CN100572608C - The asperities treatment process of Copper Foil and asperities treatment solution - Google Patents
The asperities treatment process of Copper Foil and asperities treatment solution Download PDFInfo
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- CN100572608C CN100572608C CNB2005100785671A CN200510078567A CN100572608C CN 100572608 C CN100572608 C CN 100572608C CN B2005100785671 A CNB2005100785671 A CN B2005100785671A CN 200510078567 A CN200510078567 A CN 200510078567A CN 100572608 C CN100572608 C CN 100572608C
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Abstract
A kind of asperities treatment process of Copper Foil, comprise: operation A: as the treatment solution of asperities processing usefulness, modulation contains the operation of the sulfuric acid solution of at least a following asperities substance, and described asperities substance is to contain down the chemical structure of note and the heterogeneous ring compound with the ring type structure more than 2 in molecule; Process B: use described sulfuric acid solution, the single or double to Copper Foil under the current density more than the limit current density is implemented cathode treatment, thereby forms the overshooting shape electrodeposit of copper on described copper foil surface.According to the present invention, can provide at short notice, under the situation of the danger that does not have the alligatoring particle to come off, obtain uniform alligatoring particle, be suitable for making low roughness, have high friction pull, for the also good asperities treatment process of thin foil production efficiency with resin etc.In addition, also be provided at the treatment solution that uses in the asperities treatment process of this Copper Foil.
Description
Technical field
The present invention relates to the surface treatment method of Copper Foil, in more detail, it is low to relate to roughness, the asperities treatment process of improving with the cementability of resin etc. and being used for producing effectively the Copper Foil of thin thickness.In addition, the invention still further relates to the asperities treatment solution that is used for above-mentioned this asperities treatment process.
Background technology
Copper Foil is used in a large number as the current-collecting member of printed circuit board (PCB) purposes and secondary cell, and according to method for making, Copper Foil roughly is divided into rolled copper foil and electrolytic copper foil.
Rolled copper foil is calendered to rolling press by copper ingot and reels behind the purpose thickness and make.
In addition, electrolytic copper foil is to peel off precipitate after separating out the copper of purpose thickness from the copper electrolyte electrolysis with electric deposition device, reels and makes.At this moment, by in copper electrolyte, adding suitable additive, can produce mechanical characteristics and the surface shape that is suitable for purposes.In the occasion of electrolytic copper foil, the surface property on two sides is often different, electrodepositing rollor one side is called S (Shiny) face, even surface or glossy surface, and an opposite side is called M (Matte face) or uneven surface.
Copper Foil is except being made up of the situation about constituting the single of copper, provides as Alloy Foil also control the added ingredients of trace in order to improve mechanical characteristics and electrical characteristic after.
These Copper Foils and copper alloy foil are called as " Copper Foil is untreated " in affiliated field, usually can directly not use with the form of this Copper Foil that is untreated, under the situation that will obtain copper foil for printed circuit board, then implement " asperities processing " to improve with the cementability of insulating resin and to implement various surface treatments to give chemical adhesive power, heat-resisting, resistance to chemical reagents and rust-preventing characteristic, to obtain the secondary cell current collector with under the situation of Copper Foil, then implement various surface treatments to give friction pull and the rust-preventing characteristic with active substance.
When these surface treatments, the Copper Foil that is untreated that makes coiling is given characteristic continuously by in the handler with a plurality of operations.At this moment, the several seconds within tens of second by each operation, the time, weakness science and engineering preface was short more more, roller is also few by quantity, the reason that pit takes place, weighs with wrinkle etc. wounded is suppressed, and is effective especially to making thin foil.
The common asperities processing of copper foil for printed circuit board is to form according to following form.
At first, in sulfuric acid copper is bathed with Copper Foil as negative electrode, make insoluble anode relative with treated side and put, with the dendritic processes thing of the formation of the electric current more than limit current density copper.This first step is handled and is also referred to as " the gloomy and spotted plating of coating " owing to be that dendroid thereby powder are very easy to come off, if by this form with the bonding force of insulating resin a little less than, the reason that also become pit, weighs wounded.Therefore, further in sulfuric acid copper is bathed, electroplate, make the dendritic powder stabilization with the electric current below the limit current density.This second step processing is also referred to as " lining is electroplated ".
