CN109647683A - A kind of preparation method of thick polyimide film or super thick film - Google Patents
A kind of preparation method of thick polyimide film or super thick film Download PDFInfo
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- CN109647683A CN109647683A CN201811324383.2A CN201811324383A CN109647683A CN 109647683 A CN109647683 A CN 109647683A CN 201811324383 A CN201811324383 A CN 201811324383A CN 109647683 A CN109647683 A CN 109647683A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Moulding By Coating Moulds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses the preparation methods of a kind of thick polyimide film or super thick film, comprising the following steps: mixes aromatic tetracarboxylic dianhydride with aromatic diamine compound, polyamic acid solution is made；Dehydrating agent and catalyst are added in the polyamic acid solution, is mixed to get resin solution mixture；Using spraying equipment by the resin solution mixture continuous spray on a moving belt, and the slurry pipeline transport on the conveyer belt is dried into drying device, gel polyimide film is made；The gel polyimide film is stretched, and heating removal solvent under tension, thick polyimide film or super thick film is made.Present invention process is simple, and production cost is low, wide market, is suitble to large-scale promotion application.
Description
Technical field
The present invention relates to the preparation field of polyimide film more particularly to a kind of thick polyimide film or polyimides super thick
The preparation method of film.
Background technique
Polyimides (PI) is the regular rigid polymer of a kind of chemical structure height on main chain containing imide ring, one
As be to be obtained by aromatic diamines and aromatic tetrahydric dianhydride by polycondensation reaction.Polyimide material have excellent high temperature resistant,
It is low temperature resistant, high-strength and high-modulus, high creep resistant, high dimensionally stable, low thermal coefficient of expansion, high electric insulation, low-k and loss, resistance to
The advantages that radiating, be corrosion-resistant, while having the advantages that the space materials such as vacuum volatilization part is low, volatilization condensable material is few, it can be processed into
Kapton, thermostability engineering plastic, composite material matrix resin, high temperature resistant binder, fiber and foam etc. are a variety of
Material forms, therefore have extensively in many high-technology fields such as aerospace, space, microelectronics, precision machinery, medical instrument
Wealthy application prospect and huge commercial value.
Kapton product is often classified according to its thickness, and according to the difference of thickness, polyimide film can be with
It is classified as ultrathin membrane (d≤8 μm), traditional films (8 μm of d≤50 μm <), thick film (50 μm of d≤125 μm <) and super thick film (d >
125μm).Thick polyimide film and super thick film preparation complex process, thus it is more much higher than polyimides traditional films in price.
The manufacturing technology of PI film is stirred in aprotic polar solvent with aromatic diamine and aromatic dianhydride at present
Polyamic acid (PAA) resin of polycondensation synthesis is raw material, squeezes out and salivates through vacuum defoaming, high-pressure delivery to flat-mould head, molding
PAA liquid film handles to obtain PAA gel film through hot setting, by vertically and horizontally gradually or synchro-draw (orientation), chemistry or heat
Required product is made after cooling and shaping, winding, then thermally treated, cutting after imidization processing.The heating of traditional polyimide film
Furnace is upper and lower faces heating mode, and uses a casting film-forming technology, in order to accelerate solvent to volatilize, uses blowing hot-air
Method.The above method is suitable for manufacturing the polyimide film of thickness≤30 μm.This is because the polyimides of thickness≤30 μm
Film is relatively thin, and quantity of solvent is few, and solvent evaporate into that distance in air is short, and polyimides solvent before imidization has all been waved by material
It is dry net, so foaming phenomena is not present.In addition, it is relatively thin to be also due to film, upper and lower faces almost evenly drying will not go out
Existing crimp.
