CN110229609A - A method of the polyimide paint with functional material and use the coating preparation functional form polyimide material - Google Patents
A method of the polyimide paint with functional material and use the coating preparation functional form polyimide material Download PDFInfo
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- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- 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
- 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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- 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
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- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention discloses a kind of polyimide paint with functional material, which is mixed with by polyamic acid solution and functional inorganic filling；Wherein, by dicarboxylic anhydride and diamines, reactive polymeric forms polyamic acid solution in organic solvent.The invention also discloses the method that functional form polyimide material is prepared on Kapton is coated in using the above-mentioned polyimide paint with functional material.Compared with conventional adhesive, for polyimide paint of the present invention in polyimide surface prepares coating or binding function material, coating and polyimide film have better adhesive strength, while coating is resistant to higher temperature, up to 400 DEG C or more；When with 3M600 adhesive tape test coating adhesion, coating shedding area is no more than 10%；And after carrying out bend test to coating, most of region there are no apparent wrinkle and crackle.
Description
Technical field
The present invention relates to a kind of polyimide paint with functional material, further relate to prepare using above-mentioned polyimide paint
The method of functional form polyimide material belongs to polymeric membrane technical field.
Background technique
Polyimides (PI) is a kind of with excellent heat resistance, mechanical performance, lower temperature resistance, dielectric properties, radiation hardness
High-molecular organic material, be widely used in because of its brilliant performance Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film,
The fields such as laser.The main application form of polyimides has the following aspects: 1. films；2. coating；3. advanced composite material；
4. engineering plastics；5. foamed plastics；6. adhesive；7. seperation film；8. photoresist；9. the application in microelectronic component.
Film product is polyimides using earliest one of commodity, and the basic physical properties in addition to that can meet various product are wanted
Ask outer, the multiple performances such as more standby high intensity, high tenacity, abrasion performance, high temperature resistant are also able to satisfy various set in process
Meter requires, and is a kind of high-temperature insulation material with competitive advantage.It is widely used in soft board, semiconductor packages, the photovoltaic (sun
Can) electronic fields such as the energy, liquid crystal display, it is applied to each industries such as space flight military project, machinery, automobile in motor field.However,
Since PI film surface is smooth and chemical mobility of the surface is low, cause its surface adhesive property poor, which greatly limits polyamides Asias
The application range of amine.Modified traditional polyimide surface includes soda acid processing, plasma treatment, ion beam and surface grafting etc.
Method, however usually there are various problems in these methods, soda acid processing can destroy the chemical structure of Kapton, thus shadow
Ring its performance, and the methods of plasma treatment, ion beam and surface grafting often higher cost, and be not suitable for being mass produced
Processing.And through adhesive in polyimide surface coating or bonding other materials, it tends to be difficult to meet required bonding
Intensity, while some additional problems can be caused.Polyurethane adhesive and silicon rubber bonder are usually to polyamides in traditional adhesive
Imines film has a preferable adhesive strength, but this kind of adhesive solidify after with the mechanical performance of polyimide matrix material itself
Difference is larger, and the usual non-refractory of these adhesive (200 DEG C or more), polyimide material under high temperature environment in application,
It will receive the limitation of adhesive, to influence its application range.
Polyimide material generally requires it with additional performance when being applied to certain fields.It is being applied to military affairs
When field, need the material that there is good electromagnetic wave shielding effect and camouflage effect, common polyimides is to electricity
Magnetic wave does not have good shield effectiveness, and in different topography and geomorphology operations, the various military affairs prepared by polyimide material
Tent, clothing etc. need to adapt to the color of environment, and to achieve the purpose that camouflage, this just needs to coat one on polyimide
It a little exogenous electromagnetic shielding materials and dyes on polyimide, therefore bonding coats these materials on polyimide
When, need polyimides that can keep the excellent properties such as high-low temperature resistant, dielectric properties and the mechanical performance of script substantially.Electricity at present
Magnetic shielding material is usually metal alloy powders, ferromagnetic material conducting polymer and carbon material, and above-mentioned electromagnetic shielding material is made
Applied when on polyimide film for coating, it usually needs coated on material requested in conjunction with different adhesives it is cured, and
Adhesive is applied when on polyimide film, often adhesive strength is weaker and non-refractory, and influences its application.
