CN110143023A - Flexibility coat copper plate preparation method and printed circuit board - Google Patents
Flexibility coat copper plate preparation method and printed circuit board Download PDFInfo
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- CN110143023A CN110143023A CN201910407986.7A CN201910407986A CN110143023A CN 110143023 A CN110143023 A CN 110143023A CN 201910407986 A CN201910407986 A CN 201910407986A CN 110143023 A CN110143023 A CN 110143023A
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- layer
- preparation
- copper plate
- flexibility coat
- film layer
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Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 45
- 239000010949 copper Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010410 layer Substances 0.000 claims description 110
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 41
- 239000011889 copper foil Substances 0.000 claims description 34
- 238000003475 lamination Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 22
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 16
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 13
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 13
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000012805 post-processing Methods 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 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 4
- 239000012790 adhesive layer Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000010030 laminating Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 101001045744 Sus scrofa Hepatocyte nuclear factor 1-beta Proteins 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- -1 poly- naphthalene ester Chemical class 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of preparation method of flexibility coat copper plate and contain the printed circuit board of flexibility coat copper plate.The flexibility coat copper plate that preparation method of the present invention is prepared, both there is the excellent electric property including insulating layer low-k etc., also there is mechanical property excellent including peel strength etc., and there is more preferably performance, higher dimensional accuracy and yields by the printed circuit board that it is prepared.
Description
Technical field
The present invention relates to the technical fields of printed circuit board, especially a kind of to be applied in flexible print wiring board (FPCB)
Flexibility coat copper plate (FCCL) preparation method.
Background technique
Flexibility coat copper plate (Flexible Copper Clad Laminate, abridge FCCL), refers to thin in polyimides
One kind made of copper foil is coated on the insulating substrates such as film, polyester film or poly- naphthalene ester film can be compound with the flake of alternating bending
Material.And the flexible print wiring board (FPCB) for using flexibility coat copper plate to prepare for raw material, it is most multiple in printed circuit panel products
It is miscellaneous, purposes is most widely a kind of, can especially because it is with the characteristics such as frivolous, flexible, low-voltage, low consumpting power
As the shape and size of electronic equipment inner space realize therefore the three-dimensional wiring of three-dimensional space is widely used
In being widely used in aerospace equipment, navigation equipment, aircraft instrument, military guidance system and mobile phone, digital camera, digital vedio recording
In the various electronic products and equipment such as machine, vehicle satellite direction positioning device, LCD TV, laptop.Based on this, with
The fast development of electronic technology, so that the demand steady-state growth of flexibility coat copper plate, production scale also constantly expand, especially with poly-
Imide membrane is the high-performance flexibility coat copper plate of substrate, in addition to having many advantages, such as general flexibility coat copper plate pliability and frivolous
Outside, also there is excellent electric conductivity, heating conduction and excellent heat resistance, development growth trend is especially prominent, causes
The research and development upsurge extensively sent out.
Along with the continuous miniaturization of electronic product, flexible print wiring board also constantly show slimming, densification,
The development trend of multifunction, and the requirement that various novel electron equipment are applied in high-frequency high-speed field is also higher and higher.So
And the flexibility coat copper plate of the raw material as flexible print wiring board meet constantly be thinned requirement while, material
Rigidity inevasible can also reduce, so that in the technical process for preparing flexible print wiring board, due to the behaviour such as bending
Make and cause wiring layer occur fracture and removing equivalent damage, in turn result in using flexible print wiring board manufacture electronic product and
The decrease in yield of equipment.It is reduced the problem of causing to make up above-mentioned rigidity, bonding PET film etc. can be passed through in prior art
Enhancement layer, the method removed again after having prepared flexible print wiring board realize, but due to used adhesive with
And the increase of PET film layer and subsequent strip step, it will lead to the heat resistance reduction and dimensional stability of metal laminated plate
Deng other new problems.Meanwhile under miniaturization, the trend being thinned, for the requirement such as wiring precision and electrical property, wish
Hope surface roughness as far as possible low of metal foil layer, but then, in order to be bonded well with organic film, and hope
The surface of metal foil layer has certain roughness, and this contradiction also leads in the preparation of flexibility coat copper plate that there are various problems.
