CN101297067A - Method for manufacture of electrolytic copper foil, electrolytic copper foil manufactured by the method, surface-treated copper foil manufactured using the electrolytic copper foil, and copper-clad la - Google Patents
Method for manufacture of electrolytic copper foil, electrolytic copper foil manufactured by the method, surface-treated copper foil manufactured using the electrolytic copper foil, and copper-clad la Download PDFInfo
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Abstract
Disclosed is a method for manufacture of an electrolytic copper foil having a lower profile compared to a conventional, commercially available low-profile electrolytic copper foil and also having excellent mechanical strength, with good efficiency. The method may comprise electrolyzing a sulfate-type copper electrolyte solution containing a quaternary ammonium salt polymer having a cyclic structure and a chlorine to form the electrolytic copper foil, wherein the quaternary ammonium salt polymer to be added to the sulfate-type copper electrolyte solution is a DDAC polymer composed of two or more monomer units. Preferably, the quaternary ammonium salt polymer is a diaryldimethylammonium chloride having a number average molecular weight of 300 to 10000. Preferably, the sulfate-type copper electrolyte solution comprises bis(3-sulfopropyl)disulfide or 3-mercapto-1-propanesulfonic acid which has a mercapto group.
Description
Technical field
The present invention relates to electrolytic copper foil manufacture method, electrolytic copper foil that this manufacture method obtains, use the surface treatment copper foil that this electrolytic copper foil obtains and use this electrolytic copper foil or copper clad laminate that this surface treatment copper foil obtains.Especially, relate to that to separate out the face side with it be that low profile is the manufacture method of the electrolytic copper foil of feature.
Background technology
In the past, electrolytic copper foil was extensive use of as the base mateiral of printed circuit board (PCB).And, in the electronic product and electric product of normal use printed circuit board (PCB), require so-called compactization of miniaturization, lightweight etc.In the past, such electronic product and electric product were necessary the as far as possible little spacingization of the signal circuit of employed printed circuit board (PCB) in order to realize compactization.Therefore, when making printed circuit board (PCB), the overetched setting-up time when forming circuit in order to shorten by etching improves the etching factor that forms circuit, carries out correspondence by adopting thinner Copper Foil.
Meanwhile, miniaturization, light-weighted electronic product and electric product require multifunction.Therefore, in order to guarantee parts erection space as much as possible in the area of the printed circuit board (PCB) that limits, the etching factor when forming circuit by optimizing carries out correspondence.Especially the winding of directly carrying IC chip etc. automatically in conjunction with (TAB) substrate or membrane of flip chip encapsulation (COF) substrate purposes in, in order further to optimize etching factor, require the above low profile electrolytic copper foil of common printed circuit board (PCB).In addition, as low profile be Copper Foil and substrate resin between bonding interface in concavo-convex low meaning on use.
In order to solve such problem, a kind of manufacture method of electrolytic copper foil is disclosed in the patent documentation 1, it uses the sulfuric acid copper electroplating liquid of the multipolymer that contains diallyldialkylammonihalide salt and sulfurous gas in the manufacture method of the electrolytic copper foil of electrolysis sulfuric acid copper electroplating liquid.In this sulfuric acid copper electroplating liquid, preferably contain polyoxyethylene glycol and chlorine and 3-sulfydryl-1-sulfonic acid.And, the electrolytic copper foil that obtains by this manufacture method, and the surfaceness of the bonding plane between insulating substrate (separating out surface roughness) is little, in the situation that is the electrolytic copper foil of thickness 10 μ m, is the low profile (roughness) about Rz=1.0 ± 0.5 μ m.
In addition, in patent documentation 2, even disclose a kind of gelatin or glue (Rubber of not using) etc., also can make the method for the electrolytic copper foil that surfaceness is little, unit elongation is good of the face of separating out, make in the manufacture method of electrolytic copper foil in electrolysis, used to contain polyoxyethylene glycol and chlorine and 3-sulfydryl 1-sulfonic acid sulfuric acid copper electroplating liquid as feature by the sulfuric acid copper electroplating liquid.In addition, the stickup of the electrolytic copper foil that obtains by this manufacture method the surfaceness (separating out surface roughness) of face of insulating substrate little, in the situation that is the electrolytic copper foil of thickness 10 μ m, be the low profile (roughness) about Rz=1.5 ± 0.5 μ m.
In patent documentation 3, disclose and will contain amine compound with specific skeleton and the copper electrolyte of organosulfur compound is used to make electrolytic copper foil as additive, described amine compound obtains by making the compound and the amine compound addition reaction that have an above epoxy group(ing) in a part.As described in embodiment, the surfaceness Rz of the electrolytic copper foil that this manufacture method obtains is in the scope of 0.90～1.20 μ m, and unit elongation is 6.62～8.90% under the normal temperature, and tension stress is 30.5～37.9kgf/mm under the normal temperature
2, the high temperature unit elongation is 12.1～18.2%, hot tensile power is 20.1～22.3kgf/mm
2
In patent documentation 4, disclose and to have contained quaternary ammonium compound and the copper electrolyte of organosulfur compound is used to make electrolytic copper foil as additive with specific skeleton, described quaternary ammonium compound, by making compound and the amine compound addition reaction that in a part, has an above epoxy group(ing), then, nitrogen is quaternary ammoniated and obtain.As described in embodiment, the surfaceness Rz of the electrolytic copper foil that is obtained by this manufacture method is in the scope of 0.94～1.23 μ m, and unit elongation is 6.72～9.20% under the normal temperature, and tension stress is 30.5～37.2kgf/mm under the normal temperature
2, the high temperature unit elongation is 11.9～18.2%, tension stress is 19.9～23.4kgf/mm under the high temperature
2
On the other hand, in patent documentation 5, disclose a kind of surface-treated electro-deposited copper foil, it is implemented roughened separating out of the surfaceness Rz of the face of separating out of the electrolytic copper foil that the is untreated paper tinsel identical or little with the surfaceness Rz of the glossy surface of this electrolytic copper foil that is untreated and is used as bonding plane on face.In the manufacturing of the above-mentioned electrolytic copper foil that is untreated, use added compound with sulfydryl, chloride ion, molecular weight below 10000 lower molecular weight glue and the electrolytic solution of high molecular polysaccharide.Specifically, the compound with sulfydryl is a 3-sulfydryl 1-propanesulfonic acid salt, and the molecular weight of lower molecular weight glue is below 3000, and high molecular polysaccharide is a Natvosol.
Then,, then can form the face of separating out of good low profile really, show very good character as the low profile electrolytic copper foil if use these manufacture method to make electrolytic copper foil.
[patent documentation 1] spy opens the 2004-35918 communique
[patent documentation 2] spy opens the 2004-162144 communique
[patent documentation 3] spy opens the 2004-107786 communique
[patent documentation 4] spy opens the 2004-137588 communique
[patent documentation 5] spy opens flat 9-143785 communique
Summary of the invention
The problem that invention will solve
But the clock requency as the PC of the representative of electronic product or electric product sharply rises, and calculation speed accelerates by leaps and bounds.And, do not stay in the effective simple data processing in computer Central Plains in the past, also added computer itself as the function of using in the same manner with A V machine.Promptly with headed by the music playback function, also additional successively have recording/reproduction function, the TV of DVD to accept multiple functions such as recording function, video telephone function.