Summary of the invention
Goal of the invention: technical problem to be solved by the invention is to provide a kind of polyimide paint with functional material,
It is thin with polyimides since the substrate of coating itself is also polyimide when the coating is coated in Kapton surface
Film matrix itself does not have mechanical performance difference, will not change the structure of Kapton itself, therefore not only there is no apply
The problem of covering Kapton non-refractory after coating, and just by functional material while coating coating of the present invention
Appendix saves on polyimide film and goes bonding coating functions material coating this operation step again together.
The present invention also technical problems to be solved, which are to provide for the above-mentioned polyimide paint with functional material to be coated in, gathers
The method on sub- amide film surface.
In order to solve the above technical problems, the technical scheme adopted by the invention is as follows:
A kind of polyimide paint with functional material, the polyimide paint is by polyamic acid solution and functional inorganic
Filler is mixed with；Wherein, polyamic acid solution reacts gained by dicarboxylic anhydride and diamines in organic solvent.
Wherein, the polyimide paint is prepared by the component of following mass percent:
Dicarboxylic anhydride: 5~15%；
Diamines: 5~15%；
Organic solvent: 40~60%；
Functional inorganic filling: 10~30%.
Wherein, the general structure of the dicarboxylic anhydride is as follows:
Wherein, in above-mentioned dicarboxylic anhydride R structure are as follows:
Wherein, the general structure of the diamines is as follows:
Wherein, in above-mentioned diamines M structure are as follows:
Wherein, the organic solvent is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAC) or N- first
Any one in base pyrrolidones (NMP) or any several combination.
Wherein, functional inorganic filling be with improve polyimide high temperature-resistant, intensity, electromagnetic shielding performance and
The inorganic filler of color, the inorganic filler of inorganic filler, raising polyimides electromagnetic shielding effect including high temperature resistance improve
The inorganic filler of polyimides intensity and the inorganic pigment coloured for polyimides；Wherein, the inorganic of high temperature resistance is filled out
Material is the combination of one or more of titanium dioxide, silica, calcium oxide, boron nitride or carbon nanotube；Improve polyamides
The inorganic filler of imines intensity is titanium dioxide and/or silica；Improve the inorganic filler of polyimides electromagnetic shielding effect
For copper powder and/or silver powder；Inorganic pigment for polyimides coloring is one of iron oxide, titanium dioxide or carbon black.
Wherein, the solid content (Solute mass fraction) of the polyimide paint is 10~20%, according to functional inorganic
The characteristic of filler chooses the polyimide paint of different solid contents.
Wherein, functional inorganic filling is solid particle or powder, and average grain diameter is 0.01 μm~10 μm.
The method for preparing functional form polyimide material using the above-mentioned polyimide paint with functional material, takes suitable
For coating (mixed liquor) uniformly coated on polyimide film, heating schedule solidification obtains surface appendix functional material coating
Kapton；
Specifically:
In conjunction with the mechanical strength of different functional inorganic filling and required coating, corresponding type and solid content are chosen
Polyimide paint；First functional inorganic filling and polyamic acid solution are mixed in appropriate proportions, obtain polyamides Asia coating, then
Polyimide paint is coated on polyimide base material using one of brushing method, spin-coating method or dip coating, temperature programming
Solidification, temperature-rise period are as follows: 70~90 DEG C of 2~5h of heat preservation；120~160 DEG C of 0.5~2h of heat preservation；200~240 DEG C of heat preservations 0.5~
3h；260~300 DEG C of 0.5~1.5h of heat preservation；Obtaining the polyimide of surface appendix functional material coating, (polyimides is thin
Film).
Compared with conventional adhesive, the coating based on coating preparation of the present invention has on polyimide to be preferably bonded by force
Degree, while the introducing of functional material imparts polyimide high temperature resistant, high intensity, electromagnetic shielding and coloring in coating
Function.
Polyimides causes its adhesive property poor since its chemical mobility of the surface is low, when needing to coat one on polyimide
A bit when exogenous functional material, need that functional material is coated in polyimide surface using adhesive, due to bonding
Agent adhesive strength is not high and non-refractory, therefore the strong influence application of polyimides；Polyimide paint of the invention,
It can also persistently work at high temperature while good bonding intensity is provided, and functional material can also be introduced into polyamides Asia
On amine film, to assign Kapton a variety of excellent performances.