Therefore, how a kind of satisfaction slimming, densification, high dimensional accuracy are provided, and have compared with high finished product rate and
The flexibility coat copper plate of electrical property under excellent high-frequency high-speed application environment has very important significance and very extensive application
Prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of slimming, densification, high dimensional accuracy, and with higher finished product
The flexibility coat copper plate of rate and excellent electrical.
To achieve the above object, present invention employs the following technical solutions:
A kind of preparation method of flexibility coat copper plate, it is characterised in that the preparation method comprises the following steps that:
1) preparation bonding film layer, the adhesive layer include thermoplastic polyimide layer and non-thermal plasticity polyimide layer, head
First in the two sides coating thermoplastic polyimide precursor solution of non-thermal plasticity polyimide layer, then first add at 250 DEG C or less
After heat, then in 250-300 DEG C of heating, then in 180-200 DEG C of heating, it is then gradually cooled to room temperature, to obtain bonding film layer；
2) fluororesin layer is prepared, prepares fluorinated ethylene propylene copolymer substrate, and pre-treatment is carried out to its surface, after processing
Obtain fluororesin layer；
3) copper foil layer is prepared, it is 0.01-0.05 μm that copper foil roughness, which is controlled as Ra,.
4) lamination intermediate is prepared, protective film layer, copper foil layer, bonding film layer, fluororesin layer sequence are placed in hot-roll lamination
Continuous hot-press molding is carried out in equipment, and copper foil, copper are bonded on the outside of film layer to obtain fluororesin layer two sides fitting bonding film layer, bond
The lamination intermediate of fitting protective film layer on the outside of foil；Wherein, thermoplastic polyimide layer face and copper foil and the fluorine in film layer are bonded
Resin layer is in contact；
5) flexibility coat copper plate is prepared, after lamination intermediate is cooled to room temperature, protective film layer is removed, to obtain flexible copper-clad
Plate.
Preferably, the fusing point of the thermoplastic polyimide layer is lower than 250 DEG C；Preferably, the thermoplastic polyimide
Precursor solution is the mixed solution by bis- [4- (4- amino-benzene oxygen) phenyl] propane of bibenzene tetracarboxylic dianhydride and 2,2-.
Preferably, the thermoplastic polyimide layer with a thickness of 0.3-1.5 μm.
Preferably, the surface roughness Ra of the copper foil being in contact with the thermoplastic polyimide is 0.02-0.03 μ
m。
Preferably, the pre-treatment that fluorinated ethylene propylene copolymer substrate carries out is mixed to pass it through ozone and oxygen
The dipping microvesicle processing of gas solution is closed, treatment temperature is 40-60 DEG C, and the time is 2-5 minutes；Wherein, in the mixed gas
Ozone volumetric concentration be 20-30%, and in mixed gas solution ozone volumetric concentration be 0.5-2mg/dm3；It is described micro-
The diameter of bubble is preferably 10-40 μm.
Preferably, the hauling speed of the lamination is 1-2m/min, and temperature is 280-310 DEG C, pressure 3.5-4MPa.
Preferably, step 5) further comprises 6), post-processing to flexibility coat copper plate, and the post-processing is, in 100-
Heat treatment 5-10min is carried out along the tension that flexibility coat copper plate length direction applies 5-15N at a temperature of 120 DEG C, is subsequently placed to
Under the conditions of 40-50%RH, 3-5h is stood.
The object of the invention is also to provide the flexibility coat copper plates that the preparation method of above-mentioned flexibility coat copper plate is prepared.