But if it is greater than 30 μm of polyimide film for thickness, especially using an existing casting film-forming technology
For thick film of the thickness greater than 50 μm and thickness for the super thick film greater than 125 μm, when being heated using upper and lower heating mode,
Since polyamide acid film is thicker, solvent content is more, the outermost layer of film due to after heating solvent volatilize rapidly, when evaporateing into certain journey
Degree rear surface begins to solidify as solid film, and the compactness of this solid film is high, is unfavorable for the volatilization of material internal solvent, with material
Expect internal temperature increase, vapour pressure also constantly increases, since gas cannot volatilize away unobstructedly, when material internal temperature into
One step will generate bubble when rising.In addition, be also due to film upper and lower faces heating, heating initial stage with solvent
Volatilization, the solid content of upper and lower faces can all rise and solidify at leisure, but after outer surface solidifies to a certain extent, it leans on
Solvent in the material in nearly matrix face is difficult to evaporate, and the material in these places is high containing quantity of solvent and is in softer state, together
When due in film surface solvent it is readily volatilized, with the reduction of surface solvent, material surface is in relatively hard state and generating receipts
Contracting, such film may due to surface contraction and automatic demoulding, the polyimide film of abjection generate curling.So using it is upper,
The prior heat treatment furnace of lower two sides heating mode prepares polyimides membrane process, when the thickness of the polyimide film of preparation increases to
At 30 μm or more, it just will appear some product quality problems, especially after preparing film thickness and being more than 50 μm, using existing primary
Casting film-forming technology is difficult to that smooth in appearance, smooth film is prepared.
In order to prepare smooth in appearance, smooth thick film or super thick film, can be superimposed using the Kapton of multilayer
Adhesive method (plural layers mull technique) can also use repeatedly curtain coating polyamide acid film-imidization technique (to be repeatedly cast-do
Dry membrane formation process), however use the method described in the former that can adversely affect to the mechanical property of thick polyimide film, it uses
When method described in the latter repeatedly increases film thickness at film preparation multilayer polyimide film, succeeding layer often causes brokenly front layer
It is bad, it is low so as to cause the production efficiency for preparing thick film, it is difficult to uniform thickness, smooth in appearance, smooth thick film be prepared.
Therefore, in order to solve the above the deficiencies in the prior art, it is necessary to the film-forming process in polyimides filming technology
It optimizes and improves with high temperature curing process.
The disclosure of background above technology contents is only used for auxiliary and understands design and technical solution of the invention, not necessarily
The prior art for belonging to present patent application, no tangible proof show above content present patent application the applying date
In disclosed situation, above-mentioned background technique should not be taken to the novelty and creativeness of evaluation the application.
Summary of the invention
In order to solve the above-mentioned technical problem, the present invention proposes the preparation method of a kind of thick polyimide film or super thick film, work
Skill is simple, and production cost is low, wide market, is suitble to large-scale promotion application.
In order to achieve the above object, the invention adopts the following technical scheme:
The invention discloses the preparation methods of a kind of thick polyimide film or super thick film, comprising the following steps:
S1: aromatic tetracarboxylic dianhydride is mixed with aromatic diamine compound, and polyamic acid solution is made；
S2: dehydrating agent and catalyst are added in the polyamic acid solution, is mixed to get resin solution mixture；
S3: using spraying equipment by the resin solution mixture continuous spray on a moving belt, and by the conveyer belt
On slurry pipeline transport be dried into drying device, be made gel polyimide film；
S4: the gel polyimide film is stretched, and heating removal solvent under tension, and it is sub- that polyamides is made
Amine thick film or super thick film.
Further, wherein in step S1 polyamic acid solution obtained viscosity >=100000mPas, it is preferable that virtue
The molar ratio of fragrant race tetracarboxylic dianhydride and aromatic diamine compound is 0.99:1~1.02:1.
Further, the dehydrating agent uses benzoyl oxide, and the catalyst uses the pyridine of methyl arsenic.
Further, the movement speed of conveyer belt described in step S3 is 30~50cm/s.
Further, the spraying equipment in step S3 includes gear pump and at least one spray for connecting the gear pump
Rifle, it is described to be specifically included the resin solution mixture continuous spray on a moving belt using spraying equipment: by the resin
Solution mixture is packed into the gear pump, the gear pump resin solution mixture is imported into be evenly distributed on it is described
In the spray gun above conveyer belt, the resin solution mixture is atomized by the spray gun, and is sprayed on the transmission
It takes.
Further, the output volume flow of the gear pump is 6~15ml/min.
Further, the spray pressure of the spray gun is 0.2~0.4MPa, it is preferable that the diameter of the nozzle of the spray gun
For 0.2~0.4mm.
Further, the nozzle of the spray gun is vertical with the plane of the conveyer belt, and the nozzle of the spray gun with it is described
The distance between conveyer belt is 150~200mm, it is preferable that the spray gun transverse shifting (moving along the width direction of conveyer belt)
Distance be the slurry on 0.6~0.7 times of the conveyer belt width.
Further, in step s3 using spraying equipment by the resin solution mixture continuous spray on a moving belt
Before, the concentration of the resin solution mixture is adjusted to 0.5% using N-Methyl pyrrolidone.
