEG C, 0.8 kilogram of flatting silica and 0.6 kilogram of titanium dioxide and 12.6 kilograms of polarity is organic
Solvent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 1h, obtains white under conditions of 3000 turns/min
Color dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 10h, obtains a kind of stable filler dispersion liquid, dispersion liquid solid content is under conditions of 500 turns/min
10%。
Embodiment 8:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 90.03% polyimide polymer and
9.97% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 33 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 25nm, the grain produced with vapor phase method
1.0 kilograms of the rutile type titanium white of 5 μm of diameter 0.4 μm of .3 kilograms of silica 1, the partial sizes used as flatting silica, as pole
The 14.8 kilograms of DMAC N,N' dimethyl acetamides and 14.9 kilograms of N- crassitude alcohol/ketone mixtures that property organic solvent uses.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 60 kilograms of n,N-dimethylacetamide and 60 kilograms of N- methyl pyrrolidones, adds Pyromellitic Acid
15.6 kilograms of dianhydride, the reaction time in 10h, obtains polyamic acid resin, and is 20% according to its solid content of mass percent,
Viscosity 18000mpas；
Step 2 takes 33.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 15 DEG C, by 1.0 kilograms of low conductive black, 4.5 kilograms of n,N-dimethylacetamide and 4.5 kilograms
N- crassitude alcohol/ketone mixtures mixing, be transferred in the cutter equipped with zigzag shearing disk, shear velocity be 3000 turns/
Under conditions of min, shearing dispersion 2h, after be transferred in planetary ball mill, revolving speed be 2500 turns/min, abrasive media be oxidation
Zirconium pearl, partial size are grinding distribution 4h under conditions of 1mm, obtain black dispersion liquid；
Step 2.2), at 15 DEG C, by 1.3 kilograms of flatting silica and 1.0 kilograms of titanium dioxide and 10.3 kilograms of N, N- dimethyl
Acetamide and 10.4 kilograms of N- crassitude alcohol/ketone mixtures mixing, are transferred in the cutter equipped with zigzag shearing disk,
Shearing dispersion 1h, obtains white dispersion liquid under conditions of 1800 turns/min；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 5h, obtains a kind of stable filler dispersion liquid, dispersion liquid solid content is under conditions of 1000 turns/min
10%。
Embodiment 9:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 88.24% polyimide polymer and
11.76% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 33.3 kilograms.Nothing
Machine filler dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 30nm is produced with vapor phase method
5 μm of silica of partial size as 2.0 kilograms of flatting silica, 1.0 kilograms of the rutile type titanium white of 0.4 μm of partial size, as polarity
Use 29.3 kilograms of DMAC N,N' dimethyl acetamide of organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diaminos
Yl diphenyl ether is dissolved in 120 kilograms of gamma-butyrolactons, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h obtains 150,000
Gram polyamic acid resin；Its solid content is 20%, viscosity 15000mpas；
Step 2 takes 33.3 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in sand mill,
It is 2500 turns/min in revolving speed, abrasive media is zirconium pearl, and partial size is grinding distribution 4h under conditions of 0.1mm, obtains black dispersion
Liquid；
Step 2.2), at 15 DEG C, 2.0 kilograms of flatting silica and 1.0 kilograms of titanium dioxide and 20.3 kilograms of polarity is organic
Solvent mixing, is transferred in ultrasonic disperse equipment, ultrasonic disperse 2h obtains white dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h, obtains a kind of stable filler dispersion liquid, dispersion liquid solid content is under conditions of 2000 turns/min
12%。
Embodiment 10:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 90.91% polyimide polymer and
9.09% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 30 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 30nm produces partial size with vapor phase method
For 6 μm of silica as 1.3 kilograms of flatting silica, 0.7 kilogram of the rutile type titanium white that partial size is 1.0 μm, with N, N- bis-
Methylacetamide is as 27.0 kilograms of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
To 150 kilograms of polyamic acid resins；Its solid content is 20%, viscosity 15000mpas；
