CN109400933A - A kind of preparation method reflecting anti-corrosion Kapton - Google Patents
A kind of preparation method reflecting anti-corrosion Kapton Download PDFInfo
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- CN109400933A CN109400933A CN201811422203.4A CN201811422203A CN109400933A CN 109400933 A CN109400933 A CN 109400933A CN 201811422203 A CN201811422203 A CN 201811422203A CN 109400933 A CN109400933 A CN 109400933A
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- 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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- 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
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- 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
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- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
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Abstract
The invention discloses a kind of preparation methods for reflecting anti-corrosion Kapton, it coats one layer of polyamic acid solution in one layer of metal layer of PMDA/ODA Kapton surface magnetic control sputtering, then in metal level, is subject to the baking of echelon temperature, reach imidization degree, winding.Wherein polyamic acid solution includes diamines, dianhydride, polar solvent, modified Nano powder and pigment, and the modified Nano powder includes 20-30 parts of ocratations, 10-15 parts of aluminium oxide, 30-40 parts of silica, 1-5 parts of titanium oxide, 0.1-0.3 parts of hafnium oxide by weight.Polyamic acid coating transparent is frivolous, not only combines closely with metal layer but also protects metal layer from corrosion.
Description
Technical field
The present invention relates to a kind of Kapton, especially a kind of preparation method for reflecting anti-corrosion Kapton.
Background technique
Kapton is due to its excellent lower temperature resistance (cold resistance), heat-resisting quantity, and dielectric insulation is more and more
Be applied to electric utility, such as enamel insulated wire, military boat is usually by polyamides Asia especially in ship using upper
Amine film is overlayed on ship by the way of package or fitting.But since sea going ship not only needs resistance to sea wind rotten
Erosion, while the influence of radar wave is reflected again, it is therefore desirable to researching and developing a can reflect radar wave but also corrosion-resistant polyimides
Film.
Summary of the invention
It is thin that a kind of reflection anti-corrosion polyimides is provided the purpose of the present invention is to solve above-mentioned the deficiencies in the prior art
The preparation method of film.
To achieve the goals above, the preparation method of a kind of reflection anti-corrosion Kapton designed by the present invention, packet
Include following steps:
Step 1: preparing polyamic acid solution, first diamines is put into reaction kettle, and is dissolved with polar solvent, is then placed in and changes
Property nanometer powder and pigment, dianhydride is finally added portionwise again into reaction kettle, stirs, is prepared into required polyamic acid solution;
Wherein modified Nano powder includes 20-30 parts of ocratations, 10-15 parts of aluminium oxide, 30-40 parts of silica, 1-5 parts by weight
Titanium oxide, 0.1-0.3 part hafnium oxide;The pigment green, cobalt green, iron oxide red, cadmium red, red, quinacridone, phthalocyanine, benzo for iron
Imidazolone;
Step 2: preparation reflection anti-corrosion Kapton, first takes thickness thin from 5-125 microns of PMDA/ ODA polyimides
Film, the metal layer for being then 0.05-0.3 microns in its surface magnetic control sputtering a layer thickness, then coats one in metal level again
Layer is then placed on the conveyer belt for being provided with baking oven with a thickness of 3-7 microns of polyamic acid liquid, completes the thorough of polyamic acid
Bottom imidization, then reflection anti-corrosion Kapton can be obtained in winding, and wherein the echelon temperature of baking oven is 25-380 DEG C, passes
Send the 2-15 meters/min of speed of band.
The echelon temperature of the baking oven is specially
It is heated to 120 DEG C from 25 DEG C, keeps the temperature 30-60min,
160 DEG C are heated to, 15-30min is kept the temperature,
200 DEG C are heated to, 15-30min is kept the temperature,
250 DEG C are heated to, 30-60min is kept the temperature,
300 DEG C are heated to, 15-30min is kept the temperature,
380 DEG C are heated to, 5-15min is kept the temperature.
The form for the coating that the surface that the polyamic acid liquid is coated in metal layer uses can be doctor blade method, extrusion
Any one in die head method, transfer coated method.
The PMDA/ ODA Kapton is the common domestic and international Kapton having been commercialized.
The metal layer is one of AL, Cu, Ni or Sn.
The dianhydride prepared in polyamic acid solution is pyromellitic acid anhydride (PMDA), 3,3', 4,4'- biphenyl tetracarboxylic acid
Acid dianhydride (BPDA), 3,3', 4,4'- benzophenone tetracid dianhydride (BTDA), 4,4'- biphenyl ether dianhydride (ODPA), bisphenol A dianhydride
(BPADA), one or more of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids (6FPA);
The diamines be 4,4- diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4,4- diaminodiphenyl-methane (MDA),
Bis- (the trifluoromethyl) -4,4'- benzidines (TFMB) (TFMB) of 2,2'-, 4,4- diaminobenzene sulfone (4,4-DDS), 1,4- are bis-
One or more of (4- amino -2- 4-trifluoromethylphenopendant) benzene (6FAPB);
The polar solvent is dimethyl acetamide (DMAC), N-Methyl pyrrolidone (NMP), dimethylformamide (DMF)
One or more of.
