CN104002515A - Compound double sided black copper foil and making method thereof - Google Patents
Compound double sided black copper foil and making method thereof Download PDFInfo
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- CN104002515A CN104002515A CN201310058980.6A CN201310058980A CN104002515A CN 104002515 A CN104002515 A CN 104002515A CN 201310058980 A CN201310058980 A CN 201310058980A CN 104002515 A CN104002515 A CN 104002515A
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Abstract
A compound double sided black copper foil comprises a copper foil and two blackened layers, the copper foil has a shiny side and a matte side, the two blackened layers are arranged on the shiny side and the matte side respectively, the two blackened layers are alloy layers formed by electroplating in an electroplating bath containing copper ions, cobalt ions, nickel ions, manganese ions, magnesium ions and sodium ions, and a coarsening layer is selectively respectively arranged between one of the two blackened layer and the shiny side of the copper foil and between the other one of the two blackened layer and the matte side of the copper foil. The two sides of the copper foil have the characteristics of intensely black appearance, uniformity, no speckles, no powder falling, good etching property, and effective obstruction of electromagnetic waves, near infrared lines, stray light and outside light, and can be directly processed through a laser boring technology due to strong light absorption ability. The invention also provides a making method of the compound double sided black copper foil.
Description
Technical field
The present invention relates to the Copper Foil that one has Darkening process face (layer), especially relate to one and have composite type double sided black Copper Foil and the manufacture method thereof of two-sided Darkening process face (layer).
Background technology
In recent years, the plasm display panel (PDP) that has features such as the large screen of being easy to and actuating speed be fast is just extensively used on various display devices.
In general, plasm display panel is to utilize gas discharge and produce plasma, and excites set fluorophor in unit (cell) by the line spectrum of the ultraviolet range that produced according to this, to produce the light of visible region.But, utilizing gas discharge to produce in the process of plasma, not only can produce line spectrum in ultraviolet range, even can produce wave-length coverage line spectrum widely near infrared light area.Need mention, the wavelength of above-mentioned near infrared light area, because approach the wavelength that optical communication adopts, if the problem that will have misoperation close to each other, and will cause the problem that produces microwave or ultra-low frequency electromagnetic wave.
The problem of leaking in order to block the line spectrum of this kind of electromagnetic wave or near infrared light area, is generally that the screen layer being made up of Copper Foil is set before panel, and this Copper Foil is to utilize etch processes to form thin-line-shaped reticulate body to form screen layer conventionally.But because the Copper Foil itself that forms screen layer has gloss, can will be reflected from the light of panel outside, the problem that causes picture contrast to worsen, and the light producing in picture can be reflected, and then reduction light transmittance, the problem that causes display floater identification to worsen.
In order to address the above problem, need implement black processing to the copper foil shielding layer that effectively line spectrum of electromagnetic wave shielding or near infrared light area is leaked; But known technology is all only implemented black processing at single of Copper Foil, therefore only can solve the problem of single electromagnetic wave shielding of Copper Foil, causes in downstream process and need carry out black processing to Copper Foil another side again, causes manufacturing cost to improve.On the other hand, due to densification, high performance and the microminiaturization of electronic component, therefore the distribution of printed circuit board (PCB) is also towards densification; Compared to traditional mechanical type boring, can carry out the more laser drill of microfabrication and extensively be used.But because near the reflectivity of the copper wavelength 10 μ m of carbon dioxide laser approaches 100%, therefore at the high carbon dioxide laser of versatility, Copper Foil is carried out the Laser Processing efficiency extreme difference of laser drill.
Again on the one hand, have and adopt deposited shape mask (conformal mask) method (etching method) person in HDI technique; Have to adopt and implement black brown processing at copper foil surface, copper foil surface is formed and there is the careful black oxide layer structure of strong extinction ability, and can directly carry out high efficiency laser drill person; Have the thinning of the Copper Foil of employing carry out laser drill person again, but said method still all respectively have the problems such as production efficiency is poor, production management is complicated, production cost is high.
Summary of the invention
In view of above-mentioned disappearance, inventors etc. are with working experience for many years and subject study, experiment, the discussion of determining for above-listed quasi-solution, found that Copper Foil two sides is first washed away and is attached to after lip-deep dirt or dirty thing with copper sulphate acid solution, after imposing plating with copper sulphate electroplating bath in two sides again, impose on again black electroplating processes in two sides, Copper Foil pattern before blackization is electroplated and the form of black electroplating processes can affect color and luster and the homogeneity of black coating, have completed the present invention based on this design.