Gloomy and the spotted plating of coating is electroplated with lining and is used identical sulfuric acid copper to bathe, limit current density is not only to control with electric current, also it is adjusted to suitable condition for copper concentration, and in the gloomy and spotted plating bath of coating, add the additive that form is used of separating out of control dendritic powder sometimes.That is, in the processing of 2 steps, use 2 kinds of solution.
Because the gloomy and spotted galvanized anchorage of coating is poor, thereby before the lining plating in the 2nd step is fully carried out, need coming off of powder carried out strict management, be confined to usually each face is handled.
In addition, as the anode that uses in the above-mentioned processing, use insoluble anode usually.Be because under the situation of using soluble anode, can not expect on the entire treatment face, to form uniform alligatoring particle, anode mud allows the people worry to the influence of Copper Foil, and needs to pack in treatment trough continually, take out raw material, and operability variation and electrode position precision are also unstable.
In addition, for secondary cell current collector Copper Foil, thickness is that the requirement of the requirement of the thin foilization below 10 microns and the active substance maintenance dose that improves its surperficial per unit area becomes strong gradually.
As mentioned above, for the various expectations of the one or both sides of tackling Copper Foil mutually, developing complicated asperities processing.Asperities treatment technology as proposing so far has following technology.
For example in the public clear 40-15327 communique of spy, reported, in acidic copper electrolytes, copper foil surface has been implemented cathode treatment, the asperities treatment process that dendritic powder is separated out with the current density more than the limit current density.
And, because the single processing of dendritic powder (the gloomy and spotted plating of coating), come off easily a little less than its anchorage, therefore as the method that overcomes these shortcomings, for example in the spy opens No. 3293109, clear 48-24929 communique and U.S. special permission, reported, on formed dendritic powder on the copper foil surface, further implemented lining and electroplate (capsule platings) and make 2 of dendritic powder set stably go on foot the asperities treatment processs.
But the alligatoring particle of bathing acquisition merely by copper sulfate has inhomogeneous and roughness is high, produce the shortcoming of remaining copper after the etching easily at substrate.
Therefore, technology as the defective that remedies these methods, reported by boracic, bismuth, the acidic copper bath of titanium forms the method (for example special public clear 49-28815 communique) of uneven surface, containing selenium, tellurium, boron, titanium, in the acidic copper bath of bismuth with near the method (for example special public clear 54-38053 communique) of the current electroanalysis the limit current density, but owing to there is the problem of environment aspect, boron, selenium, the use of the material that tellurium etc. are harmful is restricted, and from utilize again or the viewpoint of trade waste on, accumulating of the objectionable constituent that contain in the Copper Foil also allows the people worry.
Also have, even as the asperities treatment process that forms the powder that more than limit current density, also has anchorage, reported the method (for example the spy opens flat 7-202367 communique) that forms uneven surface by the copper sulfate electrolytic bath that contains molybdenum, tungsten, boron and chlorion, nitrate ion, the nitric acid mists etc. but this method has the bath that contains nitric acid and corrosion treatment device significantly impair the shortcoming of running cost.
As the technology that remedies above-mentioned shortcoming, the method (for example the spy opens clear 57-184295 communique) that is formed uneven surface by the acidic copper electrolytes that contains molybdenum is disclosed, the method (for example the spy opens flat 6-169169 communique) of the uneven surface that formation is made of the overshooting shape copper electrodeposit of tungstenic, the asperities processing of in these 2 patent documentations, putting down in writing, though the gloomy and spotted galvanized homogeneity of coating is all improved in a measure, but in single processing (1 step handled), not only can not satisfy anchorage, and dropping of powder take place easily, the 2nd step of the galvanized dendritic powder set stably of having implemented to be covered need be handled.