The object of the invention is also to provide the flexible copper-clads that the preparation method for including above-mentioned flexibility coat copper plate is prepared
The printed circuit board of plate.
The flexibility coat copper plate that preparation method of the present invention is prepared both had had including the excellent of insulating layer low-k etc.
Electric property, it may have the excellent mechanical property such as including peel strength, the printed circuit board being prepared have more preferably
Performance, higher dimensional accuracy and yields.
Specific embodiment
Embodiment 1
Preparation method of the invention includes:
1) preparation bonding film layer, the adhesive layer include thermoplastic polyimide layer and non-thermal plasticity polyimide layer, head
The thermoplasticity of 4 μ m-thicks is first coated on the two sides of the 17FP non-thermoplastic polyimide film layer (Kaneka Corp.'s manufacture) of 17 μ m-thicks
Polyimide precursor solution, wherein thermoplastic polyimide precursor solution is the bibenzene tetracarboxylic dianhydride that mass ratio is 3:4
The dimethyl formamide solution that total concentration with bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2- is 14wt.%；Then exist
It is heated to 200 DEG C in 2min, then again in 300 DEG C of heating 0.5min, then again in 200 DEG C of heating 0.5min, then gradually cools down
To room temperature, to obtain bonding film layer, wherein about 1 μm of thermoplastic polyimide layer thickness, fusing point are about 240 DEG C.
2) fluororesin layer is prepared, prepares 12 μm of fluorinated ethylene propylene copolymer substrates, and pre-treatment, place are carried out to its surface
Fluororesin layer is obtained after reason；Wherein, the pre-treatment carried out to fluorinated ethylene propylene copolymer substrate is to pass it through ozone
It is handled with the dipping microvesicle of oxygen mixture liquid solution, treatment temperature is 50 DEG C, time 3min；Wherein, the mixed gas
In ozone volumetric concentration be 25%, and in mixed gas solution ozone volumetric concentration be 1mg/dm3；The microvesicle it is straight
Diameter is 30 μm.
3) copper foil layer is prepared, prepares 10 μm of copper foil layer, it is 0.02 μm that the surface roughness of copper foil layer, which is controlled as Ra,.
4) lamination intermediate is prepared, protective film layer, copper foil layer, bonding film layer, fluororesin layer sequence are placed in hot-roll lamination
Continuous hot-press molding is carried out in equipment, and copper foil, copper are bonded on the outside of film layer to obtain fluororesin layer two sides fitting bonding film layer, bond
The lamination intermediate of fitting protective film layer on the outside of foil；Wherein, thermoplastic polyimide layer face and copper foil and the fluorine in film layer are bonded
Resin layer is in contact；Wherein, the hauling speed of the lamination is 1.5m/min, and temperature is 300 DEG C, pressure 3.8MPa；Wherein,
Protective film layer is the non-thermoplastic polyimide film of 70 μ m-thicks, and before hot-roll lamination, protective film layer is first preheating to 250
℃。
5) flexibility coat copper plate is prepared, after lamination intermediate slow cooling to room temperature, flexibility coat copper plate is post-processed, it is described
Post-processing is to carry out heat treatment 8min along the tension that flexibility coat copper plate length direction applies 9N at a temperature of 110 DEG C, then put
It is placed under the conditions of 45%RH, stands 4h；Then removing protective film layer, to obtain flexibility coat copper plate.
Embodiment 2-3 mainly has adjusted the surface roughness of copper foil layer, and respectively Ra is 0.03 and 0.04, remaining with reality
It is identical to apply example 1.
Embodiment 4-5 mainly has adjusted the coating thickness of thermoplastic polyimide layer, in non-thermal plasticity polyamides in embodiment 4
The two sides of imines film layer is coated with the thermoplastic polyimide precursor solution of 2 μ m-thicks, and sub- in non-thermal plasticity polyamides in embodiment 5
The two sides of amine film layer is coated with the thermoplastic polyimide precursor solution of 6 μ m-thicks, remaining is same as Example 1.
