CN108527745B - Preparation device and preparation method of polyimide thick film or polyimide ultra-thick film - Google Patents
Preparation device and preparation method of polyimide thick film or polyimide ultra-thick film Download PDFInfo
- Publication number
- CN108527745B CN108527745B CN201810206525.9A CN201810206525A CN108527745B CN 108527745 B CN108527745 B CN 108527745B CN 201810206525 A CN201810206525 A CN 201810206525A CN 108527745 B CN108527745 B CN 108527745B
- Authority
- CN
- China
- Prior art keywords
- polyimide
- thick film
- film
- polyamic acid
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 141
- 239000004642 Polyimide Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 70
- 238000001816 cooling Methods 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920005575 poly(amic acid) Polymers 0.000 claims description 76
- 239000000758 substrate Substances 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 46
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 185
- 239000000463 material Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
-
- 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
-
- 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
Abstract
The invention discloses a preparation device and a preparation method of a polyimide thick film or a polyimide ultra-thick film, and belongs to the technical field of polyimide films. The preparation facilities includes the casing, the inside metal sheet that is on a parallel with the casing bottom surface that is equipped with of casing, the metal sheet falls into two independent heating chambeies each other and is located the cooling chamber on heating chamber upper portion with casing inside, the top in heating chamber be equipped with the parallel heating pipe of metal sheet, the both sides face in cooling chamber is equipped with air intake and air outlet respectively, the casing outside is equipped with the air-blower, the air-blower passes through the air intake with cooling chamber intercommunication, the centre of metal sheet is equipped with the thermocouple. The invention also discloses a method for preparing the polyimide thick film or the polyimide ultra-thick film by using the preparation device. The invention can prepare the polyimide thick film or the polyimide ultra-thick film with the thickness of more than 50 mu m, and has simple structure and easy operation.
Description
Technical Field
The invention relates to a preparation device and a preparation method of a polyimide thick film or a polyimide ultra-thick film, belonging to the technical field of polyimide films.
Background
The polyimide has excellent high temperature resistance and low temperature resistance, good mechanical property and chemical stability, small thermal expansion coefficient and is a polymer material with the best insulating property in the world at present. Polyimide film materials are widely applied to various high and new technical fields of electronics, aviation and the like.
Depending on the thickness, polyimide films can be classified into ultrathin films (d.ltoreq.8 μm), conventional thin films (8 μm < d.ltoreq.50 μm), thick films (50 μm < d.ltoreq.125 μm), and ultrathin films (d > 125 μm). The polyimide thick and ultra-thick films are complicated in preparation process and thus much more expensive than conventional polyimide films.
Currently, the polyimide film is prepared by casting a polyamic acid solution into a film, stretching the film, and then performing high-temperature imidization. The heating furnace of the traditional polyimide film adopts an upper heating mode and a lower heating mode, and adopts a primary casting film forming technology, and adopts a hot air blowing method in order to accelerate solvent volatilization. The method is suitable for manufacturing the polyimide film with the thickness less than or equal to 30 mu m. The reason is that the polyimide film with the thickness less than or equal to 30 mu m is thinner, the solvent amount is less, the path of the solvent volatilized into the air through the material is short, and the solvent of the polyimide is completely volatilized before imidization, so that the foaming phenomenon does not exist. In addition, the upper and lower surfaces are almost uniformly dried due to the thin film, and no curling phenomenon occurs.
However, if the existing one-time casting film forming technology is used, for a polyimide film with a thickness of more than 30 μm, especially for a thick film with a thickness of more than 50 μm and an ultra-thick film with a thickness of more than 125 μm, when heating is performed by using an up-and-down heating mode, because the polyamic acid film is thick, the solvent content is high, the solvent evaporates rapidly after heating, when the surface starts to solidify into a solid film after evaporating to a certain degree, the solid film has high compactness, which is not beneficial to the evaporation of the solvent in the material, and the vapor pressure of the solid film is also increased along with the increase of the internal temperature of the material, and because the gas cannot be evaporated smoothly, bubbles are generated when the internal temperature of the material is further increased. In addition, since the upper and lower surfaces of the film are heated, the solid contents of the upper and lower surfaces are gradually solidified while increasing with the volatilization of the solvent at the initial stage of heating, but the solvent in the material near the substrate surface is hard to volatilize after the outer surface is solidified to a certain extent, the material in these places has a high solvent content and is in a soft state, and the solvent in the film surface is easy to volatilize, and the material surface is in a relatively hard state and shrinks with the decrease of the surface solvent, so that the film may be automatically released due to the shrinkage of the surface, and the released polyimide film may be curled. Therefore, in the process of preparing the polyimide film by using the traditional heat treatment furnace with the upper and lower heating modes, when the thickness of the prepared polyimide film is increased to more than 30 mu m, some product quality problems occur, and particularly, after the thickness of the prepared film exceeds 50 mu m, the film with smooth and flat appearance is difficult to prepare by using the existing one-time tape casting film forming technology.