Above-mentioned polyimide paint by different types of polyamic acid solution and the preparation of different functional inorganic filling and
At, wherein had by the coating that different polyamide acid solution and functional inorganic filling mixing coating are prepared on polyimide
Different adhesive strengths and mechanical strength.Different functional inorganic fillings is added in polyamic acid solution, can be promoted respectively
Polyimides (band coating polyimide) high temperature resistant, intensity, the performance of electromagnetic shielding, moreover it is possible to obtain the poly- of different colours
Acid imide product.In practical applications, according to necessary requirement, different functionalities inorganic filler is selected to reach different performances and need
It asks.After adding titanium dioxide, silica, calcium oxide, boron nitride in polyamic acid solution, final polyimides obtained is produced
Product high temperature resistance improves 50~120 DEG C, and tensile strength can improve 5~15MPa.In polyamic acid solution add iron oxide,
The coating of brownish red, ecru and black can be obtained after titanium dioxide, carbon black respectively.
The utility model has the advantages that the present invention is the exogenous functional material of method coating in the polymerization of polyimide upper body, it should
Method will not generate structural influence to polyimides itself, and the adhesion strength of coating and polyimide film is more preferable,
Compared with conventional adhesive, polyimide paint of the present invention is applied in polyimide surface prepares coating or binding function material
Layer has better adhesive strength with polyimide film, while coating is resistant to higher temperature, up to 400 DEG C or more；Use 3M600
When adhesive tape test coating adhesion, coating shedding area is no more than 10%；And after carrying out bend test to coating, most of region
It there are no apparent wrinkle and crackle.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 4.00g's
80mLN is added into three-necked flask in three-necked flask in 4,4- diaminodiphenyl ethers (ODA), N- dimethyl acetamide (DMAC),
The hexafluorodianhydride (6FDA) (6FDA) that 8.88g is added at one time to being completely dissolved is stirred under nitrogen protection and ice-water bath in reactant
The reaction was continued in system, under ice-water bath 12h, obtains yellowish sticky polyamic acid solution (PAA1) after the reaction was completed；It will
The titania powder that 10.00g polyamic acid solution (PAA1) and 2.40g partial size are 60nm mixes, and obtains polyimide paint
1。
During mixing, appropriate polyimide paint 1 is taken to be evenly coated at polyimide film and ceramics
On piece is subsequently placed in baking oven and solidifies, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C ×
1h,240℃×1h,290℃×1h；Obtain the Kapton 1 that surface has functional material coating.
The polyimide film of Kapton 1 made from embodiment 1 and uncoated polyimide paint 1 is carried out pair
Than the tensile strength of the polyimide film of uncoated polyimide paint 1 is 150Mpa, the tensile strength of Kapton 1
For 158Mpa；Heatproof test is carried out to the coating on 1 surface of Kapton, compares unloaded polyimide coating,
Heat-resisting quantity promotes 50~80 DEG C.
Embodiment 2
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 8.00g's
120mLN, dinethylformamide are added into three-necked flask in three-necked flask for 4,4 '-diaminodiphenyl ethers (ODA)
(DMF), it stirs under nitrogen protection and under ice-water bath to being completely dissolved, is added at one time 3,3 ', 4,4 '-biphenyl of 11.76g
Tetracarboxylic acid dianhydride (BPDA) the reaction was continued in reaction system, under ice-water bath 8h obtains sticky poly- of egg white color after the reaction was completed
Amide acid solution (PAA2)；12.00g polyamic acid solution (PAA2) and 3.00g the partial size silica for being 16nm are mixed, obtained
To polyimide paint 2.
During mixing, appropriate polyimide paint 2 is taken to be evenly coated at polyimide film and ceramics
On piece is subsequently placed in baking oven and solidifies, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C ×
1h,240℃×1h,290℃×1h.Obtain the Kapton 2 that surface has functional material coating.
The polyimide film of Kapton 2 made from embodiment 2 and uncoated polyimide paint 2 is carried out pair
Than the tensile strength of the polyimide film of uncoated polyimide paint 2 is 160Mpa, the tensile strength of Kapton 2
For 172Mpa.Heatproof test is carried out to the coating on 2 surface of Kapton, compares unloaded polyimide coating,
Heat-resisting quantity promotes 50~100 DEG C.
Embodiment 3
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 4.97g
60mL n,N-dimethylacetamide (DMAC) is added into three-necked flask in three-necked flask in 4,4 '-diaminodiphenylsulfones,
It stirs under nitrogen protection and under ice-water bath to being completely dissolved, is added at one time 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride of 5.88g
(BPDA) the reaction was continued in reaction system, under ice-water bath 10h, obtains yellowish sticky polyamic acid solution after the reaction was completed
(PAA3)；11.00g polyamic acid solution (PAA3) and 3.00g the partial size calcium oxide for being 160nm are mixed, polyimides is obtained
Coating 3.