As other asperities method, reported the mono bath of using mineral acid, with direct current or exchange with the etching of rolled copper foil surface electrochemistry, carry out the method (for example the spy opens clear 59-9050 communique) of asperities processing and carry out the gloomy and spotted plating of coating with pulse electrolysis, carry out the method (for example the spy opens clear 63-17597 communique) of asperities processing, but the etching of these mineral acid mono baths or alternating current electrolysis, only make copper foil surface become coarse, Copper Foil as high-density printed circuit board is in recent years used can not obtain sufficient bonding force.Also have, pulse electrolysis needs special power supply, and also needing simultaneously implements to be covered electroplates and the 2nd step of dendritic powder set is stably handled.
In addition, open in the 2003-258182 communique the spy, reported and utilized the method for laser with the tinsel asperitiesization, but utilize laser treatment to come the processing of asperitiesization, the treatment time is long, and splash is worrying to the influence of follow-up lamination operation, is unfavorable for industrialization.
And, open in the clear 55-29128 communique the spy, reported that the acidic copper bath by the pbz polymer agglutinant forms the method for uneven surface, but not only can not satisfy anchorage with single processing (1 step handled), and dropping of powder taken place easily, need be used for the 2nd step of the galvanized dendritic powder set stably of having implemented to be covered is handled.
In addition, open the spy and to have reported the method that forms uneven surface by the sulfuric acid copper bath that contains sulfo group benzoylimino sodium, benzoquinoline class, melamine class, aminobenzoic acids in the clear 55-30818 communique, wherein, additive except the benzoquinoline class, not only can not satisfy anchorage with single processing (1 step handled), and dropping of powder taken place easily, need be used for the 2nd step of the galvanized dendritic powder set stably of having implemented to be covered is handled.
About the benzoquinoline class, for example opening the Rz that discloses on the two sides in the flat 7-231152 communique the spy is that to be provided with length on 1～3 micron the two sides of Copper Foil be that 0.6～1.0 micron, maximum diameter are the copper foil for printed circuit board of 0.2 micron～0.8 micron contrary lacrimal fine bossing, and for forming this asperities particle, in disclosed embodiment, in sulfuric acid solution, add behind the α-Nai Kuilin of 50mg/l with 10A/dm
210 seconds of electrolysis treatment.Open this spy and to have implemented lining in the flat 7-231152 communique and electroplate, thereby under this condition, have the danger that powder drops as can be known.
In addition, open in the flat 8-222857 communique the spy and to disclose, glossy surface one side (S face side) of electrolytic copper foil is implemented to be provided with the processing (asperities processing) of projection, and at its uneven surface one side (M face side) formation needle-like or convex small electric deposition thrust, thereby implemented to be provided with the high-density multi-layered printed wiring internal layer Copper Foil of the processing of fine and uniform projection, processing as this M face one side, in disclosed embodiment, in sulfuric acid solution, add behind the α-Nai Kuilin of 50mg/l with 10A/dm
2Carry out 10 seconds of electrolysis treatment.Under this condition, the galvanized state that is not covered is estimated, and at length studied the benzoquinoline class with reference to comparative example.
In addition, open the spy and to have reported the method that forms uneven surface by the sulfuric acid copper bath that contains polythionic acid, thiosulphate, polythionate in the 2002-69691 communique, if use the gloss of sulfur-bearing is electroplated agent and the insoluble anode of sulfo-mineral compound, then owing to the oxygen bubbles that produces at anode, the spending rate of additive is very fast, bathe instability, and then need remove degradation production continuously.
In addition, proposed much to bathe the technology of carrying out the asperities processing by slightly acidic copper, but this Technology Need soluble anode, and under the situation that applies near the electric current the limiting current, the composition stability of solution lacks, under the situation of handling the long strip type paper tinsel, before and after existing characteristic deviation is arranged, need special organization to make it stable shortcoming.
In addition, processing (melanism processing) with the acicular particles of the public clear 32-137 communique of the spy formation cupric oxide that is representative, promptly be used in use in printed circuit board when way, handling as the multiple electrolytic surface of purpose after can not adapting to give chemical adhesive power, heat-resisting, resistance to chemical reagents and rust-preventing characteristic.
