CN102233699B - Extremely thin copper foil using ultralow ridge copper foil as carrier and manufacturing method of extremely thin copper foil - Google Patents
Extremely thin copper foil using ultralow ridge copper foil as carrier and manufacturing method of extremely thin copper foil Download PDFInfo
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- CN102233699B CN102233699B CN 201010169850 CN201010169850A CN102233699B CN 102233699 B CN102233699 B CN 102233699B CN 201010169850 CN201010169850 CN 201010169850 CN 201010169850 A CN201010169850 A CN 201010169850A CN 102233699 B CN102233699 B CN 102233699B
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Abstract
The invention relates to an extremely thin copper foil using an ultralow ridge copper foil as a carrier. The extremely thin copper foil consists of a carrier foil, a stripping layer and an extremely thin copper foil, wherein the carrier foil is made of the ultralow ridge copper foil of which the two surfaces are smooth; the ultralow ridge copper foil can provide the advantages of no pin hole, high thickness uniformity, low surface roughness and the like for the loaded extremely thin copper foil; and the stripping layer can influence the bonding strength between the carrier foil and the extremely thin copper foil greatly, and consists of quaternary alloy metal with stripping characteristics. In the invention, the extremely thin copper foil using the ultralow ridge copper foil as the carrier has low carrier bonding strength and relatively high environment resistance, and has the characteristics of high-temperature resistance, moisture resistance, acid resistance, alkali resistance and the like; and the carrier foil and the extremely thin copper foil still have high stripping characteristics under a high-temperature hot-press environment.
Description
Technical field
The present invention is relevant ultrathin copper foil take ultralow crest line Copper Foil as carrier, and more detailed saying by carrier foils, peel ply and ultrathin copper foil consisted of, be applied in high density and fine-line printed circuit board (PCB), multilayer board, cover the base material such as brilliant film.
Background technology
Ultrathin copper foil with carrier is used in the field of electronic industry as the printed circuit-board assembly of high density and fine-line purposes, what stress now is light, thin and short, littleization, precision requirement for circuit-line also tends to accurate, and the thinning processing demands of Copper Foil also increases day by day.Existing ultrathin copper foil with carrier generally is the carrier (Copper Foil or aluminium foil) that uses 18～35 μ m thickness, encloses the thick as thin as a wafer electrolytic copper foil of 1～6 μ m via electroplating again again.
High density volume along with various electronic building bricks, the combination of circuit substrate and circuit pattern thereof also must densifications, for example encapsulate employed printed circuit board (PCB), live width between its circuit and line-spacing are the high density fine circuits that needs about 30 μ m, if the thicker time that then can increase etching (Etching) of electrolytic copper foil of using, its result, the perpendicularity that forms a circuit pattern side ancient piece of jade, round, flat and with a hole in its centre is destroyed, requiring wider circuit at line-spacing is can not produce, but then may produce the problem of short circuit or broken string for narrower circuit.
Peel ply between carrier foils and ultrathin copper foil, the organic compounds containing nitrogen of organic system commonly used or chromium metal or the chromate binary alloy inorganic film of inorganic system.Use organic stripping film break point of organic system, not only there are plating bath and discharge of wastewater to process, increase expense and the matter of time processed, and in the circuit board preparation technology of high temperature, can produce bubble, caused the workmanship and generation electrical testing stability problem of circuit board.On the other hand, peel off rete by inorganic be that binary alloy is formed, its thicknesses of layers ratio is the key factor of control carrier foils and ultrathin copper foil bond strength, and is not good when both proportion control, peels off easily not exclusively or very easily peel off disappearances such as causing the variable color of pressing plate rear oxidation.
The ultrathin copper foil that the fine circuits pattern is used, be be on the carrier foils peel ply directly in addition electrolytic deposition form, best thickness is below the 5 μ m.Because the carrier foils surface morphology directly affects peel ply and ultrathin copper foil layer, when the carrier surface rugosity was too high, the ultrathin copper foil of follow-up plating also easily had high rugosity, and then affects etching.In addition, also can affect the thickness homogeneity of ultrathin copper foil during carrier foils surface morphology heterogeneity.When carrier foils had pin hole, ultrathin copper foil also can have pin hole simultaneously.Because carrier foils is the basis of follow-up peel ply and ultrathin copper foil, so the selecting of carrier copper foil, quite important.Known invention, mainly be with traditional HTE (High Temperature Elongation) Copper Foil or rolled copper foil as carrier copper foil, but use the HTE Copper Foil, have easily uniform surface not good, and the problem such as pin hole.On the other hand, use rolled copper foil because of problems such as fabric width and costs, and limited the usability of product.