Meanwhile, the indicating meter of PC is data display equipment simply, even the image of duplicating film etc., also requirement can be anti-in the image quality of long-time audiovisual.Further, require at a low price and the indicating meter of this quality of supply in large quantities.And such indicating meter uses liquid-crystal display mostly now, general above-mentioned winding combination (TAB) substrate or membrane of flip chip encapsulation (COF) substrate automatically of using in the driving of this liquid crystal board.Therefore, in order to make indicating meter, also require to form meticulousr circuit in the above-mentioned driving corresponding to HD image.
In addition, also preferred surface is level and smooth for the Copper Foil that uses with current collector as lithium ion battery.That is, for coating is during active substance on Copper Foil, the slurry that will contain active substance is coated on the Copper Foil with uniform coating thickness, and it is favourable that the Copper Foil of surface smoothing is used as current collector.And this negative electrode active material is the reexpansion contraction when discharging and recharging, and as current-collecting member, shrinks along with it expands, and the dimensional variations of Copper Foil also becomes greatly, in the time can not changing along with its expansion contraction, will produce disrumpent feelings phenomenon.Therefore,, shrink movement, require to have good tensile and unit elongation for anti-the expansion in multiple as the mechanical properties of the Copper Foil of current-collecting member.Further, forming electrical condenser on the Copper Foil with when the dielectric layer, using the Copper Foil of surface smoothing with gel method, is favourable too.
As known from the above, the low profile electrolytic copper foil of supply always in the market exists having the demand of the lower and electrolytic copper foil that physical strength is good of profile.
Solve the method for problem
Therefore, in order to solve above-mentioned problem, the present inventor etc. have added the QAS polymer with ring texture and the sulfuric acid that obtains is copper electrolyte and this electrolytic solution carried out electrolysis and obtain electrolytic copper foil having carried out concentrated research to use.Its result by adopting shown below creating conditions, can stably make and surpassed the low profile electrolytic copper foil of low profile Copper Foil in the past as can be known, and the profile mass deviation of resulting electrolytic copper foil is also little.
The present invention is as described below.
The manufacture method of low profile electrolytic copper foil: the manufacture method of this electrolytic copper foil is that electrolysis contains QAS polymer with ring texture and the sulfuric acid of chlorine is the manufacture method that copper electrolyte obtains electrolytic copper foil, it is characterized in that above-mentioned sulfuric acid is that the QAS polymer that contains in the copper electrolyte is used the above diallyldimethylammonium chloride polymkeric substance of dimer.
In the manufacture method of electrolytic copper foil of the present invention, above-mentioned sulfuric acid is that preferably to use number-average molecular weight be 300～10000 diallyldimethylammonium chloride polymkeric substance for the QAS polymer that contains in the copper electrolyte.
In addition, in the manufacture method of electrolytic copper foil of the present invention, above-mentioned sulfuric acid is copper electrolyte, and is preferred, contain more than one materials that are selected from two (3-sulfopropyl) disulphide or have the compound 3-sulfydryl-1-propanesulfonic acid of sulfydryl, its concentration is 0.5ppm～200ppm.
In addition, in the manufacture method of electrolytic copper foil of the present invention, above-mentioned sulfuric acid is that the concentration of the QAS polymer in the copper electrolyte is preferably 1ppm～150ppm
Further, in the manufacture method of electrolytic copper foil of the present invention, above-mentioned sulfuric acid is that the cl concn in the copper electrolyte is preferably 5ppm～120ppm.
And the above-mentioned sulfuric acid in the manufacture method of electrolytic copper foil of the present invention is that copper electrolyte is preferably at 20 ℃～60 ℃ of liquid temperature, current density 15A/dm
2～90A/dm
2Under carry out electrolysis, be used to make the electrolytic copper foil of low profile.
The electrolytic copper foil that obtains by the manufacture method of electrolytic copper foil of the present invention: the electrolytic copper foil that obtains by the manufacture method of electrolytic copper foil of the present invention, being electrolysis, above-mentioned sulfuric acid is the electrolytic copper foil that copper electrolyte obtains, the feature of this electrolytic copper foil is, its surfaceness (Rzjis) of separating out the face side is the following low profiles of 1.0 μ m, and this glossiness (Gs (60 °)) of separating out face is more than 400.
Surface treatment copper foil of the present invention: surface treatment copper foil of the present invention is an electrolytic copper foil of having implemented the one or more kinds of processing that roughened, antirust processing, silane coupling agent handle the separating out of above-mentioned electrolytic copper foil on the face.
And, it is characterized in that it is the following low profiles of 2 μ m that the mask with the applying of insulating resin base material of above-mentioned surface treatment copper foil has surfaceness (Rzjis).
Copper clad laminate of the present invention:, especially can access and be applicable to the high-quality copper clad laminate of making printed circuit board (PCB) by using above-mentioned electrolytic copper foil or surface treatment copper foil.
The invention effect
According to the manufacture method of electrolytic copper foil of the present invention, can the quality deviation little and efficient highland make the electrolytic copper foil that the low profile electrolytic copper foil profile of supplying in the market in the past is lower and have the high-strength mechanical characteristic.In addition, the composition that uses in the manufacturing of the composition of the electrolytic solution that uses in the manufacture method of electrolytic copper foil of the present invention low profile electrolytic copper foil different from the past, stability of solution is also good, can stablize and be long-term used in electrolysis, even the consideration liquid waste disposal can not cause that cost improves yet.
In addition, the low profile electrolytic copper foil that is obtained by this manufacture method as separating out at it when having implemented above-mentioned surface-treated surface treatment copper foil on the face, also can be kept low profile and good mechanical characteristics.Therefore, be highly suitable for forming to the automatic little interval circuit of the demanding winding of the low profile of Copper Foil in conjunction with (TAB) substrate or membrane of flip chip encapsulation (COF) substrate.In addition, also can be applicable to the use in the fields such as current-collecting member of the negative pole that constitutes lithium-ion secondary cell.
Embodiment
The manufacture of electrolytic copper foil of the present invention: the manufacture method of low profile electrolytic copper foil of the present invention, use contains QAS polymer with ring texture and the sulfuric acid of chlorine is copper electrolyte, and above-mentioned QAS polymer is used above diallyldimethylammonium chloride (hereinafter referred to as the DDAC) polymkeric substance of dimer.Being that aforesaid way is the single aggressiveness (monomer) of a DDAC notion in addition, is the DDAC polymkeric substance of selecting to use more than the dimer.In addition, as the DDAC of QAS polymer structure circlewise when taking polymer architecture, the part of ring texture is made of the nitrogen-atoms of quaternary ammonium.And the DDAC polymkeric substance is that above-mentioned ring texture is any one or its mixture of～7 yuan of rings of 4 yuan of rings, therefore, is representative with the compound with 5 ring structures in these polymkeric substance, is expressed as follows as formula 1.As shown in Equation 1, this DDAC polymkeric substance is the material that DDAC has the above polymer architecture of dimer.That is, the monomer of DDAC is to the not effect of low profileization of electrolytic copper foil surface.The main chain of this DDAC polymkeric substance preferably only is made of carbon atom and hydrogen atom.
