CN108541143A - A kind of preparation facilities and preparation method of polyimide copper clad lamination - Google Patents
A kind of preparation facilities and preparation method of polyimide copper clad lamination Download PDFInfo
- Publication number
- CN108541143A CN108541143A CN201810206522.5A CN201810206522A CN108541143A CN 108541143 A CN108541143 A CN 108541143A CN 201810206522 A CN201810206522 A CN 201810206522A CN 108541143 A CN108541143 A CN 108541143A
- Authority
- CN
- China
- Prior art keywords
- copper clad
- polyimide
- clad lamination
- preparation
- polyimide copper
- Prior art date
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- Granted
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229920001721 polyimide Polymers 0.000 title claims abstract description 95
- 239000010949 copper Substances 0.000 title claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 88
- 239000004642 Polyimide Substances 0.000 title claims abstract description 85
- 238000003475 lamination Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 57
- 239000011889 copper foil Substances 0.000 claims abstract description 55
- 238000001816 cooling Methods 0.000 claims abstract description 38
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000004952 Polyamide Substances 0.000 claims description 53
- 229920002647 polyamide Polymers 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 22
- 238000004064 recycling Methods 0.000 claims description 17
- 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 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- -1 4,4'- diaminodiphenyl ethers Chemical class 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 57
- 239000010410 layer Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JBCUKQQIWSWEOK-UHFFFAOYSA-N 2-(benzenesulfonyl)aniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 JBCUKQQIWSWEOK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 206010018612 Gonorrhoea Diseases 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of preparation facilities of polyimide copper clad lamination and preparation methods, belong to polyimides technical field of membrane.The preparation facilities includes shell, the enclosure interior is equipped with the metallic plate for being parallel to housing bottom surface, enclosure interior is divided into two heating chambers independent of each other and cooling chamber positioned at heating chamber top by the metallic plate, the top of the heating chamber is equipped with the heating tube parallel with the metallic plate, the two sides of the cooling chamber are respectively equipped with air inlet and air outlet, the hull outside is equipped with air blower, the air blower is connected to by the air inlet with the cooling chamber, and the centre of the metallic plate is equipped with electroheat pair.The invention also discloses the methods for preparing polyimide copper clad lamination using above-mentioned preparation facilities.The preparation facilities of the present invention, can once be coated with the polyimide copper clad lamination that polyamic acid prepares various thickness, and simple in structure on copper foil, and operation is easy.
Description
Technical field
The present invention relates to a kind of preparation facilities of polyimide copper clad lamination and preparation methods, belong to polyimides membrane technology neck
Domain.
Background technology
With the development of science and technology, to the performance of circuit board, higher requirements are also raised.Polyimides has excellent
High temperature resistant, resistance to low temperature, and there is good mechanical property and chemical stability, coefficient of thermal expansion is small, thus using poly-
The flexibility coat copper plate of acid imide material covering metallic copper is widely used in electronic product.
Flexibility coat copper plate is divided into three layers of flexibility coat copper plate and two layers of flexibility coat copper plate：Three layers of flexibility coat copper plate have used bonding
Agent, the presence of binder affect the various aspects of performance such as heat-resisting of three layers of flexibility coat copper plate；Without using adhesive in polyacids Asia
The plate material that copper is directly covered on amine film is known as two layers of flexibility coat copper plate, and this two layers of flexibility coat copper plate has size under high-temperature
The performance characteristics such as stability is good, adhesion strength is high, folding resistance is good, currently, being nearly all use without glue in middle and high end electronics industry
Two layers of flexible copper-clad panel products of stick.Prepare two layers of flexibility coat copper plate technique have rubbing method (also referred to as cladding process), laminating method,
Flexibility coat copper plate peel strength prepared by sputtering method etc., wherein rubbing method is high, so in actual production based on rubbing method.It is right
Especially work as polyimide film due to being one layer of copper foil and one layer of polyimide film in its structure in single side non-gel flexible copper-clad plate
Layer is blocked up, and the copper-clad plate of preparation is susceptible to quality problems, influences two layers of flexibility coat copper plate and uses, so this is necessary in production
It solves the problems, such as.
Traditional two layers of flexibility coat copper plate coating process of preparation are exactly one layer of polyamic acid solution of coating on copper foil, so
The copper foil for being coated with polyamic acid solution is put into all constant constant temperature oven of entire furnace chamber temperature this kind of annealer afterwards
In carry out heat treatment and vapor away most of solvent therein, finally improve after heat treatment temperature carries out hot imidization and obtain polyamides Asia
Amine copper-clad plate.