In addition, the hot pressing of the pressing of ultrathin copper foil (mat) face and epoxy resin base material, the roughening treatment of ultrathin copper foil stitching surface, antirust processing and silane coating processing etc. are all closely bound up with the then property of base material, obviously affect product quality.
Summary of the invention
The object of the present invention is to provide a kind of ultrathin copper foil and manufacture method thereof take ultralow crest line Copper Foil as carrier, to improve the defective that exists in the background technology.
For achieving the above object, the ultrathin copper foil take ultralow crest line Copper Foil as carrier provided by the invention, by carrier foils, peel ply, and ultrathin copper foil through electroplating combination and consisting of; Wherein:
(1) carrier layer is ultralow crest line Copper Foil, and its two sides light is level and smooth, and thickness is 12-70 μ m;
(2) peel ply is that the quaternary alloy electroplate liquid that contains molybdenum, nickel, chromium and potassium is plated on the carrier foils and forms, and thickness is 1～6 μ m;
(3) ultrathin copper foil is to bestow Cu at peel ply
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, 10～60 ℃ of temperature are bathed, current density: 1～5A/dm in pH=6～10
2, the plating of 15 seconds conduction time is as the peel ply diaphragm, and again with copper concentration 50～100g/L, sulfuric acid: 90～125g/L bathes 40～70 ℃ of temperature, current density: 10～50A/dm
2, conduction time: plating in 20 seconds become the Copper Foil of thickness 1～6 μ m.
Described ultrathin copper foil take ultralow crest line Copper Foil as carrier, wherein peel ply is that metal or its metal mixture by molybdenum, nickel, chromium, potassium quaternary alloy forms peel ply.
Described ultrathin copper foil take ultralow crest line Copper Foil as carrier, wherein carrier layer is ultralow crest line Copper Foil, its thickness is 12-70 μ m.
Described ultrathin copper foil take ultralow crest line Copper Foil as carrier, wherein can be used for the extremely smart circuit purposes of high density printed circuit board (PCB), multi-layer sheet printed circuit board (PCB), cover brilliant film resin base material or pi film.
Manufacture method take ultralow crest line Copper Foil as the ultrathin copper foil of carrier provided by the invention comprises:
(1) the ultralow crest line Copper Foil in the South Asia extremely excellent, that thickness is 12～70 μ m of the planarization below the glassy surface roughness 1.5 μ m is placed in by
A. nickel sulfate hexahydrate compound: 10～50g/L,
B. molybdic acid is received dihydrate: 0.5～10g/L,
c.K
4P
2O
7：50～100g/L，
D.CrO
3: in the electroplate liquid bath that 0.5～2g/L consists of, 0～50 ℃ of temperature is bathed, current density: 2.5～6A/dm in pH=6～10
2, add 20 seconds conduction time to give and electroplate that to make adsorbance be 0.05mg/dm
2～60mg/dm
2Peel ply;
(2) impose Cu at peel ply
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, 10～60 ℃ of temperature are bathed, current density 1～5A/dm in pH=6～10
2, the plating of 15 seconds conduction time is as the peel ply protective layer;
(3) again with copper concentration 50～100g/L, sulfuric acid concentration 90～125g/L bathes 40～70 ℃ of temperature, current density 10～50A/dm
2, implement the ultrathin copper foil of electroplating 1～6 μ m thickness 20 seconds conduction time.