150 kilograms of polyamic acid resins that step 2, the filler dispersion liquid for taking 30.0 kilograms and step 1) obtain, which are mixed, to be made
It obtains black polyamic acid resin to defoam black polyamic acid resin, casting film-forming according to conventional biaxial tension method, then through double
To stretching, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in sand mill,
It is 2500 turns/min in revolving speed, abrasive media is zirconium pearl, and partial size is grinding distribution 4h under conditions of 0.8 μm, obtains black dispersion
Liquid；
Step 2.2), at 15 DEG C, 1.3 kilograms of flatting silica and 0.7 kilogram of titanium dioxide and 18.0 kilograms of polarity is organic
Solvent mixing, is transferred to mulser, and emulsion dispersion 4h under the conditions of revolving speed is 2000 turns/min obtains white dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h, obtains a kind of stable filler dispersion liquid, dispersion liquid solid content is under conditions of 2000 turns/min
10%。
Embodiment 11:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 91.46% polyimide polymer and
8.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 28 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 30nm, the grain produced with the precipitation method
6 μm of silica of diameter are as 1.3 kilograms of flatting silica, 0.5 kilogram of the rutile type titanium white, organic as polarity of 0.4 μm of partial size
Use 25.2 kilograms of DMAC N,N' dimethyl acetamide of solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
To 150 kilograms of polyamic acid resins；Its solid content is 20%, viscosity 12000mpas；
Step 2 takes 28.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in sand mill,
It is 2500 turns/min in revolving speed, abrasive media is zirconium pearl, and partial size is grinding distribution 4h under conditions of 1.2 mm, obtains black dispersion
Liquid；
Step 2.2), at 15 DEG C, 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 16.2 kilograms of polarity is organic
Solvent mixing, is transferred to homogenizer, and emulsion dispersion 4h under the conditions of revolving speed is 1200 turns/min obtains white dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h, obtains a kind of stable filler dispersion liquid, dispersion liquid solid content is under conditions of 2000 turns/min
10%。
Embodiment 12:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 84.27% polyimide polymer and
15.73% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 56 kilograms.It is inorganic
Filler dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 20nm is produced with vapor phase method
0.5 kilogram of the rutile type titanium white of 6 μm of partial size 0.6 μm of .3 kilograms of silica 1, the partial sizes used as flatting silica, conduct
Use 53.2 kilograms of DMAC N,N' dimethyl acetamide of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 4.0 kilograms of 4,4- diamino
Diphenyl ether and 2.2 kilograms of p-phenylenediamine are dissolved in 135 kilograms of n,N-dimethylacetamide, add 8.8 kilograms of equal benzene tetramethyls
Acid dianhydride, reaction 5h obtain polyamic acid resin；Its solid content is 10%, viscosity 15000mpas；
Step 2, the filler dispersion liquid for taking 56 kilograms and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins are mixed
Black polyamic acid resin is made to defoam black polyamic acid resin, casting film-forming, then pass through according to conventional biaxial tension method
Biaxial tension, high temperature imidization obtain high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), step 1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of revolving speed is 3000 turns/min, shearing dispersion 2h, after be transferred to sand
It is 2500 turns/min in revolving speed in grinding machine, abrasive media is zirconium pearl, and partial size is grinding distribution 4h under conditions of 3 mm, is obtained black
Color dispersion liquid；
Step 2.2), at 15 DEG C, 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 44.2 kilograms of polarity is organic
Solvent mixing, is transferred in magnetic stirring apparatus, is dispersed with stirring 4h under the conditions of revolving speed is 1200 turns/min, obtains white dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h under conditions of 2000 turns/min, obtains a kind of stable filler dispersion liquid, and dispersion liquid solid content is 5%.