This process heat utilization rate is high, is mainly manifested in：First, for preparing thick copper foil/thin polyimide membrane type
When copper-clad plate, such as polyimide film is less than 30 μm, and since polyimide film is relatively thin, quantity of solvent is few, and solvent is volatilized by material
Short to distance in air, polyamic acid upper and lower faces almost evenly drying, the polyimide copper clad lamination presentation quality of preparation is still
Good；When the second polyimide copper clad lamination for preparing thin copper foil, polyimide copper clad lamination can be bent；Third, for thickness
When the copper-clad plate of copper foil/thick polyimide membranous type, when polyimide thickness is more than 30 μm of polyimide copper clad laminations, polyimides
Copper-clad plate is susceptible to blistering, crimp, or splitting or interlayer gonorrhoea phenomenon occurs, if using more on copper foil
Secondary coating polyimides-hot imidization method prepares thicker polyimide film, and such technics comparing is complicated, and there is also
Binding force problem between polyimide layer.
In consideration of it, it is necessary to provide a kind of preparation facilities and preparation method of new polyimide copper clad lamination, it is existing to solve
There is the deficiency of technology.
Invention content
An object of the present invention is to provide a kind of preparation facilities of polyimide copper clad lamination.The polyimides of the present invention
The preparation facilities of copper-clad plate solves and prepares the problems such as two layers of flexibility coat copper plate are easily bent in the prior art, can be thin in copper
The coating of film last time prepares polyimide copper clad lamination, by changing heat treatment mode, improves solvent from polyamic acid or polyamides
It volatilizees in imines material situation, smooth in appearance, smooth polyimide copper clad lamination can be prepared, and simple in structure, operation is easy.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of preparation facilities of polyimide copper clad lamination, packet
Include shell, the enclosure interior is equipped with the metallic plate for being parallel to housing bottom surface, the metallic plate by enclosure interior be divided into two that
This independent heating chamber and the cooling chamber positioned at heating chamber top, the top of the heating chamber is equipped with parallel with the metallic plate
The two sides of heating tube, the cooling chamber are respectively equipped with air inlet and air outlet, and the hull outside is equipped with air blower, the drum
Wind turbine is connected to by the air inlet with the cooling chamber, and the centre of the metallic plate is equipped with electroheat pair.
The principle of the present invention：
The preparation facilities of the polyimide copper clad lamination of the present invention, when being heat-treated to polyamide acid film, with the back side plus
Heat, positive cooling means carry out, i.e., when being heat-treated in heating chamber, heat is to be carried out from copper foil direction to polyamide acid film
It heats (back side heating), meanwhile, using the outer surface of low temperature flow air cooling polyamide acid film, (front is cold in cooling chamber
But) so that heat is transmitted from the inside (with copper foil contact surface) of polyamide acid film to the outside of polyamide acid film, and complete in solvent
There is certain temperature gradient before full volatilization.
Air inlet is equipped in cooling chamber, air inlet is connected with the air blower of hull outside, by air blower air blast, forms stream
Dynamic air can cool down the outer surface of polyamide acid film, and the temperature of air blower is adjustable, and cooling wind goes out from air outlet
It goes.The present invention using the outer surface of low temperature (20-30 DEG C) moving air cooling polyamide acid film, is passed through to take away from heating tube
It crosses copper foil and passes to the heat of material surface to maintain the surface low-temperature state of material.
Specifically：
It first is coated with one layer of polyamic acid solution in copper foil surface, the copper foil of covering polyamide acid film is obtained, is subsequently placed in poly-
On metallic plate in the cooling chamber of the preparation facilities of acid imide copper-clad plate, the heating tube in heating chamber is opened, is heat-treated；Heat
Polyamide acid film is heated from copper foil direction, heat is by copper foil and polyamide acid film contact surface (the polyamic acid back side) to film
It transmits outer surface (polyamic acid front)；
Air blower is opened simultaneously, polyamide acid film front is constantly in temperature relatively low (relative to the temperature in heating chamber)
In moving air so that polyamide acid film front is in lower temperature.The two sides temperature of polyamide acid film is allowed for so not
Together, heat is constantly spread to the front of low temperature from the polyamic acid back of the membrane of high temperature always, and direction temperature residing for film thickness
Also uneven, temperature closer from copper foil is higher, and temperature closer from outer surface is lower.