In order to prepare a thick film or an ultra-thick film with smooth and flat appearance, a multilayer polyimide film laminating and bonding method (multilayer film bonding method) can be adopted, and a multiple casting polyamic acid film-imidization process (multiple casting-drying film forming method) can also be adopted, so that the thick film or the ultra-thick film is prepared by a complex process flow and low production efficiency.
In view of the above, it is necessary to provide a new apparatus and method for preparing a polyimide thick film or a polyimide ultra-thick film to solve the disadvantages of the prior art.
Disclosure of Invention
The invention aims to provide a preparation device of a polyimide thick film or a polyimide ultra-thick film. The preparation device of the polyimide thick film or the polyimide ultra-thick film solves the problem that the solvent in the polyamic acid is difficult to volatilize due to the early hardening of the transition state surface of the polyamic acid in the heat treatment furnace in the prior art, can prepare the polyimide thick film or the polyimide ultra-thick film with the thickness of more than 50 mu m, and has simple structure and easy operation.
The technical scheme for solving the technical problems is as follows: the utility model provides a preparation facilities of polyimide thick film or polyimide super thick film, includes the casing, the inside metal sheet that is on a parallel with the casing bottom surface that is equipped with of casing, the metal sheet falls into two independent heating chambeies each other and is located the cooling chamber that heats chamber upper portion with casing inside, the top in heating chamber be equipped with the parallel heating pipe of metal sheet, the both sides face in cooling chamber is equipped with air intake and air outlet respectively, the casing outside is equipped with the air-blower, the air-blower passes through the air intake with cooling chamber intercommunication, the centre of metal sheet is equipped with the electric heat couple.
The principle of the invention is as follows:
the apparatus for preparing a thick polyimide film or a thick polyimide ultra-thick film according to the present invention is a device for heat-treating a polyamic acid film by back-heating and front-cooling, in which heat is applied to the polyamic acid film from the substrate direction (back-heating) and the outer surface of the polyamic acid film is cooled by low-temperature flowing air in a cooling chamber (front-cooling) so that heat is transferred from the back surface of the polyamic acid film (surface in contact with the substrate) to the outer surface of the polyamic acid film, and a certain temperature gradient is provided before the solvent is completely volatilized.
The cooling cavity is internally provided with an air inlet, the air inlet is connected with an air blower on the outer side of the shell, the air blower blows air to form flowing air, the outer surface of the polyamide acid film can be cooled, the temperature of the air blower can be adjusted, and the cooling air is discharged from the air outlet. The invention adopts low-temperature (20-30 ℃) flowing air to cool the outer surface of the polyamic acid film, and aims to carry away heat transmitted from a heating pipe to the surface of the material through a substrate so as to maintain the low-temperature state of the surface of the material.
The method comprises the following steps:
firstly, casting a layer of polyamic acid solution on the surface of a substrate to obtain a substrate covered with a polyamic acid film, then placing the substrate on a metal plate in a cooling cavity of a polyimide thick film or a polyimide thick film preparation device, starting a heater in a heating cavity, and carrying out heat treatment; heating the polyamic acid film from the direction of the substrate, the heat being transferred to the outer surface of the film (polyamic acid front surface) through the substrate-polyamic acid film contact surface (polyamic acid back surface);
at the same time, the blower was turned on and the front surface of the polyamic acid film was always in flowing air at a lower temperature (relative to the temperature in the heating chamber) so that the front surface of the polyamic acid film was at a lower temperature. This causes the two surfaces of the polyamic acid film to have different temperatures, heat is continuously diffused from the back surface of the polyamic acid film having a high temperature to the front surface having a low temperature, and the temperature in the direction of the film thickness is also not uniform, and the closer to the substrate, the higher the temperature is, the lower the temperature is, the closer to the outer surface.