Embodiment 6 mainly has adjusted dipping microvesicle processing temperature, specially 20 DEG C, handle 4min, remaining with implementation
Example 1 is identical.
The volumetric concentration that embodiment 7 mainly has adjusted ozone in mixed gas solution is 3mg/dm3, remaining is and embodiment
1 is identical.
The microbubble diameter that embodiment 8 mainly has adjusted dipping microvesicle processing is 60 μm, remaining is same as Example 1.
It is respectively 260 DEG C and 320 DEG C that embodiment 9-10, which mainly has adjusted laminating temperature in step 4), remaining is and embodiment
1 is identical.
Embodiment 11 mainly has adjusted lamination pressure 3.0MPa in step 4), remaining is same as Example 1.
The tension that embodiment 12 mainly has adjusted post-processing is 3N, remaining is same as Example 1.
The time of repose that embodiment 13 mainly has adjusted post-processing is 2h, remaining is same as Example 1.
The flexibility coat copper plate that above-described embodiment 1-13 is prepared carries out following experiment test, to obtain flexible copper-clad
As a result the properties of panel products are listed in table 1.
One, peel strength test
The test of peel strength makes sample according to " 6.5 peel strength " in JIS C6471, then with 90 degree of peel angle
Degree, 200mm/ minutes conditions, the copper foil of 3mm wide is removed, its loading (N/cm) is measured, and loading value is bigger, and removing is strong
Degree is bigger, shows that antistripping property is better.
Two, size changing rate is tested
The test of size changing rate is calculated according to JISC6481 5.16, by the quadrangle in square flexibility coat copper plate
Form the hole of diameter 1mm.After the copper foil for removing flexibility coat copper plate by corrosion treatment, placed in the thermostatic chamber of 20 DEG C of 60%RH
24 hours.Hereafter, with it is same before corrosion treatment, its distance is measured respectively to 4 holes.If the distance in each hole before copper foil removing
Measured value is D1, and the measured value of the distance in each hole after copper foil removing is D2, calculates size changing rate according to the following formula,
Size change over rate (%)=(D2-D1)/D1 × 100；
The absolute value of the size changing rate is smaller, then it represents that dimensional stability is more excellent.
Three, dielectric properties are tested
The test of dielectric properties, be using separating medium resonator method (SPDR method), in the environment of 23 DEG C, 55%RH with
The relative dielectric constant (Dk) of frequency 10GHz measurement characterizes.
Table 1
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | |
| Peel strength | 8.6 | 9.0 | 9.0 | 5.9 | 8.9 | 5.3 | 8.2 | 6.5 | 5.1 | 8.4 | 7.7 | 7.9 | 7.5 |
| Size changing rate | 0.005 | 0.005 | 0.006 | 0.005 | 0.007 | 0.005 | 0.006 | 0.005 | 0.006 | 0.007 | 0.006 | 0.009 | 0.008 |
| Dielectric constant | 2.5 | 2.6 | 2.7 | 2.5 | 2.8 | 2.7 | 2.7 | 2.8 | 2.8 | 2.5 | 2.7 | 2.6 | 2.6 |
Design below for present invention process and its parameter is further described:
The present invention selects fluorinated ethylene propylene copolymer as substrate, not only has good viscous with thermoplastic polyimide
Performance, while there are excellent dielectric properties.In order to guarantee pressing layer by layer with bonding film for fluorinated ethylene propylene copolymer substrate
Optimal dimensional stability, stripping performance and dielectric properties afterwards, the thickness of fluorinated ethylene propylene copolymer substrate and bonding film layer
Than should be between 1:1~1:2.