As the baseplate material of printed circuit board (PCB), the high heat resistant substrate material that does not use baseplate material halogen element and antimony, that pay attention to environment and be suitable for Pb-free solder attracts much attention gradually, but Copper Foil is abundant inadequately to the friction pull of these resins.In addition, be accompanied by the multifunction of mobile electronic equipment, in order to satisfy the densification of high frequency characteristics and distribution, require the thin thickness of Copper Foil, with the surface of Copper Foil with low roughness asperitiesization equably, but asperities treatment process in the past, a plurality of steps are grown, needed to treatment time, therefore poor for the logical paper tinsel of thin foil, and the alligatoring particle is inhomogeneous thereby roughness is high, and then the danger that the alligatoring particle comes off in the operation way is arranged, therefore also require to improve productivity and yield rate the uneven surface characteristic except requiring to improve.
In addition, for secondary cell current collector Copper Foil, the requirement of the thin foilization of thickness below 10 microns and the requirement of the active substance maintenance dose that improves its surperficial per unit area become strong gradually.
Summary of the invention
Therefore, the object of the present invention is to provide at short notice, under the situation of the danger that does not have the alligatoring particle to come off, can obtain uniform alligatoring particle, be suitable for making low roughness, have high friction pull, the surface treatment method (asperities treatment process) of the improved Copper Foil of logical paper tinsel of thin foil.In addition, the present invention also aims to provide the asperities treatment solution that is suitable for implementing this asperities processing.
Being used for asperities treatment process of the present invention with the processing of copper foil surface asperities is characterised in that and comprises following operation:
Operation A: as the treatment solution of asperities processing usefulness, modulation contains the operation of the sulfuric acid solution of at least a following asperities substance, and described asperities substance is to contain chemical structure of remembering down and the heterogeneous ring compound with the ring type structure more than 2 in molecule;
Change 1
Process B: use described sulfuric acid solution, the single or double to Copper Foil under the current density more than the limit current density is implemented cathode treatment, thereby forms the operation of the overshooting shape electrodeposit of copper at described copper foil surface.
In addition, the invention is characterized in that in above-mentioned asperities processing, described asperities substance is, in the aqueous solution, form complex compound and have the material of the overall stability constant β more than 14 with the cupric ion of 1 valency.
In addition, asperities treatment process of the present invention is characterised in that the described asperities substance of use is phenanthroline, pyridine or their derivative.Described asperities substance is selected from by 1,10-phenanthroline, bathophenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline, 4, one group of constituting of 7-dihydroxyl-1,10-phenanthroline, 2,2 '-bipyridine and terpyridyl.The chemical structural formula of these compounds is as follows.
Change 2
1,10-phenanthroline bathophenanthroline
2,9-dimethyl-1,10-phenanthroline
2
4,7-dihydroxyl-1,10-phenanthroline 2,2 '-bipyridine
Terpyridyl
In addition, the asperities treatment solution of the present invention that uses during with the surperficial asperities processing of Copper Foil is characterised in that, be the sulfuric acid solution that contains at least a asperities substance, described asperities substance is to contain chemical structure of remembering down and the heterogeneous ring compound with the ring type structure more than 2 in molecule.
Change 3
In addition, the invention is characterized in that the asperities substance that contains is for forming complex compound with the cupric ion of 1 valency and having the material of the overall stability constant β more than 14 in the aqueous solution in above-mentioned asperities treatment solution.
The present invention relates to the asperities processing of Copper Foil, use contains and at least aly above forms complex compound with the cupric ion of 1 valency and overall stability constant β is the sulfuric acid solution of the material more than 14 in the aqueous solution, under the current density more than the limit current density, carry out cathode treatment, thereby can be at short notice, under the situation of the danger that does not have the alligatoring particle to come off, obtain friction pull height, low, the uniform alligatoring particle of roughness, can improve productivity thin foil.
In addition, under the situation of asperities treatment process of the present invention, owing to do not need to cover electroplating work procedure, so compare with comprising the previous methods that covers electroplating work procedure, operation reduces, and can shorten total operation time that the asperities particle forms.And then the method according to this invention can not need causing pit and the powder that weighs wounded the phenomenon that drops to be carried out under the situation of strict management, with the two sides of Copper Foil asperitiesization simultaneously.