Solvent vapour pressure in polyamic acid in relatively-high temperature is high, and solvent just slow transits through cryosphere to external diffusion,
It eventually arrives at polyamide acid film front and constantly volatilizees away from outer surface.Due to polyamide acid film front be constantly in it is relatively low
Warm (relative to the temperature in heating chamber) state, comparatively solvent content want high, control heat treatment temperature so that superficial layer is molten
Agent is slowly volatilized, and the solidification of polyamide acid film front is also slow.The solidification of film layer entire in this way is since the back side simultaneously slowly to front
Direction carries out.The solvent that this mode of heating is conducive to film layer depths under suitable temperature condition slowly unobstructed diffuses out outward
Go not generate bubble, film inner layer is relatively dry before the solidification of the film of outer surface, so will not due to surface shrinkage and from
Dynamic demoulding.
After film internal solvent is evaporated completely, sample, which is transferred in common thermostatic equipment (such as Muffle furnace), carries out hot imidization, obtains
To polyimide film.
The preparation facilities of polyimide copper clad lamination using the present invention, the coated polyimide copper foil being prepared, from thickness
Solvent content is uniform from the point of view of direction, and material does not generate additional stress after imidization, so the polyimide film after demoulding is flat
Whole (not being bent).
The preparation facilities of polyimide film or polyimide copper clad lamination using the present invention, prepares polyimide copper foil process
In, the solvent in polyimide material first volatilizees with the solvent of deep layer, the gradual and orderly approach volatilized after the solvent on surface carries out
Volatilization, avoid due to surface solvent first volatilize cause film in advance solidify make deep layer solvent cause to blister from volatilizing, also avoid
Film surface shifts to an earlier date solidification shrinkage and causes demoulding or film roll bent, so polyimide copper foil prepared by this equipment is not blistering, does not take off
Film is not bent.
The preparation facilities of the polyimide copper clad lamination of the present invention ensures suitable for preparing coated polyimide copper foil in material
Solvent volatilize away as far as possible, avoid material from deforming.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the material of the metallic plate is one kind in steel plate, copper coin or aluminium sheet.
It is using above-mentioned further advantageous effect：There are two effects for metallic plate tool, first, heat transfer, i.e. heating tube generate
Heat copper foil is transmitted to by metallic plate, then the polyamic acid being coated on copper foil is heat-treated by copper foil；Second is that close
Envelope acts on, that is, avoids convection current between the hot-air in the moving air and heating chamber in cooling chamber.
Further, the hull outside is additionally provided with condensate recycling device, and the condensate recycling device passes through air outlet and institute
State cooling chamber connection.
It is using above-mentioned further advantageous effect：Air outlet connects condensate recycling device, can be realized molten with recycling design
It the recycling of agent and recycles.
The second object of the present invention provides a kind of preparation facilities progress polyimides using above-mentioned polyimide copper clad lamination
The preparation method of copper-clad plate.The preparation method of the polyimide copper clad lamination of the present invention, using the system of above-mentioned polyimide copper clad lamination
Standby device, changes the heat treatment method of the prior art, improves solvent and volatilizees from polyamic acid or polyimide material shape
Condition can prepare smooth in appearance, smooth polyimide copper clad lamination, and simple for process, and production cost is low, wide market, fit
Close large-scale promotion application.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of preparation using above-mentioned polyimide copper clad lamination
The method that device prepares polyimide copper clad lamination, includes the following steps：
Step 1：Diamines, dianhydride and solvent are taken, is uniformly mixed, after reaction, obtains polyamic acid solution；Wherein, described two
The molar ratio of amine and dianhydride is 1:1, the weight of the solvent is 4-7 times of both diamines and dianhydride total weight；
Step 2：It is coated with the polyamic acid solution that one layer of step 1 obtains on copper foil, obtains the copper of covering polyamide acid film
Foil；
Step 3：The copper foil for the covering polyamide acid film that step 2 is obtained, is placed in the preparation of above-mentioned polyimide copper clad lamination
On metallic plate in the cooling chamber of device, the heating tube in heating chamber is opened, is heat-treated；Air blower is opened simultaneously, is volatilized
Solvent in polyamide acid film obtains being covered in the drying polyamide acid film on copper foil；
Step 4：The drying polyamide acid film being covered on copper foil that step 3 is obtained carries out hot imidization to get to poly-
Acid imide copper-clad plate.