The thermoplastic polyimide film layer that the present invention selects, is examined from the angle of adherence, linear expansion coefficient, dimensional stability
Consider, the fusing point of preferred thermoplastic polyimide layer is lower than 250 DEG C, for example, by using bibenzene tetracarboxylic dianhydride and 2, bis- [4- (the 4- ammonia of 2-
Phenoxyl) phenyl] propane thermoplastic polyimide layer of the mixed solution as precursor preparation, such thermoplasticity polyamides
Imines makes final flexible copper-clad slab products have better heat resistance.Meanwhile the thickness of thermoplastic polyimide film layer
Preferably 0.3-1.5 μm, because if thermoplastic polyimide film layer less than 0.3 μm, will be unable to guarantee its adhesive property and
The peel strength of flexible copper-clad slab products；And if thermoplastic polyimide film layer is more than 1.5 μm, it will lead to heat hardening process
In due to curing shrinkage and thermal expansion so that the change in size of product is excessive, to influence properties of product.And it is bonded in preparation
During film layer, it should first be dried as far as possible below the fusing point of thermoplastic polyimide film layer organic in precursor solution
Then solvent is reacted more than thermoplastic polyimide film layer melting temperature, in order to avoid chilling causes after pyroreaction
Thermoplastic polyimide film layer sharply shrink, keep after a certain period of time, then being gradually cooled to room temperature in lower heating temperature.
The face of copper foil and the bonding contact of thermoplastic polyimide layer in the present invention, surface roughness control are in Ra
0.01-0.05μm.As documented by background technique, it is conventionally believed that, in order to improve copper foil and organic film preferably
Fitting, it is desirable to which the roughness of raising copper foil surface is to realize that copper foil is more preferably bonded with adhesive layer as anchor point as far as possible；So
And on the other hand, and hope reduces the roughness of copper foil surface as far as possible to improve assembly precision and electrical property, and this was a pair of originally
Irreconcilable contradiction.However it is a discovery of the invention that different with previous experience, although higher roughness can be made
Bond properties is improved for anchor point, but higher roughness also brings along problem, is exactly the higher roughness meeting of contact surface
So that surface generates larger bumps, and concave point and salient point be when being generated the tendency of removing division by external force, at concave point and salient point
The peel angle of copper foil and thermoplastic polyimide layer has notable difference, so that the generation of removing can be aggravated, and will in the present invention
Surface roughness control is 0.01-0.05 μm in Ra, smooth surface is obtained, so as to avoid peel angle caused by bumps
Problem, and the uniformity of peel angle can make peeling force uniformity suffered by interface, so that interface cohesion is stablized,
To increase the interfacial bond property of copper foil and thermoplastic polyimide layer, and then improve the whole stripping performance of product.Meanwhile
In order to guarantee to play the effect of above-mentioned raising peel strength, it is required that copper foil surface smooth enough, preferably Ra are less than
0.05μm；But can not be excessively smooth, in this way processing preparation cost can be caused to bear, preferably Ra is greater than 0.01 μm.