Description of drawings
Fig. 1 is the photo that is illustrated in the shape of the typical asperities processing particle that obtains in embodiment and the comparative example, all is the picture that takes from the direction of 40 degree that tilt with electron microscope.
Embodiment
If at length put down in writing asperities treatment process of the present invention, be under the situation of rolled copper foil then at the Copper Foil that is untreated, with the pickling Copper Foil that is untreated only, in the sulfuric acid electrolytic bath, carry out catholyte, thereby form the high overshooting shape electrodeposit of anchorage from the teeth outwards with the current density more than the limit current density.Then, implement inorganic mulch films such as Ni, Co, Zn monomer/alloy form organic mulch films such as processing, chromate treating, azole form handle and at least a antirust processing, the adherence of silane coupling agent in handling improve handle, heat-resisting, drug-resistant handles.
The complex compound that contains in described sulfuric acid electrolytic bath forms uses additive, promptly in the aqueous solution, form complex compound with 1 valency cupric ion, overall stability constant β is the material more than 14, can be from " chemical brief guide (compile on the basis) Japanization association " and [L.G.Sillen, A.E.Martell, " Stability Constantsof Metal Ion Complexes 1964; The Chem.Soc. "], [Stability Constants ofMetal Ion Complexes, Erix Hogfeldt, oxford; NewYork:Pergamon Press] etc. in the project of stability constant (formation constant) of complex compound in know.
The asperities substance that contains in the sulfuric acid solution that uses in asperities treatment process of the present invention (asperities treatment solution) is, in molecule, contain the chemical structure of above-mentioned [changing 1] and heterogeneous ring compound with the ring type structure more than 2, preferably in the aqueous solution, form complex compound with 1 valency cupric ion, overall stability constant β is the material more than 14, this material is the organic coordination base, further preferred nitrogen base dentate is selected from phenanthroline, pyridine or their derivative.
The concrete asperities substance that contains in asperities treatment solution of the present invention can enumerate 1,10-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline, 4,7-dihydroxyl-1,10-phenanthroline, 2,2 '-bipyridine and terpyridyl.
The overall stability constant β value of having represented the material that in following a part of embodiment and comparative example, uses below.
1,10-phenanthroline β=15.82
2,2 '-bipyridine β=14.35
Histidine β=6.20
In addition, as the organic coordination base of the Cu that knows so far (I) coordination compound, can enumerate 1,2-Ursol D, dimethylglyoxime etc. are if use overall stability constant β then can not get effect of the present invention less than 14 compound.
In addition, the catholyte condition of the process B of asperities treatment process of the present invention, change with electrolytic bath concentration, time, temperature, necessary asperities treatment capacity, therefore there is no particular limitation, but suitable is to be 1～10 second in the treatment time, bath temperature is 15～50 ℃, and current density is 10～100A/dm
2, electric weight is 20～500coul/dm
2
In addition, the concentration of the asperities substance in the asperities treatment solution, according to its kind optimum range difference, if with 1,10-phenanthroline 1 hydrate is an example, preferred 10mg/l～solubility limit 3g/l.The shape approximation of alligatoring particle is spherical, and its particle diameter be about 1 micron at the low side particle diameter of interpolation concentration, and in the high zone of concentration, it is littler that particle diameter becomes with adding change in concentration.In addition, particle diameter also is subjected to the influence of substrate roughness degree, the tendency that high substrate has particle diameter to diminish for smoothness.
Promptly, asperities substance of the present invention (complex compound forms and uses additive), according to its concentration, can make the vary in diameter of the alligatoring particle that can form, occasion at lower concentration one side (for example 10mg/l), when being used for printed circuit board (PCB), to halogen baseplate material and high heat resistant substrate material etc. be difficult in the past that the baseplate material of ball top to occur effective, also be used for electrode for secondary battery effectively.On the contrary, effective especially to the high frequency substrate material of the smoothness that requires copper foil surface when being used for printed circuit board (PCB) under the occasion of high density one side (for example 3g/l), it is also effective to become big processing as the surface-area that makes the surface of carrying out the asperities processing.