The preparation method for a kind of reflection anti-corrosion Kapton that the present invention obtains, in PMDA/ ODA polyimides
One layer of metal layer of film surface magnetron sputtering, then one layer of polyamic acid solution is coated in metal level, it is subject to the baking of echelon temperature,
Reach imidization degree, winding.Polyamic acid coating transparent is frivolous, not only combines closely with metal layer but also protects metal layer
From corrosion.
Specific embodiment
Below with reference to embodiment, the present invention is further described.
Embodiment 1:
A kind of preparation method reflecting anti-corrosion Kapton provided in this embodiment, comprising the following steps:
Step 1: preparing polyamic acid solution, first diamines is put into reaction kettle, and is dissolved with polar solvent, is then placed in and changes
Property nanometer powder and pigment, dianhydride is finally added portionwise again into reaction kettle, stirs, is prepared into required polyamic acid solution;
Wherein modified Nano powder includes 20-30 parts of ocratations, 10-15 parts of aluminium oxide, 30-40 parts of silica, 1-5 parts by weight
Titanium oxide, 0.1-0.3 part hafnium oxide;The pigment green, cobalt green, iron oxide red, cadmium red, red, quinacridone, phthalocyanine, benzo for iron
Imidazolone;
Step 2: preparation reflection anti-corrosion Kapton, first takes thickness thin from 5-125 microns of PMDA/ ODA polyimides
Film, the metal layer for being then 0.05-0.3 microns in its surface magnetic control sputtering a layer thickness, then coats one in metal level again
Layer is then placed on the conveyer belt for being provided with baking oven with a thickness of 3-7 microns of polyamic acid liquid, completes the thorough of polyamic acid
Bottom imidization, then reflection anti-corrosion Kapton can be obtained in winding, and wherein the echelon temperature of baking oven is 25-380 DEG C, passes
Send the 2-15 meters/min of speed of band.
The echelon temperature of the baking oven is specially
It is heated to 120 DEG C from 25 DEG C, keeps the temperature 30-60min,
160 DEG C are heated to, 15-30min is kept the temperature,
200 DEG C are heated to, 15-30min is kept the temperature,
250 DEG C are heated to, 30-60min is kept the temperature,
300 DEG C are heated to, 15-30min is kept the temperature,
380 DEG C are heated to, 5-15min is kept the temperature.
The form for the coating that the surface that the polyamic acid liquid is coated in metal layer uses can be doctor blade method, extrusion
Any one in die head method, transfer coated method.
The dianhydride prepared in polyamic acid solution is pyromellitic acid anhydride (PMDA), 3,3', 4,4'- biphenyl tetracarboxylic acid
Acid dianhydride (BPDA), 3,3', 4,4'- benzophenone tetracid dianhydride (BTDA), 4,4'- biphenyl ether dianhydride (ODPA), bisphenol A dianhydride
(BPADA), one or more of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids (6FPA);
The diamines be 4,4- diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4,4- diaminodiphenyl-methane (MDA),
Bis- (the trifluoromethyl) -4,4'- benzidines (TFMB) (TFMB) of 2,2'-, 4,4- diaminobenzene sulfone (4,4-DDS), 1,4- are bis-
One or more of (4- amino -2- 4-trifluoromethylphenopendant) benzene (6FAPB);
The polar solvent is dimethyl acetamide (DMAC), N-Methyl pyrrolidone (NMP), dimethylformamide (DMF)
One or more of.
The metal layer is one of AL, Cu, Ni or Sn.
Embodiment 2:
A kind of preparation method reflecting anti-corrosion Kapton provided in this embodiment, comprising the following steps:
Step 1: preparing polyamic acid solution, first diamines is put into reaction kettle, and is dissolved with polar solvent, is then placed in and changes
Property nanometer powder and pigment, dianhydride is finally added portionwise again into reaction kettle, stirs, is prepared into required polyamic acid solution;
Wherein modified Nano powder includes 20 parts of ocratations, 10 parts of aluminium oxide, 30 parts of silica, 1 part of titanium oxide, 0.1 by weight
Part hafnium oxide;The pigment is cadmium red;
Step 2: preparation reflection anti-corrosion Kapton, first takes thickness thin from 5-125 microns of PMDA/ ODA polyimides
Film, the metal layer for being then 0.05-0.3 microns in its surface magnetic control sputtering a layer thickness, then coats one in metal level again
Layer is then placed on the conveyer belt for being provided with baking oven with a thickness of 3-7 microns of polyamic acid liquid, completes the thorough of polyamic acid
Bottom imidization, then reflection anti-corrosion Kapton can be obtained in winding, and wherein the echelon temperature of baking oven is 25-380 DEG C, passes
Send the 2-15 meters/min of speed of band.