Further, step S4 is specifically included: the gel polyimide film is stretched at least 1 times at room temperature, and
Solvent is removed using 400 DEG C or more heating 10min or more under tension force effect, thick polyimide film or super thick film is made.
Compared with prior art, the beneficial effects of the present invention are thick polyimide film proposed by the present invention or super thick films
Preparation method, first be made polyamic acid solution, add dehydrating agent and catalyst obtain resin solution mixture, then adopt
Resin solution mixture is sprayed on conveyer belt with spraying equipment, and conveyer belt is transported in drying device and carries out predry
It is dry, biaxial tension is finally carried out again, while heating removal solvent under tension；The present invention is by combining spray coating method and two-way
Pulling method prepares thick polyimide film or super thick film, can be sprayed into film preparation thickness gathering greater than 50 μm by one or many
Acid imide thick film and polyimides super thick film, the material surface of preparation is smooth, smooth, than the plural layers mull technique of the prior art
It is repeatedly cast-is dried to the simple process of embrane method, production cost is low, wide market, is suitble to large-scale promotion application, energy
Enough it is suitable for Roll-to-Roll manufacturing process；And also solve plural layers mull technique in the prior art and repeatedly curtain coating-
It is dried to film forming problem existing for embrane method.
Detailed description of the invention
Fig. 1 is the flow chart of the thick polyimide film of the preferred embodiment of the present invention or the preparation method of super thick film；
Fig. 2 is the spray gun spraying process schematic of the preferred embodiment of the present invention；
Fig. 3 is the schematic diagram of the spraying film forming apparatus of the preferred embodiment of the present invention；
Fig. 4 is the schematic diagram of the hot setting device of the preferred embodiment of the present invention.
Specific embodiment
Below against attached drawing and in conjunction with preferred embodiment, the invention will be further described.
As shown in Figure 1, polyimides (PI) thick film of the preferred embodiment of the present invention or the preparation method of super thick film, including with
Lower step:
S1: aromatic tetracarboxylic dianhydride is mixed with aromatic diamine compound, and viscosity >=100000mPa is made
Polyamic acid (PAA) solution of s；
Specifically, under inert atmosphere and certain temperature, by aromatic tetracarboxylic dianhydride on the basis of raw material purifying
It reacts to obtain PAA solution with aromatic diamine compound equimolar (molal quantity is roughly equal), wherein aromatic tetracarboxylic dianhydride
Molar ratio with aromatic diamine compound is 0.99:1~1.02:1, further, aromatic tetracarboxylic dianhydride and aromatic series
The molar ratio of diamine compound is 1.005:1~1.01:1.
In the present embodiment, by adjusting the proportion of diamines and dianhydride, make the viscosity of the PAA solution of synthesis >=
100000mPas keeps PAA molecular weight higher, to guarantee that the PI of synthesis has excellent mechanical performance.
S2: being added dehydrating agent and catalyst in polyamic acid solution, and mixing obtains resin solution mixture；
Specifically, dehydrating agent and catalyst respectively added amount respectively with the aromatic diamine compound phase in step S1
Deng；Dehydrating agent can use benzoyl oxide, and catalyst can use the pyridine of methyl arsenic.
S3: using spraying equipment by resin solution mixture continuous spray on a moving belt, and by the slurry on conveyer belt
It is transported in drying device and is dried, gel polyimide film is made；
Specifically, spraying equipment includes at least one spray gun of gear pump and tooth connection wheel pump, by resin solution mixture
It is packed into gear pump, resin solution mixture is imported into the spray gun being evenly distributed on above conveyer belt by gear pump, and spray gun is adopted
Current-carrying gas is done with nitrogen, resin solution mixture is atomized, and is sprayed on a moving belt.Further, the gear pump
Output volume flow be 6~15ml/min；The spray pressure of spray gun is 0.2~0.4MPa, and the diameter of the nozzle of spray gun is 0.2
~0.4mm (such as 0.3mm), the nozzle of spray gun and the plane of conveyer belt are vertical, and between the nozzle and conveyer belt of spray gun away from
From for 150~200mm；The width for the slurry on conveyer belt that the distance of spray gun transverse shifting is 0.6~0.7 times；Conveyer belt
Movement speed is 30~50cm/s, which can be stainless steel conveyor belt.
S4: gel polyimide film is stretched, and heating removal solvent under tension, and thick polyimide is made
Film or super thick film.