Embodiment 13:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 88.93% polyimide polymer and
11.07% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 35 kilograms.It is inorganic
Filler dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 20nm is produced with the precipitation method
0.5 kilogram of the rutile type titanium white of 6 μm of partial size 1.0 μm of .3 kilograms of silica 1, the partial sizes used as flatting silica, conduct
Use 32.2 kilograms of DMAC N,N' dimethyl acetamide of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 9.9 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 127.5 kilograms of n,N-dimethylacetamide, adds 5.4 kilograms of pyromellitic acid anhydrides and 7.2 kilograms
Biphenyl acid acid anhydride, reaction 5h obtain 150 kilograms of polyamic acid resins；Its solid content is 15%, viscosity 15000mpas；
Step 2 takes 35.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, revolving speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in ball mill,
It is 2500 turns/min in revolving speed, abrasive media is zirconium pearl, and partial size is grinding distribution 4h under conditions of 4 mm, obtains black dispersion
Liquid；
Step 2.2), at 15 DEG C, 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 23.2 kilograms of polarity is organic
Solvent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 1h, obtains white under conditions of 1800 turns/min
Color dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h under conditions of 2000 turns/min, obtains a kind of stable filler dispersion liquid, and dispersion liquid solid content is 8%.
Embodiment 14:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 91.72% polyimide polymer and
8.28% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 23.3 kilograms.It is inorganic
Filler dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 20nm is produced with the precipitation method
0.5 kilogram of the rutile type titanium white of 6 μm of partial size 3.0 μm of .3 kilograms of silica 1, the partial sizes used as flatting silica, conduct
Use 20.5 kilograms of gamma-butyrolacton of polar organic solvent.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 15.8 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 117 kilograms of n,N-dimethylacetamide, adds 17.2 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
150 kilograms of polyamic acid resins；Its solid content is 22%, viscosity 12000mpas；
Step 2, the filler dispersion liquid for taking 23.3 kilograms and above-mentioned steps 1) obtain polyamic acid resin mixing be made black
Color polyamic acid resin defoams black polyamic acid resin, casting film-forming according to conventional biaxial tension method, then through two-way drawing
It stretches, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, shear velocity be 5000 turns/min under conditions of disperse 1h, after be transferred to containing grinding medium
In the milling apparatus of matter, disperses 4h under the conditions of grinding rate is 500 turns/min, obtain black dispersion liquid；Milling apparatus is row
Planetary ball mill, abrasive media are zirconium oxide bead, and the abrasive media particle size is 1mm.
Step 2.2), at 15 DEG C, by 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 11.5 kilograms of polarity
Organic solvent mixing, is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 1h, obtains under conditions of 1800 turns/min
To white dispersion liquid；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h, obtains a kind of stable filler dispersion liquid, dispersion liquid solid content is under conditions of 2000 turns/min
12%。
Comparative example 1:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 88.93% polyimide polymer and
11.07% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 28.8 kilograms.Nothing
Machine filler dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 20nm is produced with the precipitation method
6 μm of .3 kilograms of silica 1s used as flatting silica of partial size, the N used as polar organic solvent, N- dimethylacetamide
26.5 kilograms of amine.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 4.0 kilograms of 4,4- diamino
Diphenyl ether and 2.2 kilograms of p-phenylenediamine are dissolved in 135 kilograms of n,N-dimethylacetamide, add 8.8 kilograms of equal benzene tetramethyls
Acid dianhydride, reaction 5h obtain polyamic acid resin；Its solid content is 15%, viscosity 15000mpas；
Step 2, the filler dispersion liquid for taking 28.8 kilograms and above-mentioned steps 1) obtain polyamic acid resin mixing be made black
Color polyamic acid resin defoams black polyamic acid resin, casting film-forming according to conventional biaxial tension method, then through two-way drawing
It stretches, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), step 1), at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of revolving speed is 3000 turns/min, shearing dispersion 2h, after be transferred to pearl
It is 2500 turns/min in revolving speed in grinding machine, abrasive media is zirconium pearl, and partial size is grinding distribution 4h under conditions of 4 mm, is obtained black
Color dispersion liquid；
Step 2.2), at 15 DEG C, 1.3 kilograms of flatting silica is mixed with 17.5 kilograms of polar organic solvent, is transferred to and is furnished with
In the cutter of zigzag shearing disk, shearing dispersion 1h, obtains white dispersion liquid under conditions of 1800 turns/min；
Step 2.3), at 15 DEG C, by above-mentioned steps 1) the obtained white dispersion liquid of obtained black dispersion liquid and step 2 is mixed
It closes, is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:75),
Shearing dispersion 4h under conditions of 2000 turns/min, obtains a kind of stable filler dispersion liquid, and dispersion liquid solid content is 8%.