Embodiment 3:
A kind of preparation method reflecting anti-corrosion Kapton provided in this embodiment, comprising the following steps:
Step 1: preparing polyamic acid solution, first diamines is put into reaction kettle, and is dissolved with polar solvent, is then placed in and changes
Property nanometer powder and pigment, dianhydride is finally added portionwise again into reaction kettle, stirs, is prepared into required polyamic acid solution;
Wherein modified Nano powder includes 25 parts of ocratations, 12 parts of aluminium oxide, 35 parts of silica, 3 parts of titanium oxide, 0.2 by weight
Part hafnium oxide;The pigment is benzimidazolone;
Step 2: preparation reflection anti-corrosion Kapton, first takes thickness thin from 5-125 microns of PMDA/ ODA polyimides
Film, the metal layer for being then 0.05-0.3 microns in its surface magnetic control sputtering a layer thickness, then coats one in metal level again
Layer is then placed on the conveyer belt for being provided with baking oven with a thickness of 3-7 microns of polyamic acid liquid, completes the thorough of polyamic acid
Bottom imidization, then reflection anti-corrosion Kapton can be obtained in winding, and wherein the echelon temperature of baking oven is 25-380 DEG C, passes
Send the 2-15 meters/min of speed of band.
Claims (5)
1. a kind of preparation method for reflecting anti-corrosion Kapton, it is characterised in that: the following steps are included:
Step 1: preparing polyamic acid solution, first diamines is put into reaction kettle, and is dissolved with polar solvent, is then placed in and changes
Property nanometer powder and pigment, dianhydride is finally added portionwise again into reaction kettle, stirs, is prepared into required polyamic acid solution;
Wherein modified Nano powder includes 20-30 parts of ocratations, 10-15 parts of aluminium oxide, 30-40 parts of silica, 1-5 parts by weight
Titanium oxide, 0.1-0.3 part hafnium oxide;The pigment green, cobalt green, iron oxide red, cadmium red, red, quinacridone, phthalocyanine, benzo for iron
Imidazolone;
Step 2: preparation reflection anti-corrosion Kapton, first takes thickness thin from 5-125 microns of PMDA/ ODA polyimides
Film, the metal layer for being then 0.05-0.3 microns in its surface magnetic control sputtering a layer thickness, then coats one in metal level again
Layer is then placed on the conveyer belt for being provided with baking oven with a thickness of 3-7 microns of polyamic acid liquid, completes the thorough of polyamic acid
Bottom imidization, then reflection anti-corrosion Kapton can be obtained in winding, and wherein the echelon temperature of baking oven is 25-380 DEG C, passes
Send the 2-15 meters/min of speed of band.
2. a kind of preparation method for reflecting anti-corrosion Kapton according to claim 1, it is characterised in that: described poly-
The form for the coating that the surface that amic acid liquid is coated in metal layer uses can be doctor blade method, extrusion die method, transfer
Any one in coating method.
3. a kind of preparation method for reflecting anti-corrosion Kapton according to claim 1, it is characterised in that: the system
Dianhydride in standby polyamic acid solution is pyromellitic acid anhydride (PMDA), 3,3', 4,4'- biphenyltetracarboxylic dianhydride (BPDA),
3,3', 4,4'- benzophenone tetracid dianhydride (BTDA), 4,4'- biphenyl ether dianhydride (ODPA), bisphenol A dianhydride (BPADA), 4,4'-
One or more of (hexafluoro isopropyl alkene) two anhydride phthalic acids (6FPA);
The diamines be 4,4- diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4,4- diaminodiphenyl-methane (MDA),
Bis- (the trifluoromethyl) -4,4'- benzidines (TFMB) (TFMB) of 2,2'-, 4,4- diaminobenzene sulfone (4,4-DDS), 1,4- are bis-
One or more of (4- amino -2- 4-trifluoromethylphenopendant) benzene (6FAPB);
The polar solvent is dimethyl acetamide (DMAC), N-Methyl pyrrolidone (NMP), dimethylformamide (DMF)
One or more of.
4. a kind of preparation method for reflecting anti-corrosion Kapton according to claim 1, it is characterised in that: the gold
Belonging to layer is one of AL, Cu, Ni or Sn.
5. a kind of preparation method for reflecting anti-corrosion Kapton according to claim 1, it is characterised in that: the baking
The echelon temperature of case is specially
It is heated to 120 DEG C from 25 DEG C, keeps the temperature 30-60min,
160 DEG C are heated to, 15-30min is kept the temperature,
200 DEG C are heated to, 15-30min is kept the temperature,
250 DEG C are heated to, 30-60min is kept the temperature,
300 DEG C are heated to, 15-30min is kept the temperature,
380 DEG C are heated to, 5-15min is kept the temperature.
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CN110437614A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of formable polyimide film |
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CN104672901A (en) * | 2015-02-28 | 2015-06-03 | 重庆杰博科技有限公司 | Transparent polyimide film and preparation method thereof |
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CN101466544A (en) * | 2006-04-18 | 2009-06-24 | 宇部兴产株式会社 | Polyimide film for coating metal and metal-laminated polyimide film |
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