Specifically, gel polyimide film is stretched at least 1 times at room temperature, and use under tension 400 DEG C with
Upper high-temperature heating 10min or more removes solvent, and thick polyimide film or super thick film is made.
It is carried out below with preparation method of the specific embodiment to polyimides (PI) thick film or super thick film of the invention into one
Walk explanation.
Under inert atmosphere and certain temperature, aromatic tetracarboxylic dianhydride and aromatic diamine compound equimolar (are rubbed
Your number is roughly equal) obtained PAA solution is reacted, it comprises the concrete steps that: first weighing 4.0048gODA (4,4- diaminodiphenyl ether)
With 75gDMAC (n,N-dimethylacetamide) into three-necked flask, mechanical stirring 30min, after ODA is completely dissolved, optionally
It is appropriate on the rocks in water-bath, reaction temperature is controlled at 15~20 DEG C；Mixing speed is tuned up, (will be controlled by with ODA certain proportion
Acid anhydride amine ratio 0.99:1~1.02:1 processed) PMDA (pyromellitic acid anhydride) be added in flask in three times, guarantee in 0.5h
It adds；After PMDA is added, continues to be stirred to react 4h, stop stirring；Stand a night wait for bubble eliminate, obtaining sticky PAA is in
Existing light yellow, solid content is 10% or so.Then it is added in the organic solution of aggressiveness PAA before the polyimides into flask again de-
Aqua and catalyst, are sufficiently stirred 0.5-1h at room temperature, thus be prepared part imidization PAA gel solution (namely
Resin solution mixture), wherein catalyst selects picoline, and dehydrating agent selects benzoyl oxide.PMDA:ODA: it dehydrating agent: urges
The molar ratio of agent is between 0.99:1:1:1~1.02:1:1:1.
Then, using spraying equipment by resin solution mixture continuous spray on a moving belt, and by the slurry on conveyer belt
Material, which is transported in drying device, to be dried, and gel polyimide film is made；Spraying equipment includes gear pump and tooth connection wheel pump
Multiple spray guns, wherein gear pump accurate flow control and can be suitable for continuous flow using electric controller；Such as
Shown in Fig. 2, spray gun 10 can be using pressure-air by solution atomization, and droplet reaches under the promotion of load gas (such as nitrogen)
Substrate deposition and drying and forming-film；Spray coating method has easy to operate, process control, sprayable small area or big area, controllably
Fogging degree processed can spray various slurries, not limited by the shape of painting objects, and various shape object can be sprayed
Surface, spray efficiency is high, can be by selecting different spraying conditions that the film thickness prepared be adjusted the advantages that.Such as Fig. 3
Shown, conveyer belt 20 is connected between the first stainless steel belt roller 31 and the second stainless steel belt roller 32, from the first stainless steel belt roller 31
And second set gradually between stainless steel belt roller 32 spraying roller 40, measuring thickness device 50, slewing rollers 60 and hot setting device 70 (
That is drying device), conveyer belt 20 transmits operation from the first stainless steel belt roller 31 to the direction of the second stainless steel belt roller 32.It is wherein more
The top of the conveyer belt 20 of 40 top of spraying roller is arranged in a spray gun (not shown).It is filmed using spraying membrane equipment
Step specifically: current-carrying gas is done with nitrogen, by the resin compound solution atomization of configured suitable concentration, by uniformly dividing
On the cloth spray gun spraying above conveyer belt 20 to stainless steel conveyor belt 20, it is dry that heating is then carried out by hot setting device 70
Dry processing forms gel polyimide film, finally, gel mould to be stretched to 1 times at room temperature, then heating is gone under tension
Except solvent, the thick polyimide film or super thick film of thickness >=50 μm are made through biaxial tension for defoaming.
Specifically, the suitable output flow range of gear pump is 20-50r/min, and corresponding volume flow is 6ml/min-
15ml/min, so as to ensure the stabilization of spray gun spraying flow in process supply.Ideal thick polyimide film in order to obtain
Or super thick film also adjusts the concentration of resin solution mixture in the present embodiment before spraying, if slurry is thin, viscosity is low,
When spraying, easily there is sagging；If slurry is thick, large viscosity, when spraying, easy formation crenulation；So need with certain fluidity,
The slurry of stability and moderate viscosity is in the present embodiment adjusted resin solution mixture using N-Methyl pyrrolidone (NMP)
Its concentration is saved to 0.5%.