During mixing, suitable polyimide paint 3 is taken to be evenly coated at polyimide film and pottery
On tile, be subsequently placed in baking oven and solidify, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C ×
1h,240℃×1h,290℃×1h.Obtain the Kapton 3 that surface has functional material coating.
After calcium oxide is added in polyimide paint in the present embodiment, heatproof is carried out to the coating on 3 surface of Kapton
Test, compares unloaded polyimide coating, and heat-resisting quantity promotes 70~100 DEG C.
Embodiment 4
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 5.20g's
70mL n,N-dimethylacetamide is added into three-necked flask in three-necked flask for Bisphenol A Type Diether Dianhydride (BPADA)
(DMAC), it stirs under room temperature under nitrogen protection to being completely dissolved, is added at one time the 4 of 2.00g, 4 '-diaminodiphenyl ethers (ODA)
In reaction system, the reaction was continued at room temperature 16h obtains the polyamic acid solution of near colorless clear viscous after the reaction was completed
(PAA4)；The boron nitride that 9.00g polyamic acid solution (PAA4) and 2.00g partial size are 1 μm is mixed, polyimide paint is obtained
4。
During mixing, suitable polyimide paint 4 is taken to be evenly coated at polyimide film and pottery
On tile, be subsequently placed in baking oven and solidify, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C ×
1h,240℃×1h,280℃×1h.Obtain the Kapton 4 that surface has functional material coating.
After boron nitride is added in polyimide paint in the present embodiment, heatproof test is carried out to coating, compared to unloaded
Polyimide coating, heat-resisting quantity promote 100~120 DEG C.
After high-temperature resistant nano material is added, the high temperature resistance of polyimide paint respectively obtains aforementioned four embodiment
Different degrees of raising, while after adding reinforced filling, intensity can also improve.
Embodiment 5
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 5.20g's
50mL n,N-dimethylacetamide is added into three-necked flask in three-necked flask for Bisphenol A Type Diether Dianhydride (BPADA)
(DMAC), stir under room temperature under nitrogen protection to being completely dissolved, be added at one time 2.92g1, bis- (4- amino-benzene oxygen) benzene of 4- in
In reaction system, the reaction was continued at room temperature 12h obtains yellowish sticky polyamic acid solution (PAA5) after the reaction was completed；It will
6.00g polyamic acid solution (PAA5) and 2.00g copper powder mix, and obtain polyimide paint 5.
During mixing, appropriate polyimide paint 5 is taken to be evenly coated on polyimide film, then will
It, which is placed in baking oven, solidifies, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C × 1h, 240 DEG C × 1h,
280℃×1h.Obtain the Kapton 5 with coating for EMI shielding.
Kapton 5 made from embodiment 5 has electromagnetic shielding action.
Embodiment 6
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 5.20g's
56mL n,N-dimethylacetamide is added into three-necked flask in three-necked flask for Bisphenol A Type Diether Dianhydride (BPADA)
(DMAC), it stirs under room temperature under nitrogen protection to being completely dissolved, is added at one time the 2 of 4.11g, 2 '-bis- [4- (4- aminobenzene oxygen
Base phenyl)] propane (BAPP) is in reaction system, the reaction was continued at room temperature 10h, the poly- of light brown viscous is obtained after the reaction was completed
Amide acid solution (PAA6)；7.00g polyamic acid solution (PAA6) and 2.20g the partial size iron oxide for being 60nm are mixed, obtained
Polyimide paint 6.
During mixing, appropriate polyimide paint 6 is taken to be evenly coated on polyimide film, then will
It, which is placed in baking oven, solidifies, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C × 1h, 240 DEG C × 1h,
280 DEG C × 1h, the Kapton 6 of brownish red is obtained, there is brownish red coating, brownish red coating on Kapton 6
Kapton can be dyed brownish red.
Embodiment 7
The preparation method of polyimide paint of the present invention with functional material, specifically comprises the following steps: to weigh 2.94g's
The Bisphenol A Type Diether Dianhydride (BPADA) of 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA) and 5.20g in three-necked flask, to
60mL n,N-dimethylacetamide (DMAC) is added in three-necked flask, stirs under room temperature under nitrogen protection to being completely dissolved, obtains
Mixed solution A；The 4 of 4.00g are weighed, 4 '-diaminodiphenyl ethers (ODA) are dissolved in 30mL n,N-dimethylacetamide (DMAC),
Mixed solution B is obtained, slowly is added drop-wise to obtain in mixed solution A by mixed solution B with constant pressure funnel, react at room temperature
12h obtains the sticky polyamic acid solution of light brown (PAA7) after the reaction was completed；By 4.00g polyamic acid solution (PAA7) with
The titania powder that 1.20g partial size is 60nm mixes, and obtains polyimide paint 7.