The present invention take ultralow crest line Copper Foil as carrier, the ultrathin copper foil take ultralow crest line Copper Foil as carrier that consisted of of quaternary alloy peel ply and ultrathin copper foil as shown in Figure 1.Its carrier layer is used the ultralow crest line Copper Foil in South Asia, has the surface morphology homogeneous, the characteristics of the level and smooth and free of pinholes of surface roughness.And the peel ply aspect, the bond strength that its peel ply affects between carrier foils and ultrathin copper foil is maximum, this peel ply is by the molybdenum of quaternary alloy, nickel, chromium, when the potassium metal is consisted of, have more good anti-oxidation characteristics and etching characteristic than bianry alloy, simultaneously under the hot pressing environment of high temperature, carrier foils and ultrathin copper foil still have excellent peel property, and this is key property of the present invention.
Description of drawings
Fig. 1 is the Copper Foil organigram.
Fig. 2 is etching (Etching) circuit kenel.
Fig. 3 is the adhesion that carrier foils and ultrathin copper foil are applied to different substrate materials.
Primary clustering symbol description in the accompanying drawing:
1 ultrathin copper foil, 2 peel plies, 3 carrier foils, 4 circuit etching kenels, 5 etching base material kenels.
The specific embodiment
The invention provides a kind of ultrathin copper foil take ultralow crest line Copper Foil as carrier, this ultrathin copper foil has good anti-oxidation characteristics and etching characteristic, carrier foils and ultrathin copper foil still have excellent peel property under the hot pressing environment of high temperature, and carrier copper foil thickness homogeneous and pin hole quantity are few simultaneously.
The metallic carrier paper tinsel of general ultrathin copper foil with carrier has aluminium foil, Copper Foil, titanium foil, stainless steel foil etc., and its carrier foils is all with the extremely excellent metal forming of profile pattern, thickness 18～35 μ m, carrier foils glassy surface roughness (Surface Roughness; Refer to 10 average roughness value Rz, and take μ m by unit) below 1.5 μ m, consisted of.
The present invention is ultralow crest line Copper Foil (VLP Copper Foil) that as the carrier layer on the basis of peel ply and ultrathin copper foil its characteristics are that the two sides presents bright feature, and rugosity is low, thickness homogeneous and free of pinholes.Above-mentioned characteristic is all helpful for follow-up peel ply and ultrathin copper foil.Yet be stressed that, based on the follow-up good peel ply of carrying of the present invention and ultrathin copper foil layer formula, no matter the therefore kind of carrier copper foil or the variation of thickness, the carrier copper foil of its characteristic of its fundamental characteristics of ultrathin copper foil (such as peel property, etching characteristic and high-temperature stability etc.) have to(for) the present invention does not have obviously deteriorated.If but use good VLP Copper Foil, for the ultrathin copper foil with carrier copper foil, its overall permanence has lifting.
The present invention is as the peel ply of the framework of carrier foils and ultrathin copper foil, for affecting the important electrodeposited coating of adhesion maximum, the peel ply adhesion then can't be peeled off too by force, then closing lower carrier foils at high temperature hot pressing too very easily separates with ultrathin copper foil, cause the problems such as ultrathin copper foil glassy surface oxidation stain, how effectively controlling uniformity and the thickness of peel ply, is the important topic that must overcome at present.In order to overcome above-mentioned disappearance, when the present invention tests one by one discovery has a quaternary alloy of peel property when peel ply by plating the metal such as molybdenum, nickel, chromium, potassium and consists of, can overcome above-mentioned disappearance and reach purpose of the present invention.
Ultrathin copper foil of the present invention is that the cupric pyrophosphate electroplating bath that uses first pH=6～10, the copper sulphate electroplating bath plated metal carrier foils of rear use pH=1～12 form; on peel ply, electroplate first formation cupric pyrophosphate layer and do not washed off by the copper sulphate electroplating bath with the protection peel ply as the preventing layer of peel ply, affect the formation of follow-up ultrathin copper foil and the change of peel strength.Then in the copper sulphate electroplating bath, form ultrathin copper foil thickness 1～6 μ m.
Below be further to understand technical characterictic, support summary of the invention for possessing embodiment with explanation.
According to the present invention, be that the Copper Foil that planarization is extremely excellent is made carrier foils and inserted nickel sulfate hexahydrate compound concentration 10～50g/L, molybdic acid is received dihydrate concentration 0.5～10g/L, K
4P
2O
7: 50～100g/L, CrO
3: electroplate in the electroplating bath of 0.5～2g/L and form peel ply, then on peel ply, impose again Cu
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: the plating that 100～400g/L bathes is as protective layer, and again with copper concentration: 50～100g/L, the electrolyte of sulfuric acid: 90～125g/L is electroplated becomes the following ultrathin copper foil of 3 μ m.