In addition, be about 0.5 micron or by in above-mentioned asperities substance, adding at least a transition metal, can obtaining particle diameter less than 0.5 micron fine asperities particle.
As transition metal, the suitable tungsten enumerated, molybdenum, titanium.
Below, based on embodiment and comparative example preferred implementation of the present invention is described.
Embodiment
The surface treatment procedure that carries out in following embodiment and comparative example is that the Copper Foil that is untreated shown in the his-and-hers watches 1 is finished after the operation that adding washes with water in (A)～(D) each operation shown in the table 2.And, carried out drying with warm wind at last.
The detailed conditions of having represented be untreated Copper Foil kind and the asperities processing of the present invention in embodiment and comparative example, used in the table 3.
Table 1
(a) paper tinsel
(b) paper tinsel
(c) paper tinsel
※ has carried out skimming treatment in advance to rolled copper foil
Table 2
(A) acid elution operation
| Sulfuric acid | 100g/l |
| Temperature | 30℃ |
| Treatment time | 10 seconds |
(B) asperities treatment process
| The ※ condition is with reference to table 2 |
(C) electrolytic chromate operation
| The Sodium chromate dihydrate | 3g/l |
| Sodium hydroxide | 10g/l |
| Temperature | 30℃ |
| Current density | 0.5A/dm 2 |
| Treatment time | 5 seconds |
(D) utilize the operation of silane coupling agent
| γ-glycidoxy propyl-triethoxysilicane | 1.5ml/l |
| Temperature | 30℃ |
| Treatment time | 10 seconds |
Table 3
Embodiment 1～8 expression is used the chemical structure that contains above-mentioned [changing 1] in molecule and is had in the heterogeneous ring compound of the ring type structure more than 2, in the aqueous solution, form complex compound with 1 valency cupric ion, overall stability constant β is the situation of the material more than 14, and comparative example 1 and 2 expressions do not add the situation of additive fully, the situation that benzoquinoline has been added in comparative example 3～7 expression, comparative example 8 expressions have been added cupric ion with 1 valency and have been formed complex compound, the overall stability constant β situation less than 14 material.In addition, the additive shown in the table 3 all is the medicine that Tokyo changes into the industry system.
The comparative result of having represented surface property in the table 4 below.
Table 4
In above-mentioned table 4, the evaluation reference of powder dropping JIS H8504 specification 15.1 tape test methods.Use the adhesive tape of putting down in writing among the 15.1.2 as the test adhesive tape, the asperities treated side of the sample that is fixed has been used the method for putting down in writing in (1)～(3) of 15.1.4.During judgement, situation that will the alligatoring particle significantly adheres on the bonding plane of the adhesive tape of peeling off is designated as " * ", and the situation of slightly adhering to is designated as " △ ", and the situation of not adhering to is designated as " zero ".
Surfaceness is represented with roughness Rz in addition the time in " * " in the powder dropping.Roughness Rz is according to JIS B0601 specification, uses サ one Off コ one ダ one SE1700 of little slope institute system
A measures.
The shape of typical roughening treatment particle is represented with photo in Fig. 1.In addition, the shape of roughening treatment particle all is from the 40 direction photographs of spending that tilt with electron microscope.
Photo by the embodiment 1 of Fig. 1 can confirm, formed spherical particle as the effect of asperities substance of the present invention, but separated out dendritic powder under the situation of the comparative example 1 that does not add the asperities substance.And, in the embodiment 8 of Fig. 1, observe and be formed uniformly the globular minuteness particle, and under the situation of having added the benzoquinoline class (comparative example 4), observe dendroid that powder drops easily, that extend to short transverse and be similar to acicular growth, also observed uneven alligatoring particle.In addition, adding under the situation of overall stability constant β less than 14 Histidine, how many above-mentioned growths be suppressed as, but dendritic inhomogeneous shape.
In addition, be treated to example with in the past 2 steps, compared adherence with base material with the Copper Foil that obtains in the comparative example 1.
