CN102233699A - 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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- CN102233699A CN102233699A CN2010101698506A CN201010169850A CN102233699A CN 102233699 A CN102233699 A CN 102233699A CN 2010101698506 A CN2010101698506 A CN 2010101698506A CN 201010169850 A CN201010169850 A CN 201010169850A CN 102233699 A CN102233699 A CN 102233699A
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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 the relevant ultrathin copper foil that is carrier with ultralow crest line Copper Foil, and more detailed saying so is made of carrier foils, peel ply and ultrathin copper foil, be applied in high density and fine-line printed circuit board (PCB), multilayer board, cover base material such as brilliant film.
Background technology
Ultrathin copper foil with carrier is used in the printed circuit-board assembly of the field of electronic industry as 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 to use the carrier (Copper Foil or aluminium foil) of 18～35 μ m thickness, encloses the thick electrolytic copper foil as thin as a wafer of 1～6 μ m again via electroplating again.
High density volumeization 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, on the circuit of line-spacing requirement broad 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 the 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 handle, increase expense and the matter of time handled, and in the circuit board manufacture 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 not exclusively or very easily peel off disappearances such as causing the variable color of pressing plate rear oxidation easily.
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 influences 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 influences etching.In addition, also can influence 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 for use 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 be to use the HTE Copper Foil, have uniform surface not good easily, and problem such as pin hole.On the other hand, use rolled copper foil, and limited the usability of product because of problems such as fabric width and costs.
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 influence product quality.
Summary of the invention
The object of the present invention is to provide a kind of ultrathin copper foil and the manufacture method thereof that are carrier with ultralow crest line Copper Foil, to improve the defective that exists in the background technology.
For achieving the above object, the ultrathin copper foil that is carrier with ultralow crest line Copper Foil provided by the invention, by carrier foils, peel ply, and ultrathin copper foil through electroplating combination and constituting; 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 to be plated on the carrier foils with the quaternary alloy electroplate liquid that contains molybdenum, nickel, chromium and potassium to form, and thickness is 1～6 μ m;
(3) ultrathin copper foil is to bestow Cu on 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.
The described ultrathin copper foil that is carrier with ultralow crest line Copper Foil, wherein peel ply is that metal or its metal mixture by molybdenum, nickel, chromium, potassium quaternary alloy forms peel ply.
The described ultrathin copper foil that is carrier with ultralow crest line Copper Foil, wherein carrier layer is ultralow crest line Copper Foil, its thickness is 12-70 μ m.
The described ultrathin copper foil that is carrier with ultralow crest line Copper Foil, 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.
The manufacture method that is the ultrathin copper foil of carrier with ultralow crest line Copper Foil 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 constituted, 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) on peel ply, impose Cu
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 with ultralow crest line Copper Foil be carrier, quaternary alloy peel ply and ultrathin copper foil constituted with the ultralow crest line Copper Foil ultrathin copper foil that is carrier 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, its peel ply influences the bond strength maximum between carrier foils and ultrathin copper foil, this peel ply is by the molybdenum of quaternary alloy, nickel, chromium, when the potassium metal is constituted, 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 a 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 applied to the adhesion of different substrate materials for carrier foils and ultrathin copper foil.
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 that is carrier with ultralow crest line Copper Foil, 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 or the like, 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 be unit with μ m) below 1.5 μ m, constituted.
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 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 (as peel property, etching characteristic and high-temperature stability etc.) have to(for) the present invention does not have obvious deterioration.But if 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 influencing the important electrodeposited coating of adhesion maximum, the peel ply adhesion then can't be peeled off too by force, too then under the elevated temperature heat pressing carrier foils very easily separate with ultrathin copper foil, cause problems such as ultrathin copper foil glassy surface oxidation stain, how effectively controlling the 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 discovery has a quaternary alloy of peel property when peel ply by plating metal such as molybdenum, nickel, chromium, potassium one by one and constitutes, can overcome above-mentioned disappearance and reach purpose of the present invention.
Ultrathin copper foil of the present invention is that cupric pyrophosphate electroplating bath, the back of using pH=6～10 earlier use the copper sulphate electroplating bath plated metal carrier foils of pH=1～12 to form; on peel ply, electroplate formation cupric pyrophosphate layer earlier and do not washed off with the protection peel ply, influence the formation of follow-up ultrathin copper foil and the change of peel strength by the copper sulphate electroplating bath as the layer that prevents of peel ply.In the copper sulphate electroplating bath, form ultrathin copper foil thickness 1～6 μ m then.
Below be further to understand technical characterictic, support summary of the invention with explanation for possessing embodiment.
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 Cu again
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 hear 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.