Wherein, when spray gun spraying, gas pressure size is just preferred the complete micronized of slurry, if pressure is too small, slurry
Particle is coarse, makes to be formed by film and orange peel shape occurs；If pressure is excessive, easily there is sagging, bubble etc., slurry particle is easy to fly
It dissipates, wastes slurry.The spray pressure of the spray gun used in the present embodiment is 0.2-0.4MPa.
In spraying process, the nozzle of spray gun is consistent away from keeping suitable distance by spray surface；If apart from mistake
Closely, it is also easy to produce rebound and sagging occurs；If hypertelorism, slurry particle disperses, and is not attached on spray plane, be wasted slurry, and
For quick-drying slurry, during the long journey of slurry particle, is dried because of solvent volatilization and easily form film surface injustice；Nozzle and quilt
Spray plane will be kept vertically, if inclination, it will cause film coating became unevens.Small-sized spray gun spraying is used in the present embodiment
When, spray distance 150-200mm.
In spraying process, when gear pump duty is certain, the mobile speed of stainless steel conveyor belt is uniform, if speed
Too fast, the film thickness generated in unit area is relatively thin；If speed is excessively slow, the film thickness generated in unit area is thicker.Cause
This stainless steel conveyor belt excessive velocities and it is excessively slow when the non-uniform film thickness that will lead to prepare it is even, this requires that stainless steel passes
Band movement speed is sent uniformly, in the present embodiment to control the speed of stainless steel conveyor belt in 30-50cm/s.
When one timing of spray distance and spray stream section, the material trace width on surface is sprayed onto (in spray gun moving process
Spray to the width of the slurry of glass surface) it is also certain.When spraying the second billot trace, if the distance of spray gun transverse shifting is big
In material trace width, then there is drain spray place between two material traces；If it is less than material trace width, then there is overlapping between two material traces；If spray
The distance of rifle transverse shifting is equal to material trace width, although two billot traces just connect, the section of every billot trace will appear centre
Thickness, both sides are thin, the phenomenon of coating layer thickness unevenness.In order to prepare film in homogeneous thickness, when the present embodiment sprays wide surface, spray gun is horizontal
The material trace width for 0.6-0.7 times should be controlled to mobile distance.
In order to prepare the thick polyimide film or super thick film of thickness >=50 μm, the selection for spraying number needs and above-mentioned spraying
Technological parameter optimizes combination, and the combination of selection and spraying number for this to the parameter of different above-mentioned spraying process carries out
Research.Following embodiments use nozzle diameter for the spray gun of 0.3mm, and pulp density 0.5%, concrete outcome is as shown in table 1.
Spraying number requirement under the conditions of the different spraying process of table 1
As shown in Table 1, under conditions of pulp density and certain nozzle diameter, film thickness and gear pump discharge, spray gun pressure
Size, spray distance, stainless steel conveyor belt movement speed and spraying number are related；Film thickness and gear pump discharge, spray gun pressure, spray
It is directly proportional to apply number, is inversely proportional with spray distance and stainless steel conveyor belt movement speed.This is because gear pump discharge is bigger, i.e.,
The volume flow of output resin compound is also more in unit time, that is, sprays to the material on the stainless steel conveyor belt of unit area
Slurry amount is thicker；Spray gun pressure is bigger, i.e., within a certain period of time, spray rate faster, sprays to the stainless steel transmission of unit area
The slurry amount taken is also thicker；Spraying number is more, and the film layer number of formation increases, and thickness also accordingly increases；Spray distance is got over
Greatly, the shape area for the spray stream section that slurry is formed is bigger, under conditions of slurry flow is certain, on stainless steel conveyor belt
Unit area slurry loading tails off, i.e., thickness reduces；Stainless steel conveyor belt movement speed increases, certain in gear pump duty
When, stainless steel band unit area loading is smaller, and thickness also reduces accordingly.Therefore if to prepare >=125 μ in the present embodiment
The polyimides super thick film of m, most preferred spraying process condition are as follows: gear pump discharge, the spray gun pressure of 0.4MPa of 50r/min
Power, the spray distance of 150mm, the stainless steel conveyor belt movement speed of 30cm/s and spraying number >=12 time.