The solvent vapor pressure in the relatively high temperature polyamic acid is high and the solvent slowly diffuses out through the low temperature layer and eventually reaches the front surface of the polyamic acid film and constantly evaporates from the outer surface. Since the front surface of the polyamic acid film is always in a relatively low temperature state (relative to the temperature in the heating chamber), and the solvent content is relatively high, the heat treatment temperature is controlled so that the surface layer solvent is slowly volatilized, and the front surface of the polyamic acid film is slowly cured. The curing of the entire film thus starts from the back side and proceeds slowly in the direction of the front side. The heating mode is favorable for the solvent in the deep part of the film layer to slowly diffuse outwards without generating bubbles under the proper temperature condition, and the inner film layer of the film before the film curing on the outer surface is dried, so that the film can not automatically release due to the surface shrinkage.
When the solvent in the film is volatilized, the sample is transferred to a common constant temperature device (such as a muffle furnace) for thermal imidization to obtain the polyimide film.
By adopting the preparation device of the polyimide thick film or the polyimide ultra-thick film, the solvent in the polyimide material is volatilized in a progressive mode that the deep solvent is volatilized firstly and the surface solvent is volatilized later in the preparation of the polyimide film, so that the phenomenon that the deep solvent cannot volatilize to cause foaming due to the fact that the film is solidified in advance because the surface solvent is volatilized firstly is avoided, and the phenomenon that the film surface is solidified and shrunk in advance to cause demoulding and curling is also avoided, so that the polyimide film prepared by the device is not foamed and cannot be demoulded.
The preparation device of the polyimide thick film or the polyimide ultra-thick film is suitable for preparing the polyimide thick film and the polyimide ultra-thick film material, ensures that the solvent in the material is volatilized as far as possible, and avoids the deformation of the material.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the metal plate is made of one of a stainless steel plate, a copper plate or an aluminum plate.
The adoption of the further beneficial effects is as follows: the metal plate has two functions, namely heat conduction, namely heat generated by the heating pipe is transferred to the substrate through the metal plate, and then the polyamic acid cast on the substrate is subjected to heat treatment through the substrate; the second is the sealing function, namely, the convection between the flowing air in the cooling cavity and the hot air in the heating cavity is avoided.
Further, the shell outside still is equipped with condensation recovery unit, condensation recovery unit pass through the air outlet with the cooling chamber intercommunication.
The adoption of the further beneficial effects is as follows: the air outlet is connected with the condensation recovery device, so that the solvent can be recovered, and the solvent can be recovered and recycled.
The second object of the present invention is to provide a method for preparing a polyimide thick film or a polyimide ultra-thick film using the above apparatus for preparing a polyimide thick film or a polyimide ultra-thick film. The preparation method of the polyimide thick film or the polyimide ultra-thick film changes the heat treatment method in the prior art, improves the volatilization condition of the solvent from the polyamic acid or the polyimide material, can prepare the polyimide thick film or the polyimide ultra-thick film by one-time tape casting film forming, has smooth and flat surface of the prepared material, has simple process compared with the multilayer film bonding method and the multiple tape casting-drying film forming method in the prior art, has low production cost and wide market prospect, and is suitable for large-scale popularization and application.
The technical scheme for solving the technical problems is as follows: a method for preparing a polyimide thick film or a polyimide ultra-thick film by using the preparation device of the polyimide thick film or the polyimide thick film comprises the following steps:
step 1: taking diamine, dianhydride and a solvent, uniformly mixing, and reacting to obtain a polyamic acid solution; wherein the molar ratio of the diamine to the dianhydride is 1:1, and the weight of the solvent is 4-7 times of the total weight of the diamine and the dianhydride;
step 2: casting a layer of the polyamic acid solution obtained in the step 1 on a substrate to obtain a substrate covered with a polyamic acid film;
and step 3: placing the substrate covered with the polyamic acid film obtained in the step 2 on a metal plate in a cooling cavity of the polyimide thick film or the polyimide thick film preparation device, starting a heater in the heating cavity, and carrying out heat treatment; simultaneously starting an air blower to volatilize the solvent in the polyamic acid film to obtain a dry polyamic acid film covered on the substrate;
and 4, step 4: and (3) performing thermal imidization and stripping on the dried polyamic acid film covered on the substrate obtained in the step (3) to obtain the polyimide thick film or the polyimide ultra-thick film.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step 1, the diamine is one or a mixture of two or more of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine and m-phenylenediamine.