A kind of high insulation black matt polyimide multilayer film carries out as follows:
Step 1), temperature be 0 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of aromatic diamines
It is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of aromatic dianhydride, the reaction time in 3h, is gathered
Amide acid resin, and guarantee that its solid content is 20% according to mass percent, viscosity 1000mpas；
Step 2, the filler dispersion liquid for taking 28.8 kilograms and above-mentioned steps 1) 150 kilograms of polyamic acid resins be mixed, disappear
Bubble obtains high insulation black matt polyamic acid resin；
Step 3) makes to obtain in addition a 150 kilograms of polyamic acid resins again according to the method for step 1), and will be according to
Polyamic acid resin made from step 1) method is through defoaming, casting film-forming at 160 DEG C, and polyimides casting films are made.Simultaneously will
The high insulation black matt polyamic acid resin prepared in step 2 is coated in the upper surface of polyimides casting films, after imidization
High insulation black matt polyimide double-layer films are made, wherein polyimide thickness is 12.5 μm, and height insulation black matt is poly-
Acid imide coating layer thickness is 10 μm；
Step 4), the height that the insulation black matt polyamic acid resin of height made from step 2) is coated in step 3) preparation again
High insulation black matt polyimide three is made on another side in insulation black matt polyimide double-layer films, after imidization
Tunic, height insulation black matt polyimide coating layer thickness is 10 μm.
Comparative example 2:
A kind of high insulation black matt polyimide film, according to weight percent hundred be by 93.75% polyimide polymer and
6.25% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 20 kilograms.It is inorganic to fill out
Material dispersion liquid is the component according to following weight grams: 1.0 kilograms of the low conductive black of partial size 50nm, the grain produced with the precipitation method
5 μm of .0 kilograms of silica 1s used as flatting silica of diameter, the n,N-dimethylacetamide 18 used as polar organic solvent
Kilogram.
A kind of preparation method of high insulation black matt polyimide film, prepares by the following method:
Step 1), temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
Polyamic acid resin；Polyamic acid resin solid content is 20%, viscosity 15000mpas；
Step 2 takes 20.0 kilograms of filler dispersion liquid and above-mentioned steps 1) obtained 150 kilograms of polyamic acid resins mix and stir
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps:
Step 2.1), step 1), at 20 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of revolving speed is 1200 turns/min, shearing dispersion 6h, after be transferred to row
It is 4000 turns/min in revolving speed, abrasive media is zirconium oxide bead, and partial size is grinding distribution under conditions of 1mm in planetary ball mill
2h obtains black dispersion liquid；
Step 2, at 20 DEG C, 1.0 kilograms of flatting silica is mixed with 9.0 kilograms of polar organic solvent, is transferred to equipped with sawtooth
In the cutter of shape shearing disk, shearing dispersion 4h, obtains white dispersion liquid under conditions of 800 turns/min；
Step 3), at 20 DEG C, by above-mentioned steps 1) obtained black dispersion liquid mixes with the white dispersion liquid that step 2 obtains,
It is transferred in the cutter equipped with zigzag shearing disk (reaction kettle diameter: shearing disk diameter: liquid level 100:50:100),
Shearing dispersion 2h, obtains a kind of stable filler dispersion liquid, wherein dispersion liquid solid content is under conditions of 2500 turns/min
10%。
The performance of the high insulation black matt polyimide film of embodiment 1-14 and comparative example 1-2 preparation is as shown in table 1,
Comparative example and comparative example, when carbon black additive amount is identical, shaded effect is relatively preferable after adding titanium dioxide.When increase titanium white
After the partial size of powder, shading rate decline, electrical property relative drop, the partial size preferably 0.1 of titanium dioxide in black polyamide thin film ~
0.6μm.Electrical strength significantly increases after adding titanium dioxide in black polyamide thin film, up to 134kv/mm.Embodiment 1
The performance of the high insulation black matt polyimide trilamellar membrane of preparation is as shown in table 2, and electrical property is up to 180kv/mm.