In order to obtain that stronger peel strength is arranged between ultrathin copper foil surface and substrate, ultrathin copper foil of the present invention surface imposes roughening treatment, enclose in the roughening treatment surface again and have antirust and zinc, nickel metal and chromate the heat resistance effect, in order to promote the peel strength of ultrathin copper foil and base material, silane-coating makes it have the peel strength of lifting effect again.
1, with below the glassy surface roughness 1.5 μ m, planarization is extremely excellent, and the South Asia VLP Copper Foil of thickness 18 μ m is as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, K
4P
2O
7: 50～100g/L, CrO
3: 0.5～2g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 6～15A/dm
2, conduction time: electroplate in the electroplating bath of 20 seconds molybdenum, nickel, chromium, potassium quaternary alloy and make tool molybdenum, nickel, chromium, potassium-sodium alloy peel ply.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in pressing (mat) face, and then impose antirust processing and the silane-coating of zinc-plated and chromate, make the ultrathin copper foil take ultralow crest line Copper Foil as carrier, its carrier foils and ultrathin copper foil can't be peeled off after tested.
Embodiment 2
1, with below the glassy surface roughness 1.5 μ m, planarization is extremely excellent, and the South Asia VLP Copper Foil of thickness 18 μ m is as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, K
4P
2O
7: 50～100g/L, CrO
3: 0.5～2g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 1～2.5A/dm
2, conduction time: electroplate in the electroplating bath of 20 seconds molybdenum, nickel, chromium, potassium quaternary alloy and make tool molybdenum, nickel, chromium, potassium-sodium alloy peel ply.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then impose antirust processing and the silane-coating of zinc-plated and chromate, make the ultrathin copper foil take ultralow crest line Copper Foil as carrier, its carrier foils and ultrathin copper foil are almost without adhesion after tested.
Embodiment 3
1, with below the glassy surface roughness 1.5 μ m, planarization is extremely excellent, and the South Asia VLP Copper Foil of thickness 18 μ m is as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, K
4P
2O
7: 50～100g/L, CrO
3: 0.5～2g/L, PH:6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: electroplate in the electroplating bath of 20 seconds molybdenum, nickel, chromium, potassium quaternary alloy and make tool molybdenum, nickel, chromium, potassium-sodium alloy peel ply.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then imposes antirust processing and the silane-coating of zinc-plated and chromate, makes the ultrathin copper foil take ultralow crest line Copper Foil as carrier.Record carrier foils and ultrathin copper foil adhesion as 2.87g/cm take the tensile testing machine of Japanese Shimadzu company system.
Comparative example 1
1, with the South Asia VLP Copper Foil of the extremely munificent degree 18 μ m of the following planarization of glassy surface roughness 1.5 μ m as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, K
4P
2O
7: 50～100g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: make tool molybdenum, nickel, potassium-sodium alloy peel ply in the electroplating bath of 20 seconds molybdenum, nickel, potassium ternary alloy three-partalloy.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then impose antirust processing and the silane-coating of zinc-plated and chromate, make the ultrathin copper foil take ultralow crest line Copper Foil as carrier, record carrier foils and ultrathin copper foil adhesion as 5.40g/cm take the tensile testing machine of Japanese Shimadzu company system.
Comparative example 2
1, with the South Asia VLP Copper Foil of the extremely munificent degree 18 μ m of the following planarization of glassy surface roughness 1.5 μ m as carrier foils.
2, insert molybdic acid and receive dihydrate: 0.5～10g/L, K
4P
2O
7: 50～100g/L, CrO
3: 0.5～2g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: electroplate in the electroplating bath of 20 seconds molybdenum, potassium, chromium ternary alloy three-partalloy and make tool molybdenum, potassium, evanohm peel ply.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, PH:6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then imposes antirust processing and the silane-coating of zinc-plated and chromate, makes the ultrathin copper foil take ultralow crest line Copper Foil as carrier.Its carrier foils and ultrathin copper foil can't be peeled off after tested.