In step 1, the dianhydride is one or a mixture of two or more of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
Further, in the step 1, the solvent is one or a mixture of two or more of N-methylpyrrolidone, N '-dimethylacetamide and N, N' -dimethylformamide.
Further, in step 2, the substrate is made of one of a glass plate, a ceramic plate, a stainless steel plate or an aluminum plate.
Further, the heat treatment in step 4 adopts gradient temperature rise, specifically, the temperature is maintained at 70-80 ℃ for more than 1 hour, the temperature is maintained at 90-100 ℃ for more than 1 hour, the temperature is maintained at 110-120 ℃ for more than 1 hour, the temperature is maintained at 160-200 ℃ for more than 1 hour, and finally the temperature is maintained at 280-290 ℃ for more than 0.5 hour.
Further, in step 4, the thermal imidization is specifically performed at a temperature of 300-320 ℃ for more than 0.5 hour.
Further, in step 4, the thickness of the polyimide thick film or the polyimide ultra-thick film is more than 50 μm, and the number of bubbles is zero.
The invention has the beneficial effects that:
(1) the preparation device of the polyimide thick film or the polyimide ultra-thick film solves the problem that the solvent in the polyamic acid is difficult to volatilize due to the early hardening of the transition state surface of the polyamic acid in the heat treatment furnace in the prior art, can prepare the polyimide thick film or the polyimide ultra-thick film with the thickness of more than 50 mu m, and has simple structure and easy operation.
(2) The preparation method of the polyimide thick film or the polyimide ultra-thick film changes the heat treatment method in the prior art, improves the volatilization condition of the solvent from the polyamic acid or the polyimide material, can prepare the polyimide thick film or the polyimide ultra-thick film by one-time tape casting film forming, has smooth and flat surface of the prepared material, has simple process compared with the multilayer film bonding method and the multiple tape casting-drying film forming method in the prior art, has low production cost and wide market prospect, and is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a schematic structural view of an apparatus for preparing a polyimide thick film or a polyimide ultra-thick film according to the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1. the device comprises a shell, 2, a metal plate, 3, a heating cavity, 4, a cooling cavity, 5, a heating pipe, 6, an air inlet, 7, an air outlet, 8, a blower, 9, an electric thermocouple, 10 and a condensation recovery device.
Detailed Description
The principles and features of this invention are described below in conjunction with the following detailed drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1
As shown in fig. 1, the apparatus for preparing a polyimide thick film or a polyimide ultra-thick film of this embodiment includes a housing 1, a metal plate 2 parallel to the bottom surface of the housing 1 is disposed inside the housing 1, the metal plate 2 divides the housing 1 into two heating chambers 3 independent of each other and a cooling chamber 4 located above the heating chambers 3, a heating pipe 5 parallel to the metal plate 2 is disposed at the top of the heating chamber 3, two side surfaces of the cooling chamber 4 are respectively provided with an air inlet 6 and an air outlet 7, an air blower 8 is disposed outside the housing 1, the air blower 8 is communicated with the cooling chamber 4 through the air inlet 6, and an electric thermocouple 9 is disposed in the middle of the metal plate 2.
In the apparatus for producing a thick polyimide film or a thick polyimide ultra-thick film according to the present embodiment, when the polyamic acid film is heat-treated, the back heating and the front cooling are performed, that is, when the polyamic acid film is heat-treated in the heating chamber 3, the heat heats the polyamic acid film from the substrate direction (back heating), and at the same time, the outer surface of the polyamic acid film is cooled in the cooling chamber 4 using low-temperature flowing air (front cooling), so that the heat is transferred from the back surface of the polyamic acid film (the surface in contact with the substrate) to the outer surface of the polyamic acid film, and a certain temperature gradient is provided before the solvent is completely volatilized.