And the sulfuric acid that contains the composition of this DDAC polymkeric substance more than dimer by use is copper electrolyte, can stably make to have the electrolytic copper foil on the low profile surface more than the low profile electrolytic copper foil in the past.
And even the above DDAC polymkeric substance of dimer, if molecular weight is excessive, then the manufacturing capacity of its low profile electrolytic copper foil reduces.As the polymer structure, be preferably dimer～150 aggressiveness, more preferably 4 aggressiveness～14 aggressiveness.Be monomeric situation and the situation that surpasses 150 aggressiveness, the not effect of low profileization to electrolytic copper foil surface produces deviation on profile.In addition, if in preferred polymer scope, use, then can be more stable and zero deflection ground form the low profileization of electrolytic copper foil surface.
In addition, as the suitable polymers of the above DDAC polymkeric substance of dimer, from the viewpoint of number-average molecular weight, the preferred polymkeric substance in 300～10000 scope.If the number-average molecular weight of DDAC polymkeric substance is below 300, the monomeric ratio that exists uprises, and then as described later shown in the comparative example, has the become tendency of difficulty of low profileization.But the low profileization of electrolytic copper foil of the present invention is not to be to use under the good meaning survey periodic profile with the contact pin type roughmeter only.Be to compare with the low profile Copper Foil that electrolytic process in the past obtains, its glossiness of separating out face is obviously different, the material that uses on the meaning that the flatness of viewed in plan also has leap to improve.And if the number-average molecular weight of DDAC polymkeric substance surpasses 10000, even then adjust the concentration of other additive of coexistence, to the also not effect of low profileization of electrolytic copper foil, it is big that the deviation of the profile of the face of separating out of the electrolytic copper foil that obtains becomes.In addition, even this number-average molecular weight is below 10000, if surpass 7000, then for example if the concentration of two (3-sulfopropyl) disulphide (hereinafter referred to as SPS) that will not coexist is adjusted into more than the 100ppm, it is big that the deviation of the profile of the face of separating out of resulting electrolytic copper foil significantly becomes.Therefore, the deviation on the general management level of many conditions such as the liquid temperature when carrying out electrolysis procedure, concentration as if consideration, then preferably using number-average molecular weight is 300～7000, further preferred number average molecular weight is 600～2500 DDAC polymkeric substance.But, when making the DDAC polymkeric substance, the residual inevitably situation that monomer DDAC is arranged is arranged also.At this moment, residual monomer DDAC be the trace, so need not to discharge this monomer.
In addition, above-mentioned number-average molecular weight is the value that obtains by following measuring method.That is, in solvent, under condition shown below, (GPC) measures by gel permeation chromatography with sample dissolution.Detector uses polygonal light-scattering photometer (MALS).In addition, the value of supposing " second virial coefficient * concentration " is 0mol/g, and specific refractory power change in concentration (dn/dc) is calculated the standard test specimen of usefulness, uses polyethylene oxide (SRM1924); NIST.
[GPC condition determination]
Post: TSKgel α-4000, α-2500 (
7.8mm * 30cm); Dongli Ltd. makes
Solvent: water system: methyl alcohol=50: 50 (volume ratio)
Flow velocity: 0.504mL/min
Temperature: 23 ℃ ± 2 ℃
Detector: MALS (DAWN-EOS type); Wyatt Technology
Wavelength: 690nm
Temperature: 23 ℃ ± 2 ℃
Further, what use in the manufacture method of electrolytic copper foil of the present invention is the concentration of the DDAC polymkeric substance of the QAS polymer in the copper electrolyte as sulfuric acid, and the relation between the concentration of consideration and SPS or 3-sulfydryl-1-propanesulfonic acid (hereinafter referred to as MPS) decides.The concentration of DDAC polymkeric substance is preferably 1ppm～150ppm, more preferably 2ppm～100ppm, more preferably 3ppm～80ppm.At this, the DDAC polymkeric substance is the situation of the not enough 1ppm of concentration in the copper electrolyte at sulfuric acid, improves the concentration of SPS or MPS come what may, and electrolytic copper foil is separated out all roughen of face, is difficult to obtain the electrolytic copper foil of low profileization.Even the DDAC polymkeric substance is that concentration in the copper electrolyte surpasses 150ppm at sulfuric acid, it is unstable that the precipitation state of copper becomes, thereby also be difficult to obtain the low profile electrolytic copper foil.
The sulfuric acid that uses in the manufacture method of electrolytic copper foil of the present invention is copper electrolyte, by containing more than one of the compound MPS that is selected from SPS or has sulfydryl, can access the lower electrolytic copper foil of the higher profile of precision, its concentration is preferably 0.5ppm～200ppm, more preferably 4ppm～150ppm, more preferably 4ppm～50ppm.If the not enough 0.5ppm of the concentration of SPS or MPS, then the face of separating out of electrolytic copper foil becomes coarse, is difficult to obtain the low profile electrolytic copper foil.On the other hand, even the concentration of SPS or MPS surpasses 200ppm, the effect of the face of separating out of the resulting electrolytic copper foil of smoothing does not improve yet, and makes the electrolysis state become unstable on the contrary.In addition, this part invents described SPS or MPS uses on the meaning that also comprises its salt respectively, and the record value of concentration is the scaled value of the 3-sulfydryl-1-propanesulfonic acid sodium (hereinafter referred to as MPS-Na) as sodium salt.MPS is a dimerization and become the SPS structure in the copper electrolyte at sulfuric acid.Therefore, the concentration of SPS or MPS is meant except the material and salts such as MPS monomer or MPS-Na that add as SPS, also comprises as MPS to add the concentration that back poly in the electrolytic solution changes into the modifier of SPS etc. to.With the structural formula of following formula 2 expression MPS, the structural formula of formula 3 expression SPS.From these structural formulas more as can be known, the SPS structure is the dimer of MPS.
Further, above-mentioned sulfuric acid is that the cl concn in the copper electrolyte is preferably 5ppm～120ppm, more preferably 10ppm～50ppm.In the situation of the not enough 5ppm of this cl concn, the face of the separating out chap of electrolytic copper foil can't be kept low profile.On the other hand, cl concn is if surpass 120ppm, the then face of the separating out chap of electrolytic copper foil, and the electrolysis state labile can't form the face of separating out of low profile.
The above, above-mentioned sulfuric acid is that SPS or the one-tenth balance-dividing between MPS and DDAC polymkeric substance and the chlorine in the copper electrolyte is most important, if the balance of this tittle exceeds above-mentioned scope, then the result is, the face of the separating out chap of electrolytic copper foil can't be kept low profile.