For the interface binding power for improving fluorinated ethylene propylene copolymer substrate layer and thermoplastic polyimide layer, the present invention couple
Fluorinated ethylene propylene copolymer substrate surface has carried out the special pre-treatment of dipping microvesicle of ozone and oxygen mixture liquid solution, adopts
With the processing mode of ozone and oxygen mixture liquid solution, preferably the organic dirt of substrate surface can be removed clean and be formed
Substrate surface treatment layer.Wherein, treatment temperature is preferably 40-60 DEG C, and the time is 2-5 minutes, if treatment temperature is lower than 40 DEG C,
The efficiency effect that will lead to filth disposal cannot all reach ideal, and if treatment temperature is higher than 60 DEG C, it not only will not be further
The effectively efficiency effect of deduction processing, will lead to instead microvesicle more faster loss and be unable to reach the effects of needs；Processing
Time should not be less than 2 minutes, otherwise be difficult to achieve the effect that thoroughly remove surface contaminants, but also be not to be exceeded 5 minutes, because
Processing too long will increase processing cost, reduce treatment effeciency, it is often more important that may cause ozone can be with the surface of substrate layer
Overreaction and lead to problems such as substrate intensity reduce.It handling in mixed gas, the volumetric concentration of ozone should meet 20-30%,
If above-mentioned ozone concentration is not achieved, desired treatment effect cannot be reached and lead to substrate layer and thermoplastic polyimide layer
Then performance it is insufficient；But concentration is also unsuitable excessively high, it otherwise only can meaningless increase processing cost.Ozone in mixed gas solution
Volumetric concentration be preferably 0.5-2mg/dm3, above-mentioned ozone concentration is not achieved, will lead to microvesicle ozone cannot be with the processing of substrate
Surface comes into full contact with and obtains process layer, but concentration it is excessive will lead to microvesicle ozone be diffused rapidly in atmosphere and cannot be fine
It is stranded in processing solution.The diameter of microvesicle is preferably 10-40 μm, and microvesicle manufacturing cost of the diameter less than 10 μm is high and does not have
It is necessary to, and diameter is greater than 40 μm of microvesicle, the contact area of microvesicle and substrate surface to be treated deficiency can be made and can not be real
Existing desired treatment effect, and excessive microvesicle can also diffuse more readily into atmospheric environment and be difficult to stagnant in processing solution
It stays.
During continuous hot-press is molding, the hauling speed of the preferably described lamination is 1-2m/min, temperature 280-310
DEG C, pressure 3.5-4MPa.Hauling speed has if it exceeds 2m/min and is laminated insufficient problem, and hauling speed is less than
1m/min can make production efficiency be greatly reduced.Laminating temperature is at least 280 DEG C, can guarantee between each bed boundary so sufficiently
Ground bonding, the especially combination of thermoplastic polyimide film layer and fluorinated ethylene propylene copolymer substrate layer；But laminating temperature
Also can not be excessively high, it is thinner than estimated otherwise to will lead to laminate product, and the resin that lamination process medial end portions are exposed can adhere to
Cause productivity to decline on laminating roll, or even further influences lamination.Lamination pressure is at least over 3.5MPa, in this way
It can guarantee enough hauling speeds and lower lamination problem, to realize sufficient lamination, guarantee copper foil and thermoplastic poly
Bond strength between imide layer, fluorinated ethylene propylene copolymer substrate layer and thermoplastic polyimide layer；But lamination pressure
Power also should not be more than 4MPa, and the dimensional stability that excessively high lamination pressure will lead to laminate product is deteriorated.
The present invention also needs to post-process flexibility coat copper plate after laminating, and the post-processing is, in 100-120 DEG C of temperature
Heat treatment 5-10min is carried out along the tension that flexibility coat copper plate length direction applies 5-15N under degree, is subsequently placed to 40-50%
Under the conditions of RH, 3-5h is stood.In heat treatment process, if tension is too low or too high, all laminate product can be caused to be heat-treated
It deforms in the process；And time of repose should be at least 3h, then it is short be difficult to ensure dimensional accuracy, but too long time of repose pair
It will affect production efficiency instead in the no effect of the raising of precision.
The type of protective film is not required particularly in the present invention, such as can be for heat-resist, recycling is convenient
Non-thermoplastic polyimide film, and protective film layer can be such as 70 μ m-thicks, to guarantee to play enough protective effects.It is simultaneously
Avoid the dimensional problem caused by sharply heated protective film layer protective film layer is first preheating to 250 preferably before hot-roll lamination
℃。
The flexibility coat copper plate that preparation method of the present invention is prepared it can be seen from the result of table 1, both having had includes insulation
The excellent electric property of layer low-k etc., it may have the excellent mechanical property such as including peel strength, and dimensionally stable
Performance is good, has more preferably performance, higher dimensional accuracy and yields by the printed circuit board that it is prepared, especially suitable
In the particular/special requirement that various novel electron equipment are applied in high-frequency high-speed field.