Based on the above technical solution, the present invention can also be improved as follows.
Further, in step 1, the diamines is p-phenylenediamine, m-phenylene diamine (MPD), 4,4'- diaminodiphenyl ethers, 4,4'- bis-
The mixture of one or more of bis- (4- amino-benzene oxygens) benzene of aminodiphenyl sulfone, 1,3-.
Further, in step 1, the dianhydride be pyromellitic acid anhydride, 3,3', 4,4'- benzophenone tetracid dianhydrides, 3,
The mixture of one or more of 3', 4,4'- bibenzene tetracarboxylic dianhydride, 4,4'- biphenyl ether dianhydrides.
Further, in step 1, the solvent is N-Methyl pyrrolidone, n,N-dimethylacetamide, N, N- dimethyl methyls
One or more kinds of mixtures of amide.
Further, in step 2, copper thickness >=7 μm.
Further, heat treatment described in step 4 uses gradient increased temperature, and specially 70-80 DEG C is kept for 1 hour or more, 90-100
DEG C keep 1 hour or more, 110-120 DEG C is kept for 1 hour or more, then is kept for 1 hour or more at 160-200 DEG C, finally in 280-
290 DEG C are kept for 0.5 hour or more.
Further, in step 4, the hot imidization is specially to be kept for 0.5 hour or more at a temperature of 300-320 DEG C.
Further, in step 4, the thickness of the polyimide film in the polyimide copper clad lamination<50 μm, or >=50 μm,
Number of bubbles is zero.
Beneficial effects of the present invention：
(1) preparation facilities of polyimide copper clad lamination of the invention, solves and prepares two layers of flexible copper-clad in the prior art
The problems such as plate is easily bent, blisters, can once coating prepares polyimide copper clad lamination on Copper thin film, pass through change heat treatment
Mode improves solvent and volatilizees from polyamic acid or polyimide material situation, and it is sub- to prepare smooth in appearance, smooth polyamides
Amine copper-clad plate, and it is simple in structure, operation is easy.
(2) preparation method of polyimide copper clad lamination of the invention, using the preparation facilities of above-mentioned polyimide copper clad lamination,
The heat treatment method for changing the prior art improves solvent and volatilizees from polyamic acid or polyimide material situation, can make
Standby smooth in appearance, smooth polyimide copper clad lamination, and it is simple for process, production cost is low, wide market, is suitble to scale
It promotes and applies.
Description of the drawings
Fig. 1 is the structural schematic diagram of the preparation facilities of the polyimide copper clad lamination of the present invention.
In attached drawing, parts list represented by the reference numerals are as follows：
1, shell, 2, metallic plate, 3, heating chamber, 4, cooling chamber, 5, heating tube, 6, air inlet, 7, air outlet, 8, air blast
Machine, 9, electroheat pair, 10, condensate recycling device.
Specific implementation mode
Principles and features of the present invention are described below in conjunction with specific attached drawing, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1
As shown in Figure 1, a kind of preparation facilities of polyimide copper clad lamination of the present embodiment, including shell 1, the shell 1
It is internally provided with the metallic plate 2 for being parallel to 1 bottom surface of shell, the metallic plate 2 will be divided into two heating independent of each other inside shell 1
The top of chamber 3 and cooling chamber 4 positioned at 3 top of heating chamber, the heating chamber 3 is equipped with the heating tube parallel with the metallic plate 2
5, the two sides of the cooling chamber 4 are respectively equipped with air inlet 6 and air outlet 7, and 1 outside of the shell is equipped with air blower 8, the drum
Wind turbine 8 is connected to by the air inlet 6 with the cooling chamber 4, and the centre of the metallic plate 2 is equipped with electroheat pair 9.
The preparation facilities of the polyimide copper clad lamination of the present embodiment, when being heat-treated to polyamide acid film, with the back side
Heating, positive cooling means carry out, i.e., when being heat-treated in heating chamber 3, heat is from copper foil direction to polyamide acid film
It is heated (back side heating), meanwhile, in cooling chamber 4 (just using the outer surface of low temperature flow air cooling polyamide acid film
Face cools down) so that heat is transmitted from the inside (with copper foil contact surface) of polyamide acid film to the outside of polyamide acid film, and molten
There is certain temperature gradient before agent volatilization completely.