In the present embodiment, using hot setting device 70 as shown in Figure 4, which includes shell
71, the metal plate 72 for being parallel to 71 bottom surface of shell is equipped with inside shell 71, metal plate 72 will be divided into two each other inside shell 71
Independent heating chamber 73 and cooling chamber 74 positioned at heating chamber top, the top of heating chamber 73 are equipped with parallel with metal plate 72 add
Heat pipe 75, the two sides of cooling chamber 74 are respectively equipped with air inlet 76 and air outlet 77, and hull outside is equipped with air blower 78, air blower
78 are connected to by air inlet 76 with cooling chamber 74, and the centre of metal plate 72 is equipped with electroheat pair 721.The working principle of the device is:
Slurry on conveyer belt is transmitted on the metal plate 72 in cooling chamber 74 together together with conveyer belt, is carried out to polyamide acid film
When heat treatment, carried out with back side heating, positive cooling means, i.e., when being heat-treated in heating chamber, heat is from conveyer belt
Polyamide acid film is heated (back side is heated, and heating temperature is 200 DEG C) in direction, meanwhile, low temperature stream is used in cooling chamber
The outer surface (front is cooling, and cooling temperature is 20-30 DEG C) for moving the cooling polyamide acid film of air, so that hot from polyamide acid film
The inside (with conveyer belt contact surface) is transmitted to the outside of polyamide acid film, and has certain temperature ladder before solvent volatilizees completely
Degree.Air inlet 76 is equipped in cooling chamber 74, air inlet 76 is connected with the air blower 78 of hull outside, by 78 air blast of air blower,
The air for forming flowing, can cool down the outer surface of polyamide acid film, and the temperature of air blower 78 is adjustable, cooling wind from
Air outlet 77 is gone out.The present invention is to take away using the outer surface of the cooling polyamide acid film of low temperature (20-30 DEG C) moving air
The heat of material surface is passed to from heating tube 75 by conveyer belt to maintain the surface low-temperature state of material.Advantages of the present invention exists
In the tool of metal plate 72, there are two effects, first is that the heat that heat transfer, i.e. heating tube 75 generate is transmitted to conveyer belt by metal plate 72,
The polyamic acid of spraying on a moving belt is heat-treated by conveyer belt again；Second is that sealing function, that is, avoid cooling chamber 74
In moving air and heating chamber 73 in hot-air between convection current.Meanwhile air outlet 77 connects condensate recycling device 79, it can be with
Recycling design is realized the recycling of solvent and is recycled.It is able to solve at heat in the prior art by the hot setting device 70
Polyamic acid transition state surface premature hardening in reason furnace makes the solvent in polyamic acid be difficult to the problem of volatilizing.
By resin compound solution obtained in above-described embodiment, thickness can be prepared by optimal spraying film-forming process
Then the polyamide acid film of >=125 μm of degree carries out predrying at 200 DEG C by hot setting device with the speed of 30cm/s,
To which gel polyimide film be prepared；Finally gel glue polyimide film is stretched 1 times at room temperature, then made in tension
Solvent is removed using 400 DEG C of high-temperature heating 10min with lower, thick polyimide film or super thick film is made through biaxial tension in defoaming.
Present embodiment discloses a kind of methods that spray coating method-biaxial tension prepares thick polyimide film or super thick film, provide
A kind of hot setting device can be realized Roll-to-Roll production thick polyimide film, uses PMDA:ODA: de- first
Aqua: catalyst=1.005:1:1:1~1.010:1:1:1 prepares viscosity >=100000mPas polyamic acid solution, so
Use spraying process for the gear pump discharge of 50r/min, the spray pressure of 0.4MPa, the spray distance of 150mm, 30cm/s afterwards
Stainless steel conveyor belt movement speed and spraying number >=12 time prepare the polyamide acid films of thickness >=125 μm, are then passed through height
Warm solidification equipment carries out predrying at 200 DEG C with the speed of 30cm/s, to prepare gel polyimide film；It will finally coagulate
Glue film stretches 1 times at room temperature, then removes solvent, defoaming, through double using 400 DEG C of high-temperature heating 10min under tension
Thick polyimide film or super thick film is made to stretching.