Except carrying out under the following condition (B) asperities treatment process of table 2, be untreated Copper Foil and the operation identical have been adopted with embodiment 1.The uneven surface Rz that obtains is 10.2 microns.
Li asperities treatment process in the past
(the 1st step) gloomy and spotted plating of coating
Copper concentration 13g/l, acid concentration 100g/l, cl concn 10ppm, 30 ℃ of temperature, current density 50ASD, 3 seconds time
(the 2nd step) covers and electroplates
Copper concentration 65g/l, acid concentration 100g/l, cl concn 40ppm, 30 ℃ of temperature, current density 10ASD, 27 seconds time
About the evaluation of adherence strength, copper foil layer is stacked in high heat-resisting multilayer with on the baseplate material, measured according to IPC-TM-650 specification 2.4.8.5 and peeled off adherence strength.
Its result, peeling off adherence strength in example in the past is 0.97kN/m, and the Copper Foil of embodiment 1 is 1.25kN/m.
As can be known from the above results, under the occasion of the occasion of using the benzoquinoline class and electric weight little (the formation amount of alligatoring particle is few), promptly used for 1 step handled, anchorage improves really than the state that does not have to add, but confirm to exist dropping of powder, and bonding strength is also low, is not able to satisfy the level of printed circuit board (PCB) purposes in recent years.Improving electric weight (improving the formation amount of alligatoring particle) and improving under the situation of bonding strength, dropping of powder is more serious, does not reach the level that available 1 step processing is just used.
In addition, form complex compound having added in the aqueous solution with 1 valency cupric ion, under the situation of its overall stability constant β less than 14 material, a little less than the effect, thereby expression overall stability constant β need be more than 14.
Like this, the sulfuric acid solution that contains at least a above following material by use, on the one or both sides of Copper Foil, carry out cathode treatment with the current density more than the limit current density, form the overshooting shape electrodeposit of copper, can provide as the very useful Copper Foil of printed circuit board (PCB) purposes or use in electrode for secondary battery way, wherein, described material is, in molecule, contain the chemical structure of above-mentioned [changing 1] and heterogeneous ring compound, and this material forms complex compound with 1 valency cupric ion in the aqueous solution with the ring type structure more than 2, overall stability constant β is more than 14.
Asperities treatment process of the application of the invention and asperities treatment solution, can be at short notice, under the situation of the danger that does not have the alligatoring particle to come off, obtain the friction pull height, roughness is low and uniform alligatoring particle, can improve the productivity to thin foil.
Claims (4)
1. the asperities treatment process of a Copper Foil is the used method of asperities processing copper foil surface, it is characterized in that this method comprises operation A and process B;
Operation A: as the treatment solution of asperities processing usefulness, modulation contains and is selected from phenanthroline, 2, the operation of at least a sulfuric acid solution of the asperities substance in 2 '-bipyridine, terpyridyl and their derivative;
Process B: use described sulfuric acid solution, the single or double to Copper Foil under the current density more than the limit current density is implemented cathode treatment, thereby forms the operation of the overshooting shape electrodeposit of copper on described copper foil surface.
2. the asperities treatment process of Copper Foil according to claim 1 is characterized in that,
Described asperities substance, from by 1,10-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline, 4,7-dihydroxyl-1,10-phenanthroline, 2 is selected in the group that 2 '-bipyridine and terpyridyl constitute.
3. the asperities treatment solution of a Copper Foil, it is the asperities treatment solution that when asperities processing copper foil surface, uses, it is characterized in that, this asperities treatment solution is to contain to be selected from phenanthroline, 2 at least a sulfuric acid solution of the asperities substance in 2 '-bipyridine, terpyridyl and their derivative.