Air inlet 6 is equipped in cooling chamber 4, the air blower 8 on the outside of air inlet 6 and shell 1 is connected, by 8 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 8 is adjustable, cooling wind from
Air outlet 7 is gone out.The present invention is to take away using the outer surface of low temperature (20-30 DEG C) moving air cooling polyamide acid film
The heat of material surface is passed to maintain the surface low-temperature state of material from heating tube 5 by copper foil.
Wherein, the material of the metallic plate 2 is stainless steel plate.There are two effects for the tool of metallic plate 2, first, heat transfer, that is, add
The heat that heat pipe 5 generates is transmitted to copper foil by metallic plate 2, then carries out hot place to the polyamic acid being coated on copper foil by copper foil
Reason；Second is that sealing function, that is, avoid convection current between the hot-air in the moving air in cooling chamber 4 and heating chamber 3.
The outside of the shell 1 is additionally provided with condensate recycling device 10, the condensate recycling device 10 by the air outlet 7 with
The cooling chamber 4 is connected to.Air outlet 7 connects condensate recycling device 10, with recycling design, can realize recycling and the cycle profit of solvent
With.
The method that the preparation facilities using above-mentioned polyimide copper clad lamination of the present embodiment prepares polyimide copper clad lamination, packet
Include following steps：
Step 1：Under nitrogen atmosphere protection, by 13.000g p-phenylenediamine and 8.027g 4,4'- diaminodiphenyl ethers add
Enter in 360g N-Methyl pyrrolidone solvents, be stirred at room temperature dissolving, then slowly and several times addition 47.590g 3,3', 4,4'-
Bibenzene tetracarboxylic dianhydride stirs 6 hours after addition, and obtaining sticky polyamic acid polymer solution, (solid content is about
16%)；
Step 2：It is the polyamic acid solution that one layer of step 1 of coating obtains on 25 μm of copper foils in thickness, obtains covering polyamides
The copper foil of amino acid film.
Step 3：The copper foil for the covering polyamide acid film that step 2 is obtained, is placed in the preparation of above-mentioned polyimide copper clad lamination
On metallic plate in the cooling chamber of device, the heating tube in heating chamber is opened, is heat-treated；The heat treatment uses gradient liter
Temperature, specially 80 DEG C are kept for 1.5 hours, and 100 DEG C are kept for 1.5 hours, and 120 DEG C are kept for 2 hours, then kept for 1 hour at 220 DEG C,
Finally kept for 1 hour at 280 DEG C.
Air blower is opened simultaneously, and the solvent (i.e. N-Methyl pyrrolidone solution) in the polyamide acid film that volatilizees is covered
Drying polyamide acid film on copper foil.
Step 4：The drying polyamide acid film being covered on copper foil that step 3 obtains is subjected to hot imidization, the heat is sub-
Amination be specially keep at a temperature of 320 DEG C 1 hour to get to polyimide copper clad lamination.
Polyimide copper clad lamination surface obtained by the present embodiment is smooth, smooth (not being bent), number of bubbles zero, and thickness is
258μm。
Embodiment 2
The preparation facilities of a kind of polyimide copper clad lamination of the present embodiment, with embodiment 1.Wherein, the material of the metallic plate 2
Material is copper coin.
The outside of the shell 1 is additionally provided with condensate recycling device 10, the condensate recycling device 10 by the air outlet 7 with
The cooling chamber 4 is connected to.
The preparation facilities using above-mentioned polyimide copper clad lamination of the present embodiment carries out the preparation side of polyimide copper clad lamination
Method includes the following steps：
Step 1：Under nitrogen atmosphere protection, by 24.830g 4,4'- diaminodiphenylsulfones and 2.703g p-phenylenediamine add
Enter in 264g n,N-dimethylacetamide solvents, be stirred at room temperature dissolving, then slowly and several times 4 31.022g, 4'- Biphenyl Ethers
3,3', 4,4'- bibenzene tetracarboxylic dianhydride of dianhydride and 7.356g, stirs 6 hours after addition, will obtain sticky polyamic acid
Polymer solution (solid content about 20%)；
Step 2：It is the polyamic acid solution that one layer of step 1 of coating obtains on 7 μm of copper foils in thickness, obtains covering polyamide
The copper foil of sorrel.