During mixing, appropriate polyimide paint 7 is taken to be evenly coated on polyimide film, then will
It, which is placed in baking oven, solidifies, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C × 1h, 240 DEG C × 1h,
280℃×1h.The Kapton 7 of ecru is obtained, there is ecru coating, ecru coating on Kapton 7
Kapton can be dyed ecru.
Embodiment 8
The preparation method of polyimide paint of the present invention with functional material specifically comprises the following steps: to weigh 2.22g six
The 2 of fluorine dianhydride (6FDA) and 2.06g, propane (BAPP) is in three-necked flask for 2 '-bis- [4- (4- aminophenoxy phenyls)], to three
25mL n,N-dimethylacetamide (DMAC) is added in mouth flask, stirs under room temperature under nitrogen protection to being completely dissolved, is mixed
Close solution A；The Bisphenol A Type Diether Dianhydride (BPADA) for weighing 5.20g is dissolved in 25mL n,N-dimethylacetamide (DMAC), is obtained
To mixed solution B；Slowly mixed solution B is added drop-wise in mixed solution A with constant pressure funnel, reacts 12h at room temperature, is reacted
The sticky polyamic acid solution of light brown (PAA8) is obtained after the completion；By 6.00g polyamic acid solution (PAA8) and 1.60g carbon black
It mixes, obtains polyimide paint 8.
During mixing, appropriate polyimide paint 8 is taken to be evenly coated on polyimide film, then will
It, which is placed in baking oven, solidifies, program curing are as follows: 80 DEG C × 5h, 120 DEG C × 1h, 160 DEG C × 1h, 200 DEG C × 1h, 240 DEG C × 1h,
280℃×1h.Obtain the Kapton 8 with black coating.Nanoscale carbon black is a kind of inorganic pigment, can be by polyamides Asia
Amine dyes black.
Contrast sample is the coating that bicomponent epoxy resin glue mixes nano iron oxide preparation, and rigidity is larger after solidification,
Color is partially yellow, and adhesive strength is poor.Coating begins to melt and carbonize at 250 DEG C or more, and coating starts to be detached from polyamides Asia
Amine film.
In above-described embodiment, polyimide-based counterdie is the polypyromelliticimide film that DuPont Corporation releases
(Kapton), with a thickness of 0.2mm.Functional material, which is respectively provided with, improves polyimide high temperature-resistant, intensity, electromagnetic shielding and coloring
Characteristic, in polyimide paint have good dispersibility.The adhesive strength of coating material and polyimide film and
High temperature resistance
Coating quality test
Coating adhesion test: coating adhesion test uses 3M600 tape test, is the test glue of general international standard
Band.It is pasted on the coating of polyimides sample 1,2,3,4,5,6,7,8, is compressed, after five minutes by glue respectively with 3M600 adhesive tape
Band is torn.Hundred lattice methods of testing are taken to detect the area percentage of each coating shedding respectively, calculation formula is as follows:
Fall off area × 100% of the area ÷ tape-stripping of coating shedding after area (%)=test
Test result is as shown in table 1.
Coating layer thickness test: coating layer thickness is measured using digital cladding thickness measurer, measurement result is as shown in table 1.
Coating bend test: using diameter is the cylindrical shaft of 2mm as bending axis, by polyimides sample 1,2,3,4,5,
6,7,8 it is bent cladding cylindrical shaft respectively, observes coating surface result.It is chosen as if coating surface is without any wrinkle and crackle
" excellent " is chosen as " good " if there is unobvious wrinkle in coating surface only a few region, if coating surface have a little wrinkle or
Crackle be then chosen as " in ", be chosen as " poor " if there are obvious wrinkle and crackle in coating surface major part region.Analyze result such as table 1
It is shown.
1 test result of table
As shown in Table 1, conventional epoxies glue, bonding of the polyimide paint of the present invention on Kapton are compared
Intensity is good.From the point of view of polyimide paint itself, some coating non-co-planar, polarity is big, prepared by the monomer with flexible structure
The coated adhesive intensity obtained after solidification is high, and flexible, resist bending is lost preferably.