4. the asperities treatment solution of Copper Foil according to claim 3 is characterized in that, described asperities substance, from by 1,10-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline, 4,7-dihydroxyl-1,10-phenanthroline, 2 is selected in the group that 2 '-bipyridine and terpyridyl constitute.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005117990A JP4709575B2 (en) | 2005-04-15 | 2005-04-15 | Copper foil roughening treatment method and roughening treatment liquid |
| JP2005117990 | 2005-04-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1715457A CN1715457A (en) | 2006-01-04 |
| CN100572608C true CN100572608C (en) | 2009-12-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100785671A Expired - Fee Related CN100572608C (en) | 2005-04-15 | 2005-06-17 | The asperities treatment process of Copper Foil and asperities treatment solution |
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| Country | Link |
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| JP (1) | JP4709575B2 (en) |
| CN (1) | CN100572608C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103154328A (en) * | 2011-09-29 | 2013-06-12 | 油研工业股份有限公司 | Acidic aqueous composition for tin plating |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101505623B1 (en) * | 2007-09-19 | 2015-03-24 | 우에무라 고교 가부시키가이샤 | Manufacture method of buildup circuit board |
| TWI434965B (en) * | 2008-05-28 | 2014-04-21 | Mitsui Mining & Smelting Co | A roughening method for copper foil, and a copper foil for a printed wiring board which is obtained by the roughening method |
| CN102212853B (en) * | 2011-04-30 | 2012-11-14 | 山东金宝电子股份有限公司 | Surface treatment coarsening process for improving peel strength of copper foil |
| JP5407022B2 (en) * | 2011-09-02 | 2014-02-05 | 石原ケミカル株式会社 | Electronic copper plating bath, electronic parts with electrodeposition film formed by the bath |
| KR20140054435A (en) * | 2011-09-30 | 2014-05-08 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Copper foil excellent in adhesion with resin, method for manufacturing same, and printed wiring board or battery negative electrode material using electrolytic copper foil |
| KR20140019866A (en) * | 2011-12-07 | 2014-02-17 | 가부시키가이샤 씽크. 라보라토리 | Processing unit having condenser, and fully automatic gravure platemaking processing system using same |
| JP5950162B2 (en) * | 2012-09-18 | 2016-07-13 | 住友電気工業株式会社 | Method for producing aluminum film |
| CN105408525B (en) * | 2013-07-23 | 2019-03-08 | Jx日矿日石金属株式会社 | Surface treatment copper foil, Copper foil with carrier, the manufacturing method of substrate, resin base material, printing distributing board, copper-cover laminated plate and printing distributing board |
| JP6273317B2 (en) * | 2016-06-06 | 2018-01-31 | Ｊｘ金属株式会社 | Copper foil for printed circuit |
| CN111074317B (en) * | 2019-12-30 | 2022-02-18 | 禹象铜箔(浙江)有限公司 | Surface treatment method of copper foil and copper foil material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146848A (en) * | 1995-02-16 | 1997-04-02 | 三井金属矿业株式会社 | Copper foil and high-density multi-layered printed circuit board using the copper foil for inner layer circuit |
| JP2002069691A (en) * | 2000-08-31 | 2002-03-08 | Nippon Denkai Kk | Method for manufacturing copper foil for printed circuit board |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330983A (en) * | 1997-05-30 | 1998-12-15 | Fukuda Metal Foil & Powder Co Ltd | Electrolytic copper foil and its production |
| JP4258011B2 (en) * | 1999-03-26 | 2009-04-30 | 石原薬品株式会社 | Electro-copper plating bath and semiconductor device in which copper wiring is formed by the plating bath |
| JP3498306B2 (en) * | 1999-09-16 | 2004-02-16 | 石原薬品株式会社 | Void-free copper plating method |
-
2005
- 2005-04-15 JP JP2005117990A patent/JP4709575B2/en active Active
- 2005-06-17 CN CNB2005100785671A patent/CN100572608C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146848A (en) * | 1995-02-16 | 1997-04-02 | 三井金属矿业株式会社 | Copper foil and high-density multi-layered printed circuit board using the copper foil for inner layer circuit |
| JP2002069691A (en) * | 2000-08-31 | 2002-03-08 | Nippon Denkai Kk | Method for manufacturing copper foil for printed circuit board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103154328A (en) * | 2011-09-29 | 2013-06-12 | 油研工业股份有限公司 | Acidic aqueous composition for tin plating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1715457A (en) | 2006-01-04 |
| JP2006299291A (en) | 2006-11-02 |
| JP4709575B2 (en) | 2011-06-22 |
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