In addition, be copper electrolyte at sulfuric acid of the present invention, for copper concentration is 50g/l～120g/l, free sulfuric acid concentration is the solution about 60g/l～250g/l.
And using above-mentioned sulfuric acid is the situation that copper electrolyte is made electrolytic copper foil, preferably at 20 ℃～60 ℃ of liquid temperature, current density 15A/dm
2～90A/dm
2Under carry out electrolysis.The situation that liquid temperature less than is 20 ℃, speed of separating out reduces, and it is big that the deviation of mechanical properties such as unit elongation and tensile strength becomes.On the other hand, if the liquid temperature surpasses 60 ℃, then the vaporize water component increases, and the change of strength of fluid is fast, and the face of separating out of the electrolytic copper foil that obtains can't be kept good smoothness.And the preferable range of liquid temperature is 40 ℃～55 ℃.In addition, the not enough 15A/dm of current density
2Situation, the speed of separating out of copper diminishes, the industrial production variation.On the other hand, if current density surpasses 90A/dm
2, it is big that the surfaceness of the face of separating out of the electrolytic copper foil that then obtains becomes, and can't keep low profile.And the preferred scope of current density is 40A/dm
2～70A/dm
2
＜electrolytic copper foil that manufacture method of the present invention obtains 〉
The feature of the electrolytic copper foil that manufacture method of the present invention obtains is that its surfaceness (Rzjis) of separating out the face side is the following low profiles of 1.0 μ m, and this glossiness (Gs (60 °)) of separating out face is more than 400.Say on the stricti jurise that the surfaceness of the face of separating out of electrolytic copper foil is the notion according to the thickness variation of electrolytic copper foil.But, the surfaceness and the glossiness of the electrolytic copper foil that obtains according to the manufacture method of electrolytic copper foil of the present invention, in the paper tinsel of the whole thickness of the electrolytic copper foil below the producible 450 μ m thickness as electrolytic copper foil, can satisfy its surfaceness of separating out the face side (Rzjis) is that 1.0 μ m following low profile and this glossiness of separating out face (Gs (60 °)) are the condition more than 400.
" electrolytic copper foil " of the present invention is meant the Copper Foil that does not carry out any surface-treated state, is called " Copper Foil is untreated ", " paper tinsel of isolating " etc. sometimes.In this specification sheets, simply it is called " electrolytic copper foil ".In the manufacturing of this electrolytic copper foil, the general continuous production method that adopts, at the rotating cathode of making drum type with along the lead of the shape subtend of this rotating cathode configuration is between anode or the dimensional stability anode (DSA), flowing into copper sulfate is solution, utilize electrolytic reaction, it is surperficial that copper is separated out at the drum of rotating cathode.This copper of separating out becomes the paper tinsel shape, peels off continuously and curls from rotating cathode, produces electrolytic copper foil thus.In this stage, do not carry out any surface treatment of antirust processing etc., the copper after the electrolysis is active state, becomes the state by the easy oxidation of airborne oxygen.
The surface shape with the rotating cathode contact side of the electrolytic copper foil that this is peeled off has the shape of the shape on the rotating cathode surface of having made carbon copies minute surface precision work, is to have the glossy shiny surface, so this face is called glossy surface.With respect to this, separate out the surface shape of side, the result that the crystalline growth speed of general copper of separating out is different according to crystal plane demonstrates the concaveconvex shape of chevron, so this face is called uneven surface or separates out face.Usually, the face that this face of separating out becomes when making copper clad laminate and insulation layer is fitted.And this surfaceness (roughness) of separating out face is more little, the electrolytic copper foil of good low profile.Further, in electrolytic copper foil of the present invention, it is more level and smooth than the glossy surface of the Copper Foil that uses general electrolysis drum to make that this separates out the surfaceness of face, so do not use the term of uneven surface, simply is called " separating out face ".
And this electrolytic copper foil is implemented roughened and antirust processing to separating out face usually in surface treatment procedure.So-called to separating out face enforcement roughened, be meant in copper-bath and burn electrolysis under the plating condition, separate out at the face of separating out and adhere to fine shot copper, directly electrolysis under level and smooth plating condition in what is called, the plating that is covered implements to prevent the processing of disposal that fine shot copper comes off etc.Therefore, separate out the face of separating out that has adhered to fine shot copper and be called " roughened face ".Then, in surface treatment procedure, carry out on the surface of electrolytic copper foil the operation that plating etc. by zinc, zinc alloy, chromium system is carried out antirust processing, drying, batched etc., finish electrolytic copper foil as product.The product that obtains like this is commonly referred to as " surface treatment paper tinsel ".
Electrolytic copper foil of the present invention has its surfaceness of separating out the face side (Rzjis) less than 1.0 μ m and glossiness [Gs (60 °)] is the characteristic more than 400.And, more preferably surfaceness (Rzjis) less than 0.6 μ m, glossiness [Gs (60 °)] is more than 600.At first, first talk about bright glossiness.At this, the glossiness of [Gs (60 °)] is to measure light to the surface of electrolytic copper foil with 60 ° of irradiations of input angle, is determined at the value of 60 ° of following intensity of light reflected of reflection angle.In this said input angle, be with respect to the vertical direction of the shadow surface of light as 0 °.And, according to JIS Z 8741-1997, put down in writing five different mirror surface luster measuring methods of input angle, select suitable input angle according to the glossiness of sample.Wherein, input angle is set at 60 °, can in the wide scope of the sample of high glossiness, measures in examination from low-luster.Therefore, the glossiness of electrolytic copper foil of the present invention etc. has mainly adopted 60 ° in measuring.
Usually, the smoothness of the face of separating out of electrolytic copper foil has been used surfaceness Rzjis as parameter in estimating.But, only by Rzjis, can only obtain the concavo-convex information of short transverse, can't obtain the information of concavo-convex cycle or fluctuation.Glossiness is the parameter of having reacted both information, thus by and use Rzjis, can the consolidated statement surface roughness cycle, the various parameters of the interior homogeneity of fluctuation, its face etc. estimate.
The situation of electrolytic copper foil of the present invention, satisfying surfaceness (Rzjis) less than 1.0 μ m and this glossiness of separating out face [Gs (60 °)] of separating out the face side is the condition more than 400.That is, in this scope, can ensure the quality of products, can not have in the past to the electrolytic copper foil of market supply.And, by suitable use manufacture method described later, also can provide have surfaceness (Rzjis) less than 0.6 μ m, glossiness [Gs (60 °)] is the electrolytic copper foil of the face of separating out more than 700.In addition,, do not stipulate the higher limit of glossiness here, but judge that from experience [Gs (60 °)] about 800 are the upper limit.In addition, the Grossmeters VG-2000 type that the glossiness among the present invention uses Japanese electric look Industrial Co., Ltd to make is decided method JIS Z 8741-1997 based on glossiness De Measuring and is measured.