The object of this invention is to provide a kind of composite type double sided black Copper Foil, it is characterized in that the two sides to Copper Foil imposes black processing simultaneously, though be therefore bright or dark face all present thick black outward appearance, homogeneous without line spot, without dry linting occur, etching is good, is applicable to plasma display (PDP), electromagnetic shielding (EMI), high-density printed circuit board (HDI) technique, Direct Laser bore process, inner plating technique, flexible copper clad substrate (FCCL), flexible printed circuit board (FPC).
According to one embodiment of the invention, described composite type double sided black Copper Foil comprises a Copper Foil and two Darkening process layers; This Copper Foil has one bright and a dark face, described two Darkening process layers are arranged at respectively on this bright and this dark face, and described two Darkening process layers are to electroplate formed alloy-layer in the electroplating bath that comprises copper ion, cobalt ions, nickel ion, manganese ion, magnesium ion and sodium ion.
In one embodiment of this invention, also comprise two roughened layers, be arranged at respectively one of them of described two Darkening process layers and between this bright and between wherein another and this dark face of described two Darkening process layers.
The manufacture method of described composite type double sided black Copper Foil comprises the following steps: first, provide a Copper Foil, it has one bright and a dark face; Then, process bright and dark face of this Copper Foil with acid solution; Subsequently, form the first roughened layer in this bright, and form the second roughened layer in this dark face; Afterwards, form the first Darkening process layer on this first roughened layer, and form the second Darkening process layer on this second roughened layer, wherein this first Darkening process layer and this second Darkening process layer are to electroplate formed alloy-layer in the electroplating bath that comprises copper ion, cobalt ions, nickel ion, manganese ion, magnesium ion and sodium ion.
In sum, composite type double sided black Copper Foil of the present invention has at the electroplating bath that comprises copper ion, cobalt ions, nickel ion, manganese ion, magnesium ion and sodium ion electroplates formed Darkening process layer, therefore all present the outward appearance of thick black on two surfaces of Copper Foil, can effectively suppress the reflection of the reflection of light of being injected by panel outside and the light being penetrated by plasma display (light producing in picture), with the contrast of improving picture and the identification of display floater.
Moreover, described Darkening process layer has excellent shielding character, electromagnetic wave, near infrared ray, veiling glare and outer light etc. be can effectively intercept, plasma display (PDP), electromagnetic shielding (EMI), high-density printed circuit board (HDI) technique, Direct Laser bore process, inner plating technique, flexible copper clad substrate (FCCL), flexible printed circuit board (FPC) etc. are applicable to.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the manufacture method of composite type double sided black Copper Foil of the present invention;
Fig. 2 is the generalized section of composite type double sided black Copper Foil of the present invention;
Fig. 3 A is the sweep electron microscope figure of bright of the composite type double sided black Copper Foil of the embodiment of the present invention 1;
Fig. 3 B is the sweep electron microscope figure of the dark face of the composite type double sided black Copper Foil of the embodiment of the present invention 1; And
Fig. 4 is the generalized section of the composite type double sided black Copper Foil of the embodiment of the present invention 7.
Wherein, description of reference numerals is as follows:
1 composite type double sided black Copper Foil
10 Copper Foils
11 bright
12 dark faces
20 roughened layers
21 first roughened layers
22 second roughened layers
30 Darkening process layers
31 first Darkening process layers
32 second Darkening process layers
40 antirust coats
41 first antirust coats
42 second antirust coats
50 silane treatment layers
Detailed description of the invention
Refer to Fig. 1 of the present invention and 2, wherein Fig. 1 shows the schematic flow sheet of the manufacture method of composite type double sided black Copper Foil of the present invention, and Fig. 2 shows the generalized section of the made composite type double sided black Copper Foil of described manufacture method.To utilize each embodiment and comparative example to illustrate the present invention below, only interest field of the present invention not be limited by these embodiment.
Embodiment 1
Execution step S10, provides a Copper Foil 10, and it has one bright (shiny side) 11 and a dark face (matte side) 12.In this specific embodiment, the thickness of Copper Foil 10 between 6 to 35 μ m and roughness (Rz) be below 1.5; It should be noted that, described Copper Foil 10, because of the cause of operational characteristic, presents in compact grained mode in the institutional framework of the copper-clad surface near cathode electrode side, and its brightness and roughness are all better, therefore be commonly referred to as bright 11; In addition, present in the mode of column crystal in the institutional framework of the copper-clad surface near the opposite side of electroplate liquid, its roughness is greater than bright and present peach outward appearance conventionally, therefore be commonly referred to as dark face 12.