The high insulation black matt polyimide monofilm of table 1
Claims (9)
1. a kind of high insulation black matt polyimide film includes polyimide polymer and inorganic filler, which is characterized in that
Inorganic filler includes the component of following parts by weight: 1.0 parts of low conductive black, 0.4~2.0 part of flatting silica, titanium dioxide 0.1~
1.2 part.
2. high insulation black matt polyimide film according to claim 1, which is characterized in that according to weight percent
It calculates, with polyimide polymer and the total amount of inorganic filler for 100%, inorganic filler accounts for 4.35 ~ 21.88%.
3. high insulation black matt polyimide film according to claim 1, which is characterized in that it is poly- to prepare polyimides
The raw material for closing object includes aromatic diamine, aromatic dianhydride and polar organic solvent, and wherein aromatic diamine is 4,4 '-diaminos
Yl diphenyl ether, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), any one or two kinds of mixing in benzidine
Object；Aromatic dianhydride is pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracids
Dianhydride, 3, the mixture of any one or two or more any ratios in 3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides；Polarity is organic
Solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide, N- methyl pyrrolidone and gamma-butyrolacton
One or more of any ratio combination；The synthesis of polyimide polymer is used using conventional synthetic methods in industry
Any one in in-situ polymerization, solution polycondensation, random copolymerization and block polymerization, the aromatic dianhydride and aromatic diamine rub
You guarantee that synthesized polyamic acid resin solid content is 10~22% than being 0.9~1.1:1, according to mass percent, synthesis
Temperature is controlled at 0~40 DEG C, and the reaction time is 3~10h after dianhydride adds, and polyamic acid resin viscosity is measured with rotary viscosity
Control is in the mpas of 1000mpas ~ 150,000.
4. high insulation black matt polyimide film according to claim 1, which is characterized in that the low conductive black
For sheet resistance >=10 of 10~500nm of ecosystem partial size8The low electrical-conductive nanometer carbon black of nanometer；The flatting silica be vapor phase method and
Any one silica of precipitation method production, preferably fumed silica, partial size are 1~8um, are micron order titanium dioxide
Silicon；The titanium dioxide is any one in rutile-type, Detitanium-ore-type and mixed crystal type, preferably rutile-type, partial size 0.1
~3.0 μm.
5. a kind of preparation method of high insulation black matt polyimide film, which is characterized in that made in accordance with the following steps
It is standby:
Step 1), temperature be 0~40 DEG C under conditions of, according to conventional polyimide synthetic method, aromatic diamine is dissolved
In polar organic solvent, aromatic dianhydride is added, the reaction time between 3~12h, obtains polyamic acid resin, and
Guarantee that its solid content is 10~22% according to mass percent, viscosity is controlled in the mpas of 1000mpas ~ 150,000；It is wherein described
Aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1；
Step 2, the filler dispersion liquid for taking 19.5~57.4 parts according to parts by weight and above-mentioned steps 1) 150 parts of polyamic acids
Resin is mixed obtained black polyamic acid resin and defoams black polyamic acid resin according to conventional biaxial tension method, flows
Prolong film forming, then through biaxial tension, high temperature imidization obtains high insulation black matt polyimide film.