And, about electrolytic copper foil described here, do not carry out the qualification of thickness.This is that the roughness that has this to separate out face more is more little, the good tendency that glossiness also improves because thick more.Leave no choice but decide the upper limit, even be object then with the electrolytic copper foil below the 450 μ m thickness of the also worthwhile limit of industry manufacturing electrolytic copper foil.
In addition, here, the lower value of surfaceness (Rzjis) of separating out the face side is unqualified.Though also relevant with the sensitivity of tester, the lower value of saying surfaceness on the experience is about 0.1 μ m.But, in the mensuration of reality, find deviation, be about 0.2 μ m as the lower limit of the measured value that can ensure.
To this slick face of separating out, even implement the surface treatment of roughened or antirust processing etc., it is obvious also accessing the surface treatment copper foil that has more in the past than the roughened face that low profile surface treatment copper foil profile was lower.And, if this surface treatment copper foil is fitted in the insulating resin base material, then can suitably obtain the anchoring effect of physics, the concavo-convex of bonding interface also diminishes, so the intrusion of the soup of etching solution etc. is little on this interface, shows good resistance to chemical reagents.
As the mechanical characteristics of electrolytic copper foil of the present invention, the tensile strength in the normality is 33kgf/mm
2More than, unit elongation is more than 5%.And preferred heating back (180 ℃ * 60 minutes, atmospheric environment) tensile strength is 30kgf/mm
2More than, unit elongation is more than 8%.
And, in the present invention, to create conditions by optimization, the tensile strength that can make normality is 38kgf/mm
2More than, the tensile strength of heating back (180 ℃ * 60 minutes, atmospheric environment) is 33kgf/mm
2Above Copper Foil with better mechanical characteristics.Therefore, this favorable mechanical characteristic not only can be used in the bending of the abundant printed circuit board (PCB) of anti-the deflection, and can be applicable in the current-collecting member purposes of the negative pole that constitutes lithium-ion secondary cell that bearing expands shrinks movement etc.
＜surface treatment copper foil of the present invention 〉
Surface treatment copper foil of the present invention is to have implemented roughened, antirust processing, the silane coupling agent one or more kinds of Copper Foils in handling on the face the separating out of above-mentioned electrolytic copper foil.Promptly, electrolytic copper foil as used herein, be meant " its surfaceness (Rzjis) of separating out the face side is the following low profiles of 1.0 μ m, and this glossiness (Gs (60 °)) of separating out face is the electrolytic copper foil more than 400 ", " used added the sulfuric acid that QAS polymer with ring texture obtains be the electrolytic copper foil that copper electrolyte obtains ".
At this, roughened has adopted separating out of electrolytic copper foil adheres to any kind of method that forms the fine metal grain or form roughened surface with etching method on the face.At this,, enumerated and on the face of separating out, adhered to the method that forms fine shot copper as the former method that forms the fine metal grain of adhering to.This roughened operation by electrolytic copper foil separate out on the face on separate out the burning plating operation of adhering to fine shot copper and be used to prevent that the lining electroplating work procedure that this fine shot copper comes off from constituting.
Separate out on the face in the operation of adhering to fine shot copper separating out of electrolytic copper foil by electrolytic process,, adopt the plating condition of burning as electrolytic condition.Therefore, separate out the composition of the general solution that uses in the operation of adhering to fine shot copper, burn the plating condition, copper ion concentration is set at low value in order to make easily.This burns the plating condition, and there is no particular limitation, can consider that the characteristic of production line is set.For example, be solution if use copper sulfate, then can set concentration for and be respectively copper 5～20g/l, sulfuric acid 50～200g/l, other necessary additives (α-Nai Kuilin, dextrin, glue, thiocarbamide etc.), 15～40 ℃ of liquid temperature, current density 10～50 A/dm
2Condition.
For the lining electroplating work procedure that prevents that fine shot copper from coming off, be in order to prevent to separate out coming off of the fine shot copper that adheres to, under level and smooth plating condition, copper to be separated out and the operation of the fine shot copper that is covered equably.Therefore, in this operation, can use with above-mentioned copper billet (bulk copper) and form the identical solution that uses in the groove supply source as cupric ion.There is no particular limitation for this level and smooth plating condition, can consider that the characteristic of production line is set.For example, be solution if use copper sulfate, then can set copper concentration for is that 50～80g/l, sulfuric acid concentration are 50～150g/l, 40～50 ℃ of liquid temperature, current density 10～50 A/dm
2Condition.
The formation method of antirust processing layer then, is described.This antirust processing layer is the manufacturing process of the manufacturing process of copper clad laminate and printed circuit board (PCB) do not produced the mode of obstacle, to prevent the oxidized or corrosive layer of electrolytic copper foil laminar surface.As the method that adopts in the antirust processing, adopt and to have used the organic rust preventing method of benzotriazole, imidazoles etc. or to have used any one equal no problem in the inorganic rust-proofing method of zinc, chromium, zinc alloy etc.As long as the application target according to electrolytic copper foil is selected rust-proofing method.In the situation of implementing organic rust preventing, can adopt the method for dip coated, spray coating, galvanic deposit organic corrosion inhibitor etc.Implementing inorganic antirust situation, can suitably adopt with electrolysis antirust element is separated out at the method for electrolytic copper foil laminar surface and other so-called displacement liberation methods etc.For example, in the situation of implementing the antirust processing of zinc, can use zinc pyrophosphate plating bath, zinc cyanide plating bath, zinc sulfate plating bath etc.For example, if the zinc pyrophosphate plating bath then can be set zinc concentration and be 5～30g/l, potassium pyrophosphate concentration and be 50～500g/l, 20～50 ℃ of liquid temperature, pH and be 9～12, current density 0.3～10A/dm
2Condition.
The what is called silane coupling agent is handled, and is the processing of implementing after the roughened that is through with, antirust processing etc., is the processing of implementing for the connecting airtight property between raising of chemical ground and the insulation layer constituent material.There is no particular limitation for the silane coupling agent that adopts during silane coupling agent is handled herein, can consider the character of the electroplate liquid that uses in the manufacturing process of employed insulation layer constituent material or printed circuit board (PCB) etc., selecting arbitrarily to use epoxy is that silane coupling agent, amino are that silane coupling agent, sulfydryl are silane coupling agent etc.
Specifically, preferably the identical couplant of couplant that uses in the glasscloth with the laminating material (pre-preg) of use in printed circuit board is selected as the center, can use vinyltrimethoxy silane, the ethenylphenyl Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, 4-glycidyl butyl trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-3-(4-(the amino propoxy-of 3-) butoxy) propyl group-3-TSL 8330, imidazoles silane, triazine silane, γ-Qiu Jibingjisanjiayangjiguiwan etc.
And, use electrolytic copper foil of the present invention, implemented above-mentioned desirable surface-treated surface treatment copper foil on its surface and be characterised in that, it is the following low profiles of 2 μ m that the surface of the binding face between itself and insulation layer constituent material has surfaceness (Rzjis).By having the roughened face of such low profile, when fitting, can guarantee practical clog-free the connecting airtight property that with the insulation layer constituent material.And can obtain clog-free heat-resistant quality, resistance to chemical reagents in the practicality as substrate, stripping strength.