Although the preparation process and laminate product of the present invention is explained by the above embodiments flexibility coat copper plate of the present invention,
The present invention is not limited to the above embodiments.It should be clear to those skilled in the art, any improvement in the present invention,
Optimization, selection of concrete mode of equivalence replacement and technological parameter to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (9)
1. a kind of preparation method of flexibility coat copper plate, it is characterised in that the preparation method comprises the following steps that:
1) preparation bonding film layer, the adhesive layer includes thermoplastic polyimide layer and non-thermal plasticity polyimide layer, is existed first
The two sides coating thermoplastic polyimide precursor solution of non-thermal plasticity polyimide layer, then first after 250 DEG C or less heating,
It heats at 250-300 DEG C, then is heated at 180-200 DEG C again, be then gradually cooled to room temperature, to obtain bonding film layer；
2) fluororesin layer is prepared, prepares fluorinated ethylene propylene copolymer substrate, and pre-treatment is carried out to its surface, is obtained after processing
Fluororesin layer；
3) copper foil layer is prepared, it is 0.01-0.05 μm that copper foil roughness, which is controlled as Ra,.
4) lamination intermediate is prepared, protective film layer, copper foil layer, bonding film layer, fluororesin layer sequence are placed in hot-roll lamination equipment
Middle progress continuous hot-press molding bonds film layer to obtain the fitting of fluororesin layer two sides, bonds fitting copper foil on the outside of film layer, outside copper foil
The lamination intermediate of side fitting protective film layer；Wherein, thermoplastic polyimide layer face and copper foil and the fluororesin in film layer are bonded
Layer is in contact；
5) flexibility coat copper plate is prepared, after lamination intermediate is cooled to room temperature, protective film layer is removed, to obtain flexibility coat copper plate.
2. preparation method according to claim 1, it is characterised in that:
The fusing point of the thermoplastic polyimide layer is lower than 250 DEG C；Preferably, the thermoplastic polyimide precursor solution is
By the mixed solution of bis- [4- (4- amino-benzene oxygen) phenyl] propane of bibenzene tetracarboxylic dianhydride and 2,2-.
3. preparation method according to claim 1, it is characterised in that:
The thermoplastic polyimide layer with a thickness of 0.3-1.5 μm.
4. preparation method according to claim 1, it is characterised in that:
The surface roughness Ra of the copper foil being in contact with the thermoplastic polyimide is 0.02-0.03 μm.
5. preparation method according to claim 1, it is characterised in that:
It is to pass it through ozone and oxygen mixture liquid solution to the pre-treatment that fluorinated ethylene propylene copolymer substrate carries out
Dipping microvesicle processing, treatment temperature be 40-60 DEG C, the time be 2-5 minutes；Wherein, the body of the ozone in the mixed gas
Product concentration is 20-30%, and the volumetric concentration of ozone is 0.5-2mg/dm in mixed gas solution3；The diameter of the microvesicle is excellent
It is selected as 10-40 μm.
6. preparation method according to claim 1, it is characterised in that:
The hauling speed of the lamination is 1-2m/min, and temperature is 280-310 DEG C, pressure 3.5-4MPa.
7. preparation method according to claim 1, it is characterised in that:
Step 5) further comprises 6), post-processing to flexibility coat copper plate, and the post-processing is, at a temperature of 100-120 DEG C
Heat treatment 5-10min is carried out along the tension that flexibility coat copper plate length direction applies 5-15N, is subsequently placed to 40-50%RH item
Under part, 3-5h is stood.
8. a kind of flexibility coat copper plate, it is characterised in that:
The flexibility coat copper plate is prepared by any one of claim 1-7 preparation method.
9. a kind of printed circuit board, it is characterised in that:
The printed circuit board includes the flexibility coat copper plate in claim 8.
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| CN113386417A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Copper-clad plate and preparation method thereof |
| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
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