Polyimide paint of the present invention has better high temperature resistance in coating prepared by polyimide surface, up to 400
DEG C or more；And it is good with the adhesive strength of Kapton, when with 3M600 adhesive tape test coating adhesion, coating shedding area
No more than 10%；Meanwhile different functional inorganic fillings can be added in coating according to demand, to make Kapton
Product has different functions, realizes different applications.
Claims (9)
1. a kind of polyimide paint with functional material, it is characterised in that: the polyimide paint by polyamic acid solution and
Functional inorganic filling is mixed with；Wherein, polyamic acid solution reacts poly- by dicarboxylic anhydride and diamines in organic solvent
It closes.
2. the polyimide paint according to claim 1 with functional material, it is characterised in that: the polyimide paint
It is prepared by the component of following mass percent:
Dicarboxylic anhydride: 5~15%；
Diamines: 5~15%；
Organic solvent: 40~60%；
Functional inorganic filling: 10~30%.
3. the polyimide paint according to claim 2 with functional material, it is characterised in that: the structure of the dicarboxylic anhydride
General formula is as follows:
Wherein, in above-mentioned dicarboxylic anhydride R structure are as follows:
4. the polyimide paint according to claim 2 with functional material, it is characterised in that: the structure of the diamines is logical
Formula is as follows:
Wherein, in above-mentioned diamines M structure are as follows:
5. the polyimide paint according to claim 2 with functional material, it is characterised in that: the organic solvent is N,
Any one in dinethylformamide, n,N-dimethylacetamide or N-Methyl pyrrolidone or any several combination.
6. the polyimide paint according to claim 2 with functional material, it is characterised in that: functional inorganic filling packet
It includes the inorganic filler of high temperature resistance, the inorganic filler for improving polyimides electromagnetic shielding effect, improve polyimides intensity
Inorganic filler and the inorganic pigment coloured for polyimides；Wherein, the inorganic filler of high temperature resistance is titanium dioxide, two
The combination of one or more of silica, calcium oxide, boron nitride or carbon nanotube；The inorganic of polyimides intensity is improved to fill out
Material is titanium dioxide and/or silica；The inorganic filler for improving polyimides electromagnetic shielding effect is copper powder and/or silver powder；
Inorganic pigment for polyimides coloring is one of iron oxide, titanium dioxide or carbon black.
7. the polyimide paint according to claim 2 with functional material, it is characterised in that: the polyimide paint
Solid content be 10~20%.
8. the polyimide paint according to claim 6 with functional material, it is characterised in that: functional inorganic filling is
Solid particle or powder, average grain diameter are 0.01 μm~10 μm.
9. a kind of prepare functional form polyimide material using the polyimide paint described in claim 1 with functional material
Method, it is characterised in that: polyimide paint is coated in by polyimides using one of brushing method, spin-coating method or dip coating
On substrate, temperature programming solidification, temperature-rise period are as follows: 70~90 DEG C of 2~5h of heat preservation；120~160 DEG C of 0.5~2h of heat preservation；200
~240 DEG C of 0.5~3h of heat preservation；260~300 DEG C of 0.5~1.5h of heat preservation；The polyamides for obtaining surface appendix functional material coating is sub-
Amine.
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| CN111017921A (en) * | 2019-12-27 | 2020-04-17 | 深圳烯湾科技有限公司 | Preparation method of polyimide graphite film |
| CN111584808A (en) * | 2020-04-16 | 2020-08-25 | 山东工业陶瓷研究设计院有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| EP3831815A1 (en) | 2019-12-03 | 2021-06-09 | Shandong University | A benzoxazine adhesive for polyimide and the preparation and application method thereof |
| CN113214736A (en) * | 2021-05-10 | 2021-08-06 | 常熟市方舟绝缘材料有限责任公司 | Polyimide film, preparation method thereof and quick winding device thereof |
| CN114452446A (en) * | 2020-11-10 | 2022-05-10 | 脉通医疗科技(嘉兴)有限公司 | Medical tube and preparation method thereof |
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| EP3831815A1 (en) | 2019-12-03 | 2021-06-09 | Shandong University | A benzoxazine adhesive for polyimide and the preparation and application method thereof |
| CN111017921A (en) * | 2019-12-27 | 2020-04-17 | 深圳烯湾科技有限公司 | Preparation method of polyimide graphite film |
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| CN116410662A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气集团有限公司 | High-performance polyimide temperature-resistant coating and preparation method and application thereof |
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