6. a kind of preparation method of high insulation black matt polyimide film according to claim 5, which is characterized in that institute
Filler dispersion liquid is stated to be prepared in accordance with the following steps:
Step 2.1), at 10~40 DEG C, 1.0 parts of low conductive blacks and 9.0 parts of polar organic solvents are mixed according to parts by weight
Close, be transferred in cutter, shear velocity be 500~5000 turns/min under conditions of disperse 1~10h, after be transferred to containing grind
In the milling apparatus of medium, 0~4h is dispersed under the conditions of grinding rate is 500~5000 turns/min, obtains black dispersion liquid；
Step 2.2), at 10~40 DEG C, according to parts by weight by 0.4~2.0 part of partial size be 1~8 μm of flatting silica and 0.1~
1.2 parts of partial sizes are that 0.1~3.0 μm of titanium dioxide is mixed with 9.0~44.2 parts of polar organic solvents, be transferred to shearing, ultrasound, emulsification,
Homogeneous dissipates, magnetic force divides in any one in dispersing apparatus, and 1 ~ 5h is dispersed under conditions of rate is 500 ~ 5000 turns/min, is obtained
To white dispersion liquid；
Step 2.3), at 10~40 DEG C, by above-mentioned steps 2.1) the obtained white of obtained white dispersion liquid and step 2.2)
Dispersion liquid mixing, is transferred in cutter, 0.5~10h of shearing dispersion under conditions of shear velocity is 500~5000 turns/min,
Obtain filler dispersion liquid.
7. a kind of preparation method of high insulation black matt polyimide film according to claim 6, which is characterized in that
Milling apparatus is any one in ball mill, sand mill, planetary ball mill or three-roll grinder in step 2.1), wherein pearl
Grinding machine, sand mill, planetary ball mill are in zirconium oxide bead, zirconium pearl, ceramic bead, bead and stainless shot equipped with abrasive media
Any one, the abrasive media particle size is 0.1~5mm.
8. a kind of preparation method of high insulation black matt polyimide film according to claim 6, which is characterized in that on
State cutter involved in step 2.1) to step 2.3) equipped with shearing disk material be stainless steel, polytetrafluoro material it is any one
Kind, preferably stainless steel shearing disk, the edge of the shearing disk are zigzags, the matched shearing disk of the cutter being related to, reactor
Follow following ratio: reaction kettle diameter with the unit sizes of liquid level: shearing disk diameter: liquid level is 100:(25 ~ 75):
(50 ~ 100).
9. a kind of high insulation black matt polyimide multilayer film, which is characterized in that prepared as follows:
Step 1), temperature be 0~40 DEG C under conditions of, according to conventional polyamide acid synthetic method, aromatic diamine is dissolved
In polar organic solvent, aromatic dianhydride is added, the reaction time between 3~12h, obtains polyamic acid resin, and
Guarantee that its solid content is 10~22% according to mass percent, viscosity is controlled in the mpas of 1000mpas ~ 150,000；It is wherein described
Aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1；
Step 2, by 19.5~57.4 parts of filler dispersion liquid and above-mentioned steps 1) 150 parts of polyamic acid resins be mixed
Mixing, defoaming obtain high insulation black matt polyamic acid resin；Wherein filler dispersion liquid is prepared according to claim 6；
Step 3), by polyamic acid resin made from step 1) through defoaming, casting film-forming, be made polyimides casting films, and will
The high insulation black matt polyamic acid resin prepared in step 2 be coated in the upper surface of polyimides casting films and/or in the following,
High insulation black matt polyimide plural layers are made after imidization, wherein Kapton is high with a thickness of 8 μm~50 μm
The black matt polyimide coating layer thickness that insulate is 2 μm~50 μm.
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| CN110126390A (en) * | 2019-05-21 | 2019-08-16 | 浙江福斯特新材料研究院有限公司 | A kind of preparation method of low-k high-dimensional stability coated polyimide metal plate |
| CN111793360A (en) * | 2020-07-09 | 2020-10-20 | 安徽国风塑业股份有限公司 | Black polyimide film with high electrical strength and high shielding property and preparation process thereof |
| CN113561637A (en) * | 2021-01-18 | 2021-10-29 | 东台市盛源智能装备制造有限公司 | Material-holding printing screen |
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