An air inlet 6 is arranged in the cooling cavity 4, the air inlet 6 is connected with an air blower 8 on the outer side of the shell 1, air is blown by the air blower 8 to form flowing air, the outer surface of the polyamide acid film can be cooled, the temperature of the air blower 8 can be adjusted, and cooling air is discharged from an air outlet 7. The invention adopts low-temperature (20-30 ℃) flowing air to cool the outer surface of the polyamic acid film, and aims to carry away heat transmitted to the surface of the material from a heating pipe 5 through a substrate so as to maintain the low-temperature state of the surface of the material.
Wherein, the metal plate 2 is made of stainless steel plate. The metal plate 2 has two functions, namely, heat conduction, namely, heat generated by the heating pipe 5 is transferred to the substrate through the metal plate 2, and then the polyamic acid cast on the substrate is subjected to heat treatment through the substrate; the second is a sealing function, i.e. to avoid convection between the air flowing in the cooling chamber 4 and the hot air in the heating chamber 3.
The shell 1 outside still is equipped with condensation recovery unit 10, condensation recovery unit 10 pass through air outlet 7 with cooling chamber 4 intercommunication. The air outlet 7 is connected with a condensation recovery device 10, so that the solvent can be recovered, and the solvent can be recovered and recycled.
The method for preparing the polyimide thick film or the polyimide ultra-thick film by using the preparation device for the polyimide thick film or the polyimide thick film comprises the following steps:
step 1: under the protection of nitrogen atmosphere, 40.00g of 4,4' -diaminodiphenyl ether was added to 315g of N-methylpyrrolidone solution, and stirred at room temperature to dissolve, and then 43.60g of pyromellitic dianhydride was slowly added in several portions, and stirred for 6 hours after the completion of the addition, to obtain a viscous polyamic acid solution (solid content about 20%).
Step 2: and (3) casting a layer of the polyamic acid solution obtained in the step (1) on the substrate of the glass plate to obtain the substrate covered with the polyamic acid film.
And step 3: placing the substrate covered with the polyamic acid film obtained in the step 2 on a metal plate in a cooling cavity of the polyimide thick film or the polyimide thick film preparation device, starting a heater in the heating cavity, and carrying out heat treatment; the heat treatment adopts gradient heating, specifically, the temperature is kept at 80 ℃ for 1.5 hours, at 100 ℃ for 1.5 hours, at 120 ℃ for 2 hours, at 220 ℃ for 1 hour, and at last at 280 ℃ for 1 hour.
And simultaneously turning on the blower to volatilize the solvent (namely N-methyl pyrrolidone solution) in the polyamic acid film to obtain the dry polyamic acid film covered on the substrate.
And 4, step 4: and (3) performing thermal imidization on the dried polyamic acid film covered on the substrate obtained in the step (3), wherein the thermal imidization is specifically to keep the polyimide film at the temperature of 320 ℃ for 1 hour, and demoulding to obtain the polyimide thick film or the polyimide ultra-thick film.
The polyimide thick film or polyimide ultra-thick film obtained in this example has a smooth and flat (non-bending) surface, zero bubble number, and a thickness of 242 μm.
Example 2
The apparatus for preparing a polyimide thick film or a polyimide ultra-thick film of this example was the same as in example 1. Wherein, the metal plate 2 is made of copper plate.
The shell 1 outside still is equipped with condensation recovery unit 10, condensation recovery unit 10 pass through air outlet 7 with cooling chamber 4 intercommunication.
The method for preparing the polyimide thick film or the polyimide ultra-thick film by using the preparation device for the polyimide thick film or the polyimide thick film comprises the following steps:
step 1: under the protection of nitrogen atmosphere, 20.00g of 3,4 '-diaminodiphenyl ether is added into 330g of N, N-dimethylacetamide solution, stirred and dissolved at room temperature, and 29.39g of 3,4' -diaminodiphenyl ether is slowly added in multiple times
3,3',4,4' -biphenyltetracarboxylic dianhydride was stirred for 6 hours after the completion of the addition to obtain a viscous polyamic acid solution (solid content about 12.5%).