Embodiment 1
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, utilizing known roughening treatment technology to implement copper particle in pressing (mat) face again handles, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be 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, utilizing known roughening treatment technology to implement copper particle in stitching surface again handles, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier, its carrier foils and ultrathin copper foil almost do not have 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, utilize known roughening treatment technology to implement copper particle again and handle, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier in stitching surface.Record carrier foils and the ultrathin copper foil adhesion is 2.87g/cm with the tensile testing machine of Japanese Shimadzu corporate 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, utilizing known roughening treatment technology to implement copper particle in stitching surface again handles, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier records carrier foils and the ultrathin copper foil adhesion is 5.40g/cm with the tensile testing machine of Japanese Shimadzu corporate 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, utilize known roughening treatment technology to implement copper particle again and handle, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier in stitching surface.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, utilizing known roughening treatment technology to implement copper particle in stitching surface again handles, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be 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, utilize known roughening treatment technology to implement copper particle again and handle, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier in stitching surface.Record carrier foils and the ultrathin copper foil adhesion is 11.45g/cm with the tensile testing machine of Japanese Shimadzu corporate 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, utilize known roughening treatment technology to implement copper particle again and handle, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier in stitching surface.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 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, utilize known roughening treatment technology to implement copper particle again and handle, and then impose the antirust processing and the silane-coating of zinc-plated and chromate, the ultrathin copper foil that to make with ultralow crest line Copper Foil be carrier in stitching surface.Record carrier foils and the ultrathin copper foil adhesion is 10.8g/cm with the tensile testing machine of Japanese Shimadzu corporate system.
In the foregoing description, 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 and does not almost have adhesion between carrier foils and ultrathin copper foil, as embodiment 2.The 2.87g/cm with the carrier adhesion 5.40g/cm of the ultralow crest line Copper Foil ultrathin copper foil that is carrier and embodiment 3 of comparative example 1 is quite approaching, the problem that does not have fissility between carrier foils and ultrathin copper foil, but the glassy surface oxidation resistance deficiency of the ultrathin copper foil of comparative example 1 has the slight oxidation phenomenon.
The ultrathin copper foil that is carrier with ultralow crest line Copper Foil 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 though 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 ultrathin copper foil that is carrier with ultralow crest line Copper Foil 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 embodiment quaternary alloy or lower with the carrier foils adhesion that quaternary alloy was become as comparative example 4 formed peel ply metals, preferable processing characteristics is arranged, and do not have problems such as plating bath turbidity sediment and discharge of wastewater, so it is indispensable to form the metal of quaternary alloy.The present invention is low with the adhesion of the carrier foils of the ultralow crest line Copper Foil ultrathin copper foil that is carrier and ultrathin copper foil, and the technical scheme that forms the quaternary alloy combination of peel ply does not see that open report is arranged.
The embodiment of the invention with the ultralow crest line Copper Foil ultrathin copper foil that is carrier, quite excellent for the environment tolerance, the carrier peel strength is low to have high temperature resistant, moisture-proof gas, 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 do the elevated temperature heat pressing with resin base material, remove carrier foils after the pressing, observe the ultrathin copper foil glassy surface and do not have 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 as table 2 and shown in Figure 3, visible carrier foils and ultrathin copper foil adhesion are excellent.
Of the present invention with the ultralow crest line Copper Foil ultrathin copper foil that is carrier except excellent peel property and tolerance for environment are arranged, 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 problems such as short circuit or broken string.This characteristic helps the 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 (5)
1. ultrathin copper foil that is carrier with ultralow crest line Copper Foil, by carrier foils, peel ply, and ultrathin copper foil through electroplating combination and constituting; 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 to be plated on the carrier foils with the quaternary alloy electroplate liquid that contains molybdenum, nickel, chromium and potassium to form, and thickness is 1～6 μ m;
(3) ultrathin copper foil is to bestow Cu on 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 that is carrier with ultralow crest line Copper Foil according to 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 that is carrier with ultralow crest line Copper Foil according to claim 1, wherein, carrier layer is ultralow crest line Copper Foil, its thickness is 12-70 μ m.
4. the ultrathin copper foil that is carrier with ultralow crest line Copper Foil according to 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.
5. the manufacture method that is the ultrathin copper foil of carrier with ultralow crest line Copper Foil according to claim 1 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 constituted, 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) on peel ply, impose Cu
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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| CN105979710A (en) * | 2015-03-11 | 2016-09-28 | 福田金属箔粉工业株式会社 | Composite metal foil and manufacturing method thereof, 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 |
| CN112226790A (en) * | 2020-10-19 | 2021-01-15 | 九江德福科技股份有限公司 | Production method of ultrathin high-strength electronic copper foil |
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| CN104584699A (en) * | 2012-08-08 | 2015-04-29 | Jx日矿日石金属株式会社 | Copper foil with carrier attached thereto |
| CN104584699B (en) * | 2012-08-08 | 2017-09-26 | Jx日矿日石金属株式会社 | Copper foil with carrier |
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