Step 3：The copper foil for the covering polyamide acid film that step 2 is obtained, is placed in the preparation of above-mentioned polyimide copper clad lamination
On metallic plate in the cooling chamber of device, the heating tube in heating chamber is opened, is heat-treated；The heat treatment uses gradient liter
Temperature, specially 70 DEG C are kept for 1 hour, and 90 DEG C are kept for 1 hour, and 110 DEG C are kept for 1 hour, then kept for 1 hour at 200 DEG C, are finally existed
290 DEG C are kept for 0.5 hour.
Air blower is opened simultaneously, and the solvent (i.e. n,N-dimethylacetamide solution) in the polyamide acid film that volatilizees is covered
Cover the drying polyamide acid film on copper foil.
Step 4：The copper foil of the step 3 covering polyamide acid film that obtains that treated is subjected to hot imidization, the hot imines
Change be specially keep at a temperature of 300 DEG C 1 hour to get to polyimide copper clad lamination.
Polyimide copper clad lamination surface obtained by the present embodiment is smooth, smooth (not being bent), number of bubbles zero, thickness 43
μm。
Embodiment 3
The preparation facilities of a kind of polyimide copper clad lamination of the present embodiment, with embodiment 1.Wherein, the material of the metallic plate 2
Material is aluminium sheet.
The outside of the shell 1 is additionally provided with condensate recycling device 10, the condensate recycling device 10 by the air outlet 7 with
The cooling chamber 4 is connected to.
The preparation facilities using above-mentioned polyimide copper clad lamination of the present embodiment carries out the preparation side of polyimide copper clad lamination
Method includes the following steps：
Step 1：Under nitrogen atmosphere protection, by 24.830g 4,4'- diaminodiphenylsulfones (DDS), 7.308g 1,3- is bis-
(4- amino-benzene oxygens) benzene is added in 475g n,N-Dimethylformamide solvents, is stirred at room temperature dissolving, then adds slowly and several times
Enter 38.788g 4,4'- biphenyl ether dianhydrides (ODPA).It is stirred 6 hours after addition, sticky polyamic acid polymer will be obtained
Solution (solid content about 13%)；
Step 2：It is the polyamic acid solution that one layer of step 1 of coating obtains on 50 μm of copper foils in thickness, obtains covering polyamides
The copper foil of amino acid film.
Step 3：The copper foil for the covering polyamide acid film that step 2 is obtained, is placed in the preparation of above-mentioned polyimide copper clad lamination
On metallic plate in the cooling chamber of device, the heating tube in heating chamber is opened, is heat-treated；The heat treatment uses gradient liter
Temperature, specially 70 DEG C are kept for 1.5 hours, and 90 DEG C are kept for 1.5 hours, and 120 DEG C are kept for 2 hours, then kept for 1.5 hours at 200 DEG C,
Finally kept for 1 hour at 290 DEG C.
Air blower is opened simultaneously, and the solvent (i.e. n,N-Dimethylformamide solution) in the polyamide acid film that volatilizees is covered
Cover the drying polyamide acid film on copper foil.
Step 4：The copper foil of the step 3 covering polyamide acid film that obtains that treated is subjected to hot imidization, the hot imines
Change be specially keep at a temperature of 300 DEG C 1 hour to get to polyimide copper clad lamination.
Polyimide copper clad lamination surface obtained by the present embodiment is smooth, smooth (not being bent), number of bubbles zero, and thickness is
129μm。
Comparative example
Comparative example is with unlike embodiment 1, in step 3, the copper foil for the covering polyamide acid film that step 2 is obtained is set
In high temperature oven (entire baking oven is in some steady temperature, is heated up and down to film) common in the prior art, hot place is carried out
It manages, the heat treatment uses gradient increased temperature, and specially 70 DEG C are kept for 1.5 hours, and 90 DEG C are kept for 1.5 hours, and 120 DEG C of holdings 2 are small
When, then kept at 200 DEG C 1.5 hours, finally kept for 1 hour at 290 DEG C.Remaining step is all identical.
The many bubbles of polyimide film surface that this comparative example obtains, and be in rolled state, it is smooth, flat that surface cannot be obtained
The polyimide copper clad lamination of whole (not being bent).