The mode of copper clad laminate of the present invention: above-mentioned electrolytic copper foil is a Copper Foil of not implementing roughened, antirust processing etc., implement hot pressing processing by ordinary method and wait this electrolytic copper foil and be that the pliability of laminating material and polyimide resin film etc. is that base material is the various insulation layer constituent materials of representative of fitting, obtain copper clad laminate thus with the hard of glass-Resins, epoxy base material, glass-polyimide base material etc.In addition, when making the pliability copper clad laminate, also can form the polyimide resin substrate layer with casting process.
But, in order to ensure the connecting airtight property between electrolytic copper foil and the insulation layer constituent material, suitable enforcement can improve the roughened of connecting airtight property, antirust processing, silane coupling agent processing etc., fit this face and insulation layer constituent material on the binding face of this electrolytic copper foil mostly.At this moment, when selecting the low profile binding face, under the situation of electrolytic copper foil of the present invention, the face of separating out is also more smooth than glossy surface, and all it doesn't matter so which selects make binding face.
Described here copper clad laminate comprises that so-called hard is copper clad laminate and contains the pliability copper clad laminate that COF band carries etc.And, about this manufacture method, can adopt any one method in the known method.Below, describe embodiments of the invention in detail.
Embodiment
The manufacturing of electrolytic copper foil: having prepared sulfuric acid in this embodiment is copper electrolyte, and its copper concentration is that 80g/l, free sulfuric acid concentration are that the concentration of 140g/l and its SPS or MPS, DDAC polymer concentration, the cl concn of stated number average molecular weight (309,1220,2170,7250) are recorded in table 1.In addition, number-average molecular weight is the dimer that 309 DDAC polymkeric substance means DDAC.In addition, add SPS and MPS with sodium-salt form.
Table 1
And negative electrode adopts the titanium plate electrode, and the surface of this titanium plate electrode implements to grind with the #2000 pouncing paper, and its surface roughness Ra is adjusted into 0.20 μ m, and anode adopts DSA, and the liquid temperature is made as 50 ℃, and current density is 60 A/dm in embodiment 1～embodiment 6
2, current density is 52 A/dm among embodiment 7 and the embodiment 8
2Under carry out electrolysis.Made embodiment 1,3,5 like this, 5 kinds of electrolytic copper foils of 12 μ m thickness in 7,8 and 3 kinds of electrolytic copper foils of 210 μ m thickness among the embodiment 2,4,6 have obtained 8 kinds of electrolytic copper foils altogether.In addition, the crystalline texture of these electrolytic copper foils random orienting in fact on whole thickness direction.
According to the surfaceness of this electrolytic copper foil of mensuration shown below and glossiness etc.The evaluation result of separating out face is shown in table 2.In addition, the surfaceness of above-mentioned titanium plate electrode (Ra 0.20 μ m) is to estimate the value of the glossiness of confirming the gained electrolytic copper foil.
Surfaceness: the surfaceness meter S E-3500 that adopts little slope institute (strain) to make, measure based on JIS B 0601-1994, the Rz of gained is the Rzjis value.
Glossiness: the Grossmeters V G-2000 type that adopts Japanese electric look Industrial Co., Ltd to make, measure based on glossiness measuring method JIS Z 8741-1997.
Table 2
The mean value of the surfaceness of the face of separating out that table 2 is put down in writing and standard deviation are the mean value and the standard deviations of 30 measured value.And, about glossiness, also show the mean value and the standard deviation of 30 measured value.In addition, the surfaceness of surface treatment copper foil is to show the mean value of having implemented 30 measured value after the roughened.
The manufacturing of surface treatment copper foil: as the surface treatment of above-mentioned all electrolytic copper foils, separate out to separate out on the face at this and adhere to fine shot copper and form the roughened face, implement antirust processing.Before forming this roughened face, wash on the surface of this electrolytic copper foil of cleanup acid treatment.The dilution heat of sulfuric acid that this cleanup acid treatment condition has adopted 30 ℃ of concentration 100g/l, liquid temperature flooded 30 seconds.
After cleanup acid treatment finishes,, implement to be used on the face of separating out, separating out the burning plating operation of adhering to fine shot copper and be used to the lining electroplating work procedure that prevents that this fine shot copper from coming off as the operation that forms fine shot copper on the face of separating out at electrolytic copper foil.Adhere in the burning plating operation of fine shot copper the former separating out, adopting copper concentration is that 15g/l, free sulfuric acid concentration are that the copper sulfate of 140g/l is solution, is negative electrode with electrolytic copper foil, and anode uses DSA, at 25 ℃ of liquid temperature, current density 25 A/dm
2Condition under 5 seconds of electrolysis.
And, form fine shot copper if on the face of separating out, adhere to, then as the lining electroplating work procedure that is used to prevent that fine shot copper from coming off, under level and smooth plating condition, evenly separate out copper with the fine shot copper that is covered.The electrolytic condition of this moment is level and smooth plating condition, and adopting copper concentration is that 70g/l, free sulfuric acid concentration are the copper-bath of 80g/l, is negative electrode with electrolytic copper foil, and anode adopts DSA, at 45 ℃ of liquid temperature, current density 25A/dm
2Condition under 10 seconds of electrolysis.
After above-mentioned roughened operation finishes, then on two surfaces of this Copper Foil, implement antirust processing.Adopted the inorganic antirust of the following stated condition at this.Adopting the zinc sulfate of sulfuric acid concentration 70g/l, zinc concentration 20g/l to bathe, is negative electrode with the electrolytic copper foil, and anode adopts zine plate, at 40 ℃ of liquid temperature, current density 15A/dm
2In 5 seconds of following electrolysis, implement the antirust processing of zinc.
Further, in the situation of present embodiment, on above-mentioned zinc rustproof layer, form chromate coating by electrolysis.The electrolytic condition of this moment is that employing chromic acid 5.0g/l, pH are 11.5 solution, and electrolytic copper foil is a negative electrode, and anode adopts the SUS plate, at 35 ℃ of liquid temperature, current density 8 A/dm
25 seconds of following electrolysis.
If be through with above-described antirust processing, then wash, directly in the silane coupling agent treatment trough, on the antirust processing layer of roughened face, adsorb silane coupling agent.The composition of the solution that adopt this moment is to be solvent with the ion exchanged water, adds γ-glycidoxypropyltrime,hoxysilane, is 5g/l.And, carry out adsorption treatment by this solution of spray spraying.
After the silane coupling agent processing finishes, spend 4 seconds by adjusting envrionment temperature by electricradiator heating so that the paper tinsel temperature become in 140 ℃ the stove, vaporization moisture, promote the condensation reaction of silane coupling agent, finally obtained the surface-treated electro-deposited copper foil of 5 kinds of thickness 12 μ m and the surface treatment copper foil of 3 kinds of thickness 210 μ m.The surfaceness of the roughened face after this surface treatment is divided into the paper tinsel of 12 μ m thickness and the paper tinsel of 210 μ m thickness is remembered in table 2 side by side.