Comparative example 3
1, with the South Asia VLP Copper Foil of the extremely munificent degree 18 μ m of the following planarization of glassy surface roughness 1.5 μ m as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, K
4P
2O
7: 50～100g/L, CrO
3: 0.5～2g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: make tool nickel, potassium, evanohm peel ply in the electroplating bath of 20 seconds nickel, potassium, chromium ternary alloy three-partalloy.
3. then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then impose antirust processing and the silane-coating of zinc-plated and chromate, make the ultrathin copper foil take ultralow crest line Copper Foil as carrier, its carrier foils and ultrathin copper foil can't be peeled off after tested.
Comparative example 4
1, with the South Asia VLP Copper Foil of the extremely munificent degree 18 μ m of the following planarization of glassy surface roughness 1.5 μ m as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, CrO
3: 0.5～2g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: make tool nickel, molybdenum, evanohm peel ply in the electroplating bath of 20 seconds nickel, molybdenum, chromium ternary alloy three-partalloy.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4. again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then imposes antirust processing and the silane-coating of zinc-plated and chromate, makes the ultrathin copper foil take ultralow crest line Copper Foil as carrier.Record carrier foils and ultrathin copper foil adhesion as 11.45g/cm take the tensile testing machine of Japanese Shimadzu company system.
Comparative example 5
1, with the South Asia VLP Copper Foil of the extremely munificent degree 18 μ m of the following planarization of glassy surface roughness 1.5 μ m as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, CrO
3: 0.5～2g/L, natrium citricum: 100～350g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: make tool nickel, molybdenum, chromium, sodium alloy peel ply in the electroplating bath of 20 seconds nickel, molybdenum, chromium, sodium quaternary alloy.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then imposes antirust processing and the silane-coating of zinc-plated and chromate, makes the ultrathin copper foil take ultralow crest line Copper Foil as carrier.Its carrier foils and ultrathin copper foil can't be peeled off after tested.
Comparative example 6
1, with below the glassy surface roughness 1.5 μ m, planarization is extremely excellent, and the South Asia HTE Copper Foil of thickness 18 μ m is as carrier foils.
2, insert nickel sulfate hexahydrate compound: 10～50g/L, molybdic acid is received dihydrate: 0.5～10g/L, K
4P
2O
7: 50～100g/L, CrO
3: 0.5～2g/L, pH=6～10, bathe temperature: 10～50 ℃, current density: 2.5～6A/dm
2, conduction time: electroplate in the electroplating bath of 20 seconds molybdenum, nickel, chromium, potassium quaternary alloy and make tool molybdenum, nickel, chromium, potassium-sodium alloy peel ply.
3, then impose Cu in the peel ply top
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, pH=6～10, bathe temperature: 10～60 ℃, current density: 1～5A/dm
2, conduction time: 15 seconds plating is as the peel ply protective layer.
4, again with copper concentration: 50～100g/L, sulfuric acid: 90～125g/L, bathe temperature: 40～70 ℃, current density: 25A/dm
2, conduction time: the ultrathin copper foil that becomes thickness 3 μ m is electroplated in execution in 20 seconds.
5, the known roughening treatment technology of recycling is implemented the copper particle processing in stitching surface, and then imposes antirust processing and the silane-coating of zinc-plated and chromate, makes the ultrathin copper foil take ultralow crest line Copper Foil as carrier.Record carrier foils and ultrathin copper foil adhesion as 10.8g/cm take the tensile testing machine of Japanese Shimadzu company system.
In above-described embodiment, comparative example and table 1, embodiment 1 improves the electroplating current density of quaternary alloy, causes the carrier adhesion to cross by force and can't peel off.Otherwise the electroplating current density of reduction quaternary alloy then carrier adhesion dies down, and causes between carrier foils and ultrathin copper foil almost without adhesion, such as embodiment 2.The carrier adhesion 5.40g/cm take ultralow crest line Copper Foil as the ultrathin copper foil of carrier of comparative example 1 and the 2.87g/cm of embodiment 3 are quite approaching, the problem that does not have fissility between carrier foils and ultrathin copper foil, but the glassy surface oxidation resistance of the ultrathin copper foil of comparative example 1 is not enough, and the slight oxidation phenomenon is arranged.