It can be seen that the preparation facilities of the polyimide copper clad lamination of the present invention, solves in heat-treatment furnace in the prior art
Polyamic acid transition state surface premature hardening the problem of making the solvent in polyamic acid be difficult to volatilize, can be prepared poly-
Acid imide copper-clad plate, and it is simple in structure, operation is easy.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation facilities of polyimide copper clad lamination, which is characterized in that including shell (1), the shell (1) is internally provided with
It is parallel to the metallic plate (2) of shell (1) bottom surface, the metallic plate (2) will be divided into two heating independent of each other inside shell (1)
Chamber (3) and the cooling chamber (4) for being located at heating chamber (3) top, the top of the heating chamber (3) is equipped with puts down with the metallic plate (2)
The two sides of capable heating tube (5), the cooling chamber (4) are respectively equipped with air inlet (6) and air outlet (7), and the shell (1) is outside
Side is equipped with air blower (8), and the air blower (8) is connected to by the air inlet (6) with the cooling chamber (4), the metallic plate
(2) centre is equipped with electroheat pair (9).
2. a kind of preparation facilities of polyimide copper clad lamination according to claim 1, which is characterized in that the metallic plate
(2) material is one kind in stainless steel plate, copper coin or aluminium sheet.
3. a kind of preparation facilities of polyimide copper clad lamination according to claim 1 or 2, which is characterized in that the shell
(1) outside is additionally provided with condensate recycling device (10), and the condensate recycling device (10) passes through air outlet (7) and the cooling chamber
(4) it is connected to.
4. a kind of preparation facilities using claim 1-3 any one of them polyimide copper clad laminations prepares polyimide copper-clad
The method of plate, which is characterized in that include the following steps：
Step 1：Diamines, dianhydride and solvent are taken, is uniformly mixed, after reaction, obtains polyamic acid solution；Wherein, the diamines and
The molar ratio of dianhydride is 1:1, the weight of the solvent is 4-7 times of both diamines and dianhydride total weight；
Step 2：It is coated with the polyamic acid solution that one layer of step 1 obtains on copper foil, obtains the copper foil of covering polyamide acid film；
Step 3：The copper foil for the covering polyamide acid film that step 2 is obtained, is placed in the preparation facilities of above-mentioned polyimide copper clad lamination
Cooling chamber in metallic plate on, open heating chamber in heating tube, be heat-treated；Air blower is opened simultaneously, and volatilize polyamides
Solvent in amino acid film obtains being covered in the drying polyamide acid film on copper foil；
Step 4：The drying polyamide acid film being covered on copper foil that step 3 is obtained carries out hot imidization to get sub- to polyamides
Amine copper-clad plate.
5. the preparation method of polyimide copper clad lamination according to claim 4, which is characterized in that in step 1, the diamines
For p-phenylenediamine, m-phenylene diamine (MPD), 4,4'- diaminodiphenyl ethers, 4,4' diaminodiphenyl sulfone, 1,3- bis- (4- amino-benzene oxygens)
The mixture of one or more of benzene.
6. the preparation method of polyimide copper clad lamination according to claim 4, which is characterized in that in step 1, the dianhydride
For pyromellitic acid anhydride, 3,3', 4,4'- benzophenone tetracid dianhydrides, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'- biphenyl
The mixture of one or more of ether dianhydride.
7. the preparation method of polyimide copper clad lamination according to claim 4, which is characterized in that in step 1, the solvent
For N-Methyl pyrrolidone, one or more kinds of mixtures of DMAC N,N' dimethyl acetamide, N,N-dimethylformamide.
8. the preparation method of polyimide copper clad lamination according to claim 4, which is characterized in that in step 2, the copper foil
Thickness >=7 μm.
9. according to the preparation method of claim 4 to 8 any one of them polyimide copper clad lamination, which is characterized in that step 3
In, the heat treatment uses gradient increased temperature, and specially 70-80 DEG C is kept for 1 hour or more, and 90-100 DEG C is kept for 1 hour or more,
110-120 DEG C is kept for 1 hour or more, then is kept at 160-200 DEG C 1 hour or more, is finally kept for 0.5 hour at 280-290 DEG C
More than.
10. according to the preparation method of claim 4 to 8 any one of them polyimide copper clad lamination, which is characterized in that step 4
In, the hot imidization is specially to be kept for 0.5 hour or more at a temperature of 300-320 DEG C；It is poly- in the polyimide copper clad lamination
The thickness of acid imide film<50 μm, or >=50 μm, number of bubbles zero.
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| CN108541143B (en) | 2021-07-13 |
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