Step 2: and (3) casting a layer of the polyamic acid solution obtained in the step (1) on the aluminum plate substrate to obtain the substrate covered with the polyamic acid film.
And step 3: placing the substrate covered with the polyamic acid film obtained in the step 2 on a metal plate in a cooling cavity of the preparation device for the polyimide thick film or the polyimide thick film, starting a heater in the heating cavity, and carrying out heat treatment; the heat treatment adopts gradient heating, specifically, the temperature is kept at 70 ℃ for 1 hour, the temperature is kept at 90 ℃ for 1 hour, the temperature is kept at 110 ℃ for 1 hour, then the temperature is kept at 200 ℃ for 1 hour, and finally the temperature is kept at 290 ℃ for 0.5 hour.
Meanwhile, the blower is turned on to volatilize the solvent (i.e., the N, N-dimethylacetamide solution) in the polyamic acid film, and a dry polyamic acid film coated on the substrate is obtained.
And 4, step 4: and (3) performing thermal imidization on the substrate covered with the polyamic acid film obtained in the step (3), wherein the thermal imidization is specifically to keep the substrate at the temperature of 300 ℃ for 1 hour, and demoulding to obtain the polyimide thick film or the polyimide ultra-thick film.
The polyimide thick film or polyimide ultra-thick film obtained in this example has a smooth and flat (non-bending) surface, zero bubble number, and a thickness of 55 μm.
Example 3
The apparatus for preparing a polyimide thick film or a polyimide ultra-thick film of this example was the same as in example 1. Wherein, the metal plate 2 is made of an aluminum plate.
The shell 1 outside still is equipped with condensation recovery unit 10, condensation recovery unit 10 pass through air outlet 7 with cooling chamber 4 intercommunication.
The method for preparing the polyimide thick film or the polyimide ultra-thick film by using the preparation device for the polyimide thick film or the polyimide thick film comprises the following steps:
step 1: 13.00 g of p-phenylenediamine and 8.03g of 4,4' -diaminodiphenyl ether are added to a 390g N, N-dimethylformamide solution under the protection of nitrogen atmosphere, the mixture is stirred and dissolved at room temperature, 47.60g of 3,3',4,4' -biphenyltetracarboxylic dianhydride is slowly added in multiple portions, and the mixture is stirred for 6 hours after the addition is finished, so that a viscous polyamic acid solution (the solid content is about 15%) is obtained.
Step 2: and (3) casting a layer of the polyamic acid solution obtained in the step (1) on a stainless steel plate substrate to obtain a substrate covered with a polyamic acid film.
And step 3: placing the substrate covered with the polyamic acid film obtained in the step 2 on a metal plate in a cooling cavity of the polyimide thick film or the polyimide thick film preparation device, starting a heater in the heating cavity, and carrying out heat treatment; the heat treatment adopts gradient heating, specifically, the temperature is kept at 70 ℃ for 1.5 hours, at 90 ℃ for 1.5 hours, at 120 ℃ for 2 hours, at 200 ℃ for 1.5 hours, and at last at 290 ℃ for 1 hour.
Meanwhile, the blower is turned on to volatilize the solvent (i.e., the N, N-dimethylformamide solution) in the polyamic acid film, and a dry polyamic acid film coated on the substrate is obtained.
And 4, step 4: and (3) performing thermal imidization on the substrate covered with the polyamic acid film obtained in the step (3), wherein the thermal imidization is specifically to keep the substrate at the temperature of 300 ℃ for 1 hour, and demoulding to obtain the polyimide thick film or the polyimide ultra-thick film.
The polyimide thick film or polyimide ultra-thick film obtained in this example had a smooth and flat (non-curved) surface, zero number of bubbles, and a thickness of 155. mu.m.
Comparative example
Comparative example a difference from example 1 was that in step 3, the substrate covered with the polyamic acid film obtained in step 2 was placed in a high temperature oven (the whole oven was at a constant temperature, the film was heated up and down) common in the art, and subjected to a heat treatment using a gradient of temperature rise, specifically 70 ℃ for 1.5 hours, 90 ℃ for 1.5 hours, 120 ℃ for 2 hours, 200 ℃ for 1.5 hours, and finally 290 ℃ for 1 hour. The remaining steps are the same.