The ultrathin copper foil take ultralow crest line Copper Foil as carrier of comparative example 4 is that the carrier adhesion is higher, the problem that does not also have fissility between carrier foils and ultrathin copper foil, but its quaternary alloy plating bath has the phenomenon of turbidity and precipitation, can increase a lot of processing times and expense for problems such as the management of plating bath and discharge of wastewater.All having peel property although form the metal of the peel ply of comparative example 1 and comparative example 4, the shortcoming of oxidation resistance deficiency and plating bath turbidity and precipitation is arranged, is not best selection.
The metal of other comparative example 2,3 and 5 formation peel ply all has the carrier adhesion to cross strong and can't be smoothly and the problem peeled off of ultrathin copper foil.Its carrier adhesion of the ultrathin copper foil take ultralow crest line Copper Foil as carrier of tool quaternary alloy of the present invention is low, the problem that does not have fissility between carrier foils and ultrathin copper foil, compared to comparative example 1 to comparative example 5, the quaternary alloy of embodiment 3 has that the carrier adhesion is lower, free of pinholes, without problems such as Bath mudding precipitation and discharge of wastewater, so it is indispensable to form the metal of quaternary alloy.Carrier foils and the adhesion of ultrathin copper foil of the present invention take ultralow crest line Copper Foil as the ultrathin copper foil of carrier is low, forms the technical scheme of quaternary alloy combination of peel ply there are no open report.
The ultrathin copper foil take ultralow crest line Copper Foil as carrier of the embodiment of the invention, quite excellent for the environment tolerance, the carrier peel strength is low to have high temperature resistant, moisture-proof gas, the characteristic such as acidproof, alkaline-resisting, carrier foils and ultrathin copper foil still have excellent peel property under the hot pressing environment of high temperature, for example doing high temperature hot pressing with resin base material closes, remove carrier foils after the pressing, observe the ultrathin copper foil glassy surface without oxidized variable color, quite excellent for the environment tolerance; The performance of normal temperature adhesion is also very excellent in table 1; Do hot pressing with the base material of various high glass transition temperatures, the adhesion after the pressing between carrier foils and ultrathin copper foil also is quite excellent, and such as table 2 and shown in Figure 3, visible carrier foils and ultrathin copper foil adhesion are excellent.
Ultrathin copper foil take ultralow crest line Copper Foil as carrier of the present invention is except having excellent peel property and the tolerance for environment, etching characteristic is also quite excellent, the perpendicularity that forms a circuit pattern side ancient piece of jade, round, flat and with a hole in its centre after the etching is good, the noresidue of circuit pattern side ancient piece of jade, round, flat and with a hole in its centre lower edge, and can not produce the problems such as short circuit or broken string.This characteristic helps electrical reliability and the quality stability of printed circuit board (PCB).See Fig. 2 for details.
Table 1: peel ply forms the adhesion relation between metal and carrier
Table 2: carrier foils and ultrathin copper foil are applied to the adhesion of different substrate materials
| Base material | BT(g/cm) | NPG180IA(g/cm) | NP180(g/cm) |
| Adhesion | 11.96 | 4.61 | 12.89 |
Note:
Gas company of BT=Mitsubishi resin, Bismelaimide Triazene, bismaleimide-triazine resin, trade name BT.
NPG180IA=South Asia company halogen-free resin, 180 ℃ of glass transition temperatures (Tg), trade name NPG180IA.
NP180=South Asia company halide resin, 180 ℃ of glass transition temperatures (Tg), trade name NP180.
Claims (4)
1. ultrathin copper foil take ultralow crest line Copper Foil as carrier, by carrier foils, peel ply, and ultrathin copper foil through electroplating combination and consisting of; Wherein:
(1) carrier layer is ultralow crest line Copper Foil, and its two sides light is level and smooth, and thickness is 12-70 μ m;
(2) peel ply is that the quaternary alloy electroplate liquid that contains molybdenum, nickel, chromium and potassium is plated on the carrier foils and forms, and thickness is 1～6 μ m;
(3) ultrathin copper foil is to bestow Cu at peel ply
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, 10～60 ℃ of temperature are bathed, current density: 1～5A/dm in pH=6～10
2, the plating of 15 seconds conduction time is as the peel ply diaphragm, and again with copper concentration 50～100g/L, sulfuric acid: 90～125g/L bathes 40～70 ℃ of temperature, current density: 10～50A/dm
2, conduction time: plating in 20 seconds become the Copper Foil of thickness 1～6 μ m.