Preparation method of the invention can pass through one or many polyimides for being sprayed into film preparation thickness and being greater than 50 μm
Thick film and polyimides super thick film, the material surface of preparation is smooth, smooth, than the prior art plural layers mull technique and repeatedly
It is cast-is dried to the simple process of embrane method, production cost is low, wide market, is suitble to large-scale promotion application, can be applicable in
In Roll-to-Roll manufacturing process；And it also solves plural layers mull technique in the prior art and is repeatedly cast-is dried to
Film forming problem existing for embrane method.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those skilled in the art to which the present invention belongs, it is not taking off
Under the premise of from present inventive concept, several equivalent substitute or obvious modifications can also be made, and performance or use is identical, all answered
When being considered as belonging to protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of thick polyimide film or super thick film, which comprises the following steps:
S1: aromatic tetracarboxylic dianhydride is mixed with aromatic diamine compound, and polyamic acid solution is made；
S2: dehydrating agent and catalyst are added in the polyamic acid solution, is mixed to get resin solution mixture；
S3: using spraying equipment by the resin solution mixture continuous spray on a moving belt, and will be on the conveyer belt
Slurry pipeline transport is dried into drying device, and gel polyimide film is made；
S4: the gel polyimide film is stretched, and heating removal solvent under tension, and thick polyimide is made
Film or super thick film.
2. preparation method according to claim 1, which is characterized in that wherein polyamic acid solution obtained in step S1
Viscosity >=100000mPas, it is preferable that aromatic tetracarboxylic dianhydride and the molar ratio of aromatic diamine compound are 0.99:1
~1.02:1.
3. preparation method according to claim 1, which is characterized in that the dehydrating agent uses benzoyl oxide, the catalysis
Agent uses the pyridine of methyl arsenic.
4. preparation method according to claim 1, which is characterized in that the movement speed of conveyer belt described in step S3 is 30
~50cm/s.
5. preparation method according to claim 1, which is characterized in that the spraying equipment in step S3 includes gear pump
It is described that the resin solution mixture continuous spray is existed using spraying equipment at least one spray gun for connecting the gear pump
It specifically includes: the resin solution mixture being packed into the gear pump, the gear pump is molten by the resin on conveyer belt
Liquid mixture is imported into the spray gun being evenly distributed on above the conveyer belt, and the spray gun mixes the resin solution
Object is atomized, and is sprayed on the conveyer belt.
6. preparation method according to claim 5, which is characterized in that the output volume flow of the gear pump be 6~
15ml/min。
7. preparation method according to claim 5, which is characterized in that the spray pressure of the spray gun is 0.2~0.4MPa,
Preferably, the diameter of the nozzle of the spray gun is 0.2~0.4mm.
8. preparation method according to claim 5, which is characterized in that the plane of the nozzle of the spray gun and the conveyer belt
Vertically, and the distance between the nozzle of the spray gun and the conveyer belt are 150~200mm, it is preferable that the spray gun laterally moves
The width for the slurry on the conveyer belt that dynamic distance is 0.6~0.7 times.
9. preparation method according to claim 1, which is characterized in that use spraying equipment by the resin in step s3
Solution mixture continuous spray on a moving belt before, using N-Methyl pyrrolidone by the concentration of the resin solution mixture
It is adjusted to 0.5%.
10. preparation method according to any one of claims 1 to 9, which is characterized in that step S4 is specifically included: will be described
Gel polyimide film stretches at least 1 times at room temperature, and uses 400 DEG C or more heating 10min with up under tension
Except solvent, thick polyimide film or super thick film is made.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110253904A (en) * | 2019-07-18 | 2019-09-20 | 桂林电器科学研究院有限公司 | A kind of thick polyimide film or super thick film and preparation method thereof |
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| CN105295374A (en) * | 2014-07-25 | 2016-02-03 | 富士施乐株式会社 | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article |
| CN106133025A (en) * | 2015-03-05 | 2016-11-16 | 株式会社Lg化学 | For producing the compositions of the polyimide film of the flexible board of photoelectric device |
| CN108659242A (en) * | 2018-04-13 | 2018-10-16 | 广东丹邦科技有限公司 | A kind of corona-resistant polyimide film and preparation method thereof |
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| CN103694702A (en) * | 2006-06-26 | 2014-04-02 | 沙伯基础创新塑料知识产权有限公司 | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
| CN105295374A (en) * | 2014-07-25 | 2016-02-03 | 富士施乐株式会社 | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article |
| CN106133025A (en) * | 2015-03-05 | 2016-11-16 | 株式会社Lg化学 | For producing the compositions of the polyimide film of the flexible board of photoelectric device |
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| CN110253904A (en) * | 2019-07-18 | 2019-09-20 | 桂林电器科学研究院有限公司 | A kind of thick polyimide film or super thick film and preparation method thereof |
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