Comparative example
Comparative example 1
In this comparative example, the DDAC polymkeric substance in the copper electrolyte that the DDAC that adopts single aggressiveness replaces adopting among the embodiment, other adopt the condition identical with embodiment 1～embodiment 6 to obtain electrolytic copper foil.The measurement result and the embodiment of the surfaceness of the face of separating out of this electrolytic copper foil and glossiness etc. together remember in table 2.Then, implement to obtain surface treatment copper foil in the same manner with embodiment 1, the surfaceness and the embodiment of its roughened face together are shown in Table 2.
Comparative example 2
This comparative example is the tracking test of patent documentation 1 disclosed embodiment 1.Copper sulfate (reagent) and sulfuric acid (reagent) are dissolved in the pure water, have prepared the aqueous solution of copper sulfate (converting) 280g/l, free sulfuric acid concentration 90g/l with 5 hydrates.To the multipolymer that wherein adds diallyldialkylammonihalide salt and sulfurous gas (trade(brand)name PAS-A-5, weight-average molecular weight 4000:4ppm, Nitto Boseki Co. Ltd makes) and polyoxyethylene glycol (molecular-weight average 1000:10ppm) and MPS (1ppm), further use sodium-chlor, cl concn is adjusted to 20ppm, prepares the sulfuric acid copper electroplating liquid.
And negative electrode uses the titanium plate electrode, and the surface of this titanium plate electrode is ground with the pouncing paper of #2000 and made its surface roughness Ra be adjusted into 0.20 μ m, and anode employing stereotype is at 40 ℃ of liquid temperature, current density 50A/dm
2The above-mentioned electrolytic solution of following electrolysis obtains the electrolytic copper foil of 12 μ m thickness and 210 μ m thickness.The measurement result and the embodiment of the surfaceness of the face of separating out of this electrolytic copper foil and glossiness etc. together are illustrated in the table 2.
Then, handle this electrolytic copper foil in the same manner with embodiment 1 and obtain surface treatment copper foil.The surfaceness of this roughened face and embodiment together are shown in table 2.
Comparative example 3
The sulfuric acid of preparation copper concentration 90g/l, free sulfuric acid concentration 110g/l is copper electrolyte, carries out purifying treatment through activated charcoal filter.Then, in this electrolytic solution, add respectively reagent make MPS-Na (1ppm), as the Natvosol (5ppm) and the lower molecular weight glue (number-average molecular weight 1560:4ppm) of high molecular polysaccharide, cl concn 30ppm has prepared electrolytic solution.Use this electrolytic solution, negative electrode adopts the titanium plate electrode, and the surperficial pouncing paper with #2000 of this titanium plate electrode grinds and makes its surface roughness Ra be adjusted into 0.20 μ m, and anode uses DSA, at 58 ℃ of liquid temperature, current density 50 A/dm
2Under carry out electrolysis, obtain the electrolytic copper foil of 12 μ m thickness and 210 μ m thickness.The surfaceness of the face of separating out of this electrolytic copper foil and the measurement result of glossiness and embodiment together are shown in table 2.
Then, handle this electrolytic copper foil in the same manner with embodiment 1 and obtain surface treatment copper foil.The surfaceness of this roughened face and embodiment together are shown in table 2.
The contrast of＜embodiment 1,3,5 and embodiment 7,8 〉
At this, the situation that employing is had the compound MPS of sulfydryl compares with the situation that adopts SPS.Unit elongation after tensile strength after the face of the separating out surfaceness of the electrolytic copper foil that obtains as known from Table 2,, glossiness, normality and the heating, normality and the heating, the surfaceness of surface treatment copper foil are almost equal.Therefore, SPS that uses in the preparation of copper electrolyte or MPS also can SPS add obtaining identical effect except salts such as MPS monomer or MPS-Na.
The contrast of＜embodiment and comparative example 〉
Separate out the surfaceness of face: with the situation of Ra contrast table surface roughness, no matter the differing between the face of separating out of the electrolytic copper foil that obtains in the face of separating out of the electrolytic copper foil of the present invention that obtains among embodiment 1～embodiment 8 and the comparative example 1～comparative example 3 is that mean value or standard deviation value are all little.But, if with Rzjis contrast table surface roughness, the electrolytic copper foil that obtains than comparative example then, the electrolytic copper foil that embodiment obtains relatively has the more face of separating out of low profile from mean value.And, from relatively comparative example 1 and embodiment as can be known, the single aggressiveness of DDAC and DDAC polymer phase ratio, the smoothing effect is bad.In addition, from the comparison of standard deviation (and coefficient of variation), the face of separating out of the electrolytic copper foil that obtains of embodiment shows the few stable profile of deviation as can be known, and surface uniformity is good.And it is not subjected to the influence of paper tinsel thickness and has identical tendency.
Promptly, only judge from the profile (Rzjis) that adopts the face of separating out that the contact pin type roughmeter measures, the electrolytic copper foil that comparative example 1～comparative example 3 obtains has also entered in the scope with good low profile electrolytic copper foil, but the electrolytic copper foil of embodiment 1～embodiment 8 has formed further more even and good low profileization.In addition, comparative examples 2 and embodiment, even the polymkeric substance of ammonium salt, main chain only can form more even and good low profile by the DDAC polymkeric substance that carbon atom and hydrogen atom constitute.
And comparison surface is handled Copper Foil, also obtains the correlated identical result with the surfaceness (Rzjis) of electrolytic copper foil.Promptly, adopted the surfaceness (Rzjis) of roughened face of the surface treatment copper foil of the electrolytic copper foil that obtains in the comparative example to show about 3 μ m, with respect to this, used the surfaceness (Rzjis) of roughened face of the surface treatment copper foil of the electrolytic copper foil that obtains among embodiment 1～embodiment 8 to be below the 2 μ m the better low profile that can access.
Glossiness: with respect to the mean value of each glossiness of the electrolytic copper foil that obtains in the comparative example, the glossiness of the electrolytic copper foil that obtains among embodiment 1～embodiment 8 is quite high value, shows diverse scope.It can be said that each electrolytic copper foil that obtains in comparative example 1～comparative example 3, each electrolytic copper foil that obtains among embodiment 1～embodiment 8 has more smooth and approaches the face of separating out uniformly of minute surface.
Tensile strength and unit elongation: the electrolytic copper foil that each electrolytic copper foil of the embodiment that adopting preferably creates conditions obtains obtains in the comparative example, tensile strength after normality and heating also with comparative example 1 and comparative example 2 in the electrolytic copper foil that obtains equally matched.But the tensile strength of the electrolytic copper foil that obtains in comparative example 3 is obviously variant, and its tensile strength under normal conditions is little, reduces by heating.And, about in unit elongation and the comparison each comparative example, have excellent characteristic.Especially by the situation after the contrast heating, it is remarkable that its difference becomes.Therefore, electrolytic copper foil of the present invention can be applicable in the purposes of being heated well.