The polyimide film obtained in this comparative example had many bubbles on the surface, and the whole film had already separated from the substrate and was in a curled state, and a polyimide thick film or a polyimide ultra-thick film having a smooth and flat (non-curved) surface could not be obtained.
Therefore, the device for preparing the polyimide thick film or the polyimide ultra-thick film solves the problem that the solvent in the polyamic acid is difficult to volatilize due to the early hardening of the transition state surface of the polyamic acid in the heat treatment furnace in the prior art, can prepare the polyimide thick film or the polyimide ultra-thick film with the thickness of more than 50 microns, and has the advantages of simple structure and easy operation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A method for preparing a polyimide thick film or a polyimide ultra-thick film is characterized by comprising the following steps:
step 1: taking diamine, dianhydride and a solvent, uniformly mixing, and reacting to obtain a polyamic acid solution; wherein the molar ratio of the diamine to the dianhydride is 1:1, and the weight of the solvent is 4-7 times of the total weight of the diamine and the dianhydride;
step 2: casting a layer of the polyamic acid solution obtained in the step 1 on a substrate to obtain a substrate covered with a polyamic acid film;
and step 3: placing the substrate covered with the polyamic acid film obtained in the step 2 on a metal plate in a cooling cavity of a preparation device of the polyimide thick film or the polyimide ultra-thick film, starting a heater in the heating cavity, and carrying out heat treatment; simultaneously starting an air blower to volatilize the solvent in the polyamic acid film to obtain a dry polyamic acid film covered on the substrate; wherein the heat treatment adopts gradient temperature rise, specifically, the temperature is kept at 70-80 ℃ for more than 1 hour, the temperature is kept at 90-100 ℃ for more than 1 hour, the temperature is kept at 110-120 ℃ for more than 1 hour, the temperature is kept at 160-200 ℃ for more than 1 hour, and finally the temperature is kept at 280-290 ℃ for more than 0.5 hour; the preparation device of the polyimide thick film or the polyimide ultra-thick film comprises a shell (1), a metal plate (2) parallel to the bottom surface of the shell (1) is arranged in the shell (1), the metal plate (2) divides the interior of the shell (1) into two heating cavities (3) which are independent from each other and a cooling cavity (4) which is positioned at the upper part of the heating cavities (3), the top of the heating cavity (3) is provided with a heating pipe (5) which is parallel to the metal plate (2), two side surfaces of the cooling cavity (4) are respectively provided with an air inlet (6) and an air outlet (7), the outer side of the shell (1) is provided with a blower (8), the blower (8) is communicated with the cooling cavity (4) through the air inlet (6), an electric thermocouple (9) is arranged in the middle of the metal plate (2), and the metal plate (2) is made of one of a stainless steel plate, a copper plate or an aluminum plate;
and 4, step 4: carrying out thermal imidization and stripping on the dried polyamic acid film covered on the substrate obtained in the step 3 to obtain a polyimide thick film or a polyimide super-thick film; wherein the thermal imidization is specifically kept for more than 0.5 hour at the temperature of 300-320 ℃; the thickness of the polyimide thick film or the polyimide super-thick film is larger than 50 mu m, and the number of bubbles is zero.
2. The method of claim 1, wherein in step 1, the diamine is one or a mixture of two or more selected from the group consisting of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine and m-phenylenediamine.
3. The method of claim 1, wherein in step 1, the dianhydride is one or a mixture of two or more of pyromellitic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
4. The method of claim 1, wherein the solvent is one or a mixture of two or more of N-methylpyrrolidone, N-dimethylacetamide and N, N-dimethylformamide in step 1.
5. The method of claim 1, wherein in step 2, the substrate is made of one of glass plate, ceramic plate, stainless steel plate or aluminum plate.