2. the ultrathin copper foil take ultralow crest line Copper Foil as carrier as claimed in claim 1, wherein, peel ply is to form peel ply by the metal of molybdenum, nickel, chromium, potassium quaternary alloy or its metal mixture.
3. the ultrathin copper foil take ultralow crest line Copper Foil as carrier as claimed in claim 1, wherein, can be used for the extremely smart circuit purposes of high density printed circuit board (PCB), multi-layer sheet printed circuit board (PCB), cover brilliant film resin base material or pi film.
4. the manufacture method take ultralow crest line Copper Foil as the ultrathin copper foil of carrier as claimed in claim 1 comprises:
(1) the ultralow crest line Copper Foil planarization below the glassy surface roughness 1.5 μ m is extremely excellent, that thickness is 12～70 μ m be placed in by
A. nickel sulfate hexahydrate compound: 10～50g/L,
B. sodium molybdate dihydrate: 0.5～10g/L,
c.K
4P
2O
7：50～100g/L，
D.CrO
3: in the electroplate liquid bath that 0.5～2g/L consists of, 0～50 ℃ of temperature is bathed, current density: 2.5～6A/dm in pH=6～10
2, add 20 seconds conduction time to give and electroplate that to make adsorbance be 0.05mg/dm
2～60mg/dm
2Peel ply;
(2) impose Cu at peel ply
2P
2O
7.3H
2O:10～60g/L, K
4P
2O
7: 100～400g/L, 10～60 ℃ of temperature are bathed, current density 1～5A/dm in pH=6～10
2, the plating of 15 seconds conduction time is as the peel ply protective layer;
(3) again with copper concentration 50～100g/L, sulfuric acid concentration 90～125g/L bathes 40～70 ℃ of temperature, current density 10～50A/dm
2, implement the ultrathin copper foil of electroplating 1～6 μ m thickness 20 seconds conduction time.
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| JP5228130B1 (en) * | 2012-08-08 | 2013-07-03 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| JP5859155B1 (en) * | 2015-03-11 | 2016-02-10 | 福田金属箔粉工業株式会社 | Composite metal foil, method for producing the same, and printed wiring board |
| TWI690607B (en) * | 2018-06-15 | 2020-04-11 | 南亞塑膠工業股份有限公司 | Method for manufacturing porous super-thin copper foil and collector plate |
| CN112226790B (en) * | 2020-10-19 | 2022-04-22 | 九江德福科技股份有限公司 | Production method of ultrathin high-strength electronic copper foil |
| CN117737653B (en) * | 2023-12-19 | 2024-08-16 | 深圳市知音科技有限公司 | Strippable copper carrier plate, preparation method thereof and application thereof in advanced packaging |
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|---|---|---|---|---|
| CN101374388A (en) * | 2008-03-28 | 2009-02-25 | 苏陟 | Method for preparing fine line flexible circuit board with high peeling strength |
| CN101466875A (en) * | 2006-06-12 | 2009-06-24 | 日矿金属株式会社 | Rolled copper or copper alloy foil with roughened surface and method of roughening rolled copper or copper alloy foil 289494 |
| CN101476138A (en) * | 2008-12-30 | 2009-07-08 | 广东梅县梅雁电解铜箔有限公司 | Method for manufacturing ultrathin electrolytic copper foil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466875A (en) * | 2006-06-12 | 2009-06-24 | 日矿金属株式会社 | Rolled copper or copper alloy foil with roughened surface and method of roughening rolled copper or copper alloy foil 289494 |
| CN101374388A (en) * | 2008-03-28 | 2009-02-25 | 苏陟 | Method for preparing fine line flexible circuit board with high peeling strength |
| CN101476138A (en) * | 2008-12-30 | 2009-07-08 | 广东梅县梅雁电解铜箔有限公司 | Method for manufacturing ultrathin electrolytic copper foil |
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