Industrial applicibility
Manufacture method with electrolytic copper foil of the present invention is made electrolytic copper foil, in market in the past The low profile electrolytic copper foil of supply can more effectively provide the more low profile electrolytic copper foil of stabilised quality. And the electrolytic copper foil that obtains as its product has considerably beyond the low profile of supplying on the market in the past The flat surfaces of electrolytic copper foil. Therefore, implement surface treatment at its face of separating out, the enforcement roughening is processed Situation also can easily obtain the in the past low profile surface treatment copper foil of unexistent level. Therefore, Can be applicable to effectively that winding is automatically in conjunction with (TAB) substrate or thin membrane flip chip encapsulation (COF) substrate etc. The formation purposes of little interval circuit in. In addition, the rough surface of the face of separating out of electrolytic copper foil of the present invention Below the surface roughness of degree Wei Guang swamp face, the two sides is glossiness even surface. And, than with Past low profile electrolytic copper foil is owing to good hot strength and percentage elongation, therefore, be suitable for doing For the current-collecting member of the negative pole that consists of lithium rechargeable battery uses.
Claims (11)
1. the manufacture method of an electrolytic copper foil, electrolysis contain QAS polymer with ring texture and the sulfuric acid of chlorine is that copper electrolyte obtains electrolytic copper foil, it is characterized in that,
Above-mentioned sulfuric acid is that the QAS polymer that contains in the copper electrolyte is used the above diallyldimethylammonium chloride polymkeric substance of dimer.
2. the manufacture method of electrolytic copper foil as claimed in claim 1 is characterized in that, above-mentioned sulfuric acid is that the QAS polymer that contains in the copper electrolyte is that number-average molecular weight is 300～10000 diallyldimethylammonium chloride polymkeric substance.
3. the manufacture method of electrolytic copper foil as claimed in claim 1 or 2, it is characterized in that, above-mentioned sulfuric acid is that copper electrolyte contains more than one in the compound 3-sulfydryl-1-propanesulfonic acid that is selected from two (3-sulfopropyl) disulphide and has sulfydryl, and its concentration is 0.5ppm～200ppm.
4. as the manufacture method of any described electrolytic copper foil in the claim 1～3, it is characterized in that above-mentioned sulfuric acid is that the concentration of the QAS polymer in the copper electrolyte is 1ppm～150ppm.
5. as the manufacture method of any described electrolytic copper foil in the claim 1～4, it is characterized in that above-mentioned sulfuric acid is that the cl concn in the copper electrolyte is 5ppm～120ppm.
6. as the manufacture method of any described electrolytic copper foil in the claim 1～5, it is characterized in that, at 20 ℃～60 ℃ of liquid temperature, current density 15 A/dm
2～90A/dm
2Condition under the above-mentioned sulfuric acid of electrolysis be copper electrolyte.
7. an electrolytic copper foil obtains by any described manufacture method in the claim 1～6, it is characterized in that, its surfaceness of separating out the face side is the following low profiles of 1.0 μ m, and this glossiness Gs (60 °) that separates out face is more than 400.
8. copper clad laminate, it adopts the described electrolytic copper foil of claim 7 to obtain.
9. surface treatment copper foil, it is separated out on the face the described electrolytic copper foil of claim 7, implement roughened, antirust processing, silane coupling agent in handling any one or two or more.
10. surface treatment copper foil as claimed in claim 9 is characterized in that, it is low profile below the 2 μ m that the mask of fitting with the insulating resin base material of above-mentioned surface treatment copper foil has surfaceness.
11. a copper clad laminate, it adopts claim 9 or 10 described surface treatment copper foils to obtain.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP317174/2005 | 2005-10-31 | ||
| JP2005317174 | 2005-10-31 | ||
| JP294778/2006 | 2006-10-30 |
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| CN101297067A true CN101297067A (en) | 2008-10-29 |
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| CNA2006800396784A Pending CN101297067A (en) | 2005-10-31 | 2006-10-31 | Method for manufacture of electrolytic copper foil, electrolytic copper foil manufactured by the method, surface-treated copper foil manufactured using the electrolytic copper foil, and copper-clad la |
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| CN (1) | CN101297067A (en) |
| TW (1) | TW200728515A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812944A (en) * | 2012-11-20 | 2015-07-29 | Jx日矿日石金属株式会社 | Copper foil with carrier |
| TWI503454B (en) * | 2012-11-20 | 2015-10-11 | Jx Nippon Mining & Metals Corp | Method for manufacturing copper foil, attached copper foil, printed wiring board, printed circuit board, copper clad sheet, and printed wiring board |
| CN105386088A (en) * | 2010-07-01 | 2016-03-09 | 三井金属矿业株式会社 | Electrodeposited copper foil and process for production thereof |
| CN106968000A (en) * | 2017-03-21 | 2017-07-21 | 佛冈建滔实业有限公司 | The production method and copper foil electrolysis installation of a kind of electrolyte of copper foil and copper foil |
| CN107022774A (en) * | 2012-05-11 | 2017-08-08 | Jx日矿日石金属株式会社 | Surface treatment copper foil and the manufacture method using its laminated plates, copper foil, printing distributing board, e-machine and printing distributing board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5379528B2 (en) * | 2009-03-24 | 2013-12-25 | 三井金属鉱業株式会社 | Electrolytic copper foil with carrier foil, method for producing electrolytic copper foil with carrier foil, and copper-clad laminate obtained using the electrolytic copper foil with carrier foil |
-
2006
- 2006-10-31 CN CNA2006800396784A patent/CN101297067A/en active Pending
- 2006-10-31 TW TW095140188A patent/TW200728515A/en not_active IP Right Cessation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105386088A (en) * | 2010-07-01 | 2016-03-09 | 三井金属矿业株式会社 | Electrodeposited copper foil and process for production thereof |
| CN105386088B (en) * | 2010-07-01 | 2018-06-29 | 三井金属矿业株式会社 | Electrolytic copper foil and its manufacturing method |
| CN107022774A (en) * | 2012-05-11 | 2017-08-08 | Jx日矿日石金属株式会社 | Surface treatment copper foil and the manufacture method using its laminated plates, copper foil, printing distributing board, e-machine and printing distributing board |
| CN104812944A (en) * | 2012-11-20 | 2015-07-29 | Jx日矿日石金属株式会社 | Copper foil with carrier |
| TWI503454B (en) * | 2012-11-20 | 2015-10-11 | Jx Nippon Mining & Metals Corp | Method for manufacturing copper foil, attached copper foil, printed wiring board, printed circuit board, copper clad sheet, and printed wiring board |
| CN104812944B (en) * | 2012-11-20 | 2019-02-19 | Jx日矿日石金属株式会社 | Copper foil with carrier |
| CN106968000A (en) * | 2017-03-21 | 2017-07-21 | 佛冈建滔实业有限公司 | The production method and copper foil electrolysis installation of a kind of electrolyte of copper foil and copper foil |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI328623B (en) | 2010-08-11 |
| TW200728515A (en) | 2007-08-01 |
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Application publication date: 20081029 |