6. The method for preparing the polyimide thick film or the polyimide ultra-thick film according to the claim 1, wherein in the step 3, a condensation recovery device (10) is further arranged on the outer side of the shell (1), and the condensation recovery device (10) is communicated with the cooling cavity (4) through an air outlet (7).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810206525.9A CN108527745B (en) | 2018-03-13 | 2018-03-13 | Preparation device and preparation method of polyimide thick film or polyimide ultra-thick film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810206525.9A CN108527745B (en) | 2018-03-13 | 2018-03-13 | Preparation device and preparation method of polyimide thick film or polyimide ultra-thick film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108527745A CN108527745A (en) | 2018-09-14 |
| CN108527745B true CN108527745B (en) | 2021-03-02 |
Family
ID=63484611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810206525.9A Expired - Fee Related CN108527745B (en) | 2018-03-13 | 2018-03-13 | Preparation device and preparation method of polyimide thick film or polyimide ultra-thick film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108527745B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888129B (en) * | 2019-01-30 | 2020-12-08 | 武汉华星光电半导体显示技术有限公司 | Apparatus and method for removing bubbles in flexible substrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1515338A (en) * | 1995-09-18 | 2004-07-28 | 美国3M公司 | Drying system of coated bottom material |
| CN101648180A (en) * | 2008-07-10 | 2010-02-17 | 富士胶片株式会社 | Method for drying coating film |
| CN101649055A (en) * | 2008-08-14 | 2010-02-17 | 比亚迪股份有限公司 | Polyamide acid solution, polyimide plate and method for preparing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672477B (en) * | 2015-03-01 | 2017-10-24 | 中国乐凯集团有限公司 | A kind of application of the preparation method of low roughness polyimide film, product and product |
-
2018
- 2018-03-13 CN CN201810206525.9A patent/CN108527745B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1515338A (en) * | 1995-09-18 | 2004-07-28 | 美国3M公司 | Drying system of coated bottom material |
| CN101648180A (en) * | 2008-07-10 | 2010-02-17 | 富士胶片株式会社 | Method for drying coating film |
| CN101649055A (en) * | 2008-08-14 | 2010-02-17 | 比亚迪股份有限公司 | Polyamide acid solution, polyimide plate and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108527745A (en) | 2018-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106928481A (en) | The optimization preparation method of Kapton | |
| CN103442870B (en) | The preparation method of polyimide film, the preparation facilities of polyimide film and polyimide film | |
| JPS6153087B2 (en) | ||
| CN102089365A (en) | Aromatic polyimide film, laminate and solar cell | |
| JP4119693B2 (en) | Insulating graphite film and method for producing the same | |
| CN110358085A (en) | A kind of preparation method of silica aerogel/polyimides compound heat-insulation film | |
| CN110626030B (en) | High-thermal-conductivity polyimide multilayer composite film and preparation method thereof | |
| CN107698785A (en) | A kind of polyimides based coextruded film and preparation method thereof | |
| CN108527745B (en) | Preparation device and preparation method of polyimide thick film or polyimide ultra-thick film | |
| CN108541143B (en) | Preparation device and preparation method of polyimide copper-clad plate | |
| CN108794748A (en) | A kind of Kapton of low-k and preparation method thereof | |
| TWI666239B (en) | Method for manufacturing polyimide laminate and method for manufacturing flexible circuit board | |
| CN103889710A (en) | Method for manufacturing polyimide metal laminate | |
| Ni et al. | Combining Microwave‐Assisted Foaming and Post Curing Process to Prepare Lightweight Flexible Polyimide Foams for Thermal Insulation Applications | |
| CN108327377B (en) | Polyimide film or polyimide copper-clad plate's preparation facilities | |
| TWI741030B (en) | Polyimide film | |
| JP4406764B2 (en) | Gas barrier polyimide film and metal laminate using the same | |
| CN108587163A (en) | A kind of high transparency low bulk Kapton and the preparation method and application thereof | |
| CN108727587B (en) | Heat-resistant polyimide containing imidazolyl aromatic ring structure and preparation method thereof | |
| CN207931244U (en) | A kind of preparation facilities of polyimide film or polyimide copper clad lamination | |
| JP4078630B2 (en) | Carbon film manufacturing method and carbon film obtained thereby | |
| CN112409595B (en) | Polyimide film and preparation method thereof | |
| JP5709018B2 (en) | Metal laminate | |
| JP2011131456A (en) | Gas-barrier polyimide film and metal layered product using the same | |
| CN115340703B (en) | Polyimide film with directional heat dissipation function and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210302 |