Execution step S11, with bright 11 and dark face 12 of acid solution cleaning Copper Foil 10.Particularly, described acid solution comprises the sulfuric acid that copper sulfate pentahydrate that concentration is 255g/L and concentration are 95g/L, and the time of cleaning is 8 seconds, in order to remove the dirt or the dirty thing that are attached on bright 11 of Copper Foil 10 and dark face 12; And clean with water after pickling completes, remain acid solution and affect subsequent technique on the two sides of Copper Foil 10 avoiding.
Execution step S12, forms roughened layer 20, comprises and forms the first roughened layer 21 in bright 11, and form the second roughened layer 22 in dark face 12.Particularly, first Copper Foil 10 being inserted to the electroplating bath that comprises the sodium phosphotungstate 18 water compound that copper sulfate pentahydrate that concentration is 86g/L, sulfuric acid that concentration is 95g/L and concentration are 15ppm electroplates; The bath temperature of wherein electroplating is that 25 DEG C, current density are between 10.8A/dm
2to 20.6A/dm
2between (ampere/square centimeter) and the time be 6.5 seconds, carry out pretreatment with bright 11 to Copper Foil 10 and dark face 12.
Then, after cleaning with water, use identical electroplating bath to electroplate; The current density of wherein electroplating is between 1.34A/dm
2to 2.59A/dm
2between and the time be 9.7 seconds, to form respectively the alligatoring structure (not shown) being formed by copper in bright 11 and dark face 12 of Copper Foil 10; Similarly, after cleaning with water, use identical electroplating bath and condition to electroplate, use and form complete roughened layer 20 in bright 11 and dark face 12 of Copper Foil 10, thus the bond strength of lifting composite type double sided black Copper Foil 1 and an outside base material (not shown).
Execution step S13, forms Darkening process layer 30, comprises and forms the first Darkening process layer 31 on the first roughened layer 21, and form the second Darkening process layer 32 on the second roughened layer 22.Particularly, after first cleaning with water, then the Copper Foil 10 that is formed with complete roughened layer 20 is inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 20g/L, magnesium sulfate 7 hydrate that concentration is 35g/L and concentration are 95g/L and electroplate.
In the present embodiment, the bath temperature of plating is that 35 DEG C, pH value are 5.5, current density is between 6A/dm
2to 8A/dm
2between and the time be 15 seconds, use and form complete Darkening process layer 30 on the first roughened layer 21 and the second roughened layer 22, thereby be formed with the outward appearance of thick black on the two sides of Copper Foil 10.Moreover, referring to Fig. 3 A and 3B, its outward appearance homogeneous that shows described the first Darkening process layer 31 and the second Darkening process layer 32 is without line spot, occur without dry linting.
Execution step S14, forms antirust coat 40, comprises and forms the first antirust coat 41 on the first Darkening process layer 31, and form the second antirust coat 42 on the second Darkening process layer 32.Particularly, after first cleaning with water, then the Copper Foil 10 that is formed with complete roughened layer 20 and Darkening process layer 30 is inserted to the electroplating bath that comprises the liquid caustic soda that ZINC SULFATE HEPTAHYDRATE that concentration is 3g/L, chromic acid that concentration is 2g/L and concentration are 25g/L and electroplate; The bath temperature of wherein electroplating is that 60 DEG C, current density are 1A/dm
2and the time is 7 seconds, uses and form complete antirust coat 40 on the first Darkening process layer 31 and the second Darkening process layer 32, to add antirust effect on Copper Foil 10.
Execution step S15, forms a silane treatment layer 50 in one of them of the first antirust coat 41 and the second antirust coat 42.Particularly, after first cleaning with water, again with the amino trimethyl silane aqueous solution of the 3-of 0.5wt% (concentration expressed in percentage by weight) spray coating on the first antirust coat 41 or the second antirust coat 42, utilize afterwards baking oven at the temperature of 150 DEG C, to toast 8 seconds, use and form silane treatment layer 50 on the first antirust coat 41 or the second antirust coat 42.
Supplement mention be, according to the demand of practical application, silane treatment layer 50 of the present invention can be used as insulating coating, optical coating, release coating, antifogging coating etc., or in functions such as the additional hydrophily in the surface of upgrading, hydrophobicity, directionality, absorption and electric charge transmission.Each property list of the composite type double sided melanism Copper Foil obtaining through above-mentioned steps is shown in table 2.
Embodiment 2
Embodiment 2 is step S12 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, first Copper Foil 10 being inserted to the electroplating bath that includes the arsenic trioxide that copper sulfate pentahydrate that concentration is 86g/L, sulfuric acid that concentration is 95g/L and concentration are 400ppm electroplates; The bath temperature of wherein electroplating is that 25 DEG C, current density are between 13.8A/dm
2to 22.6A/dm
2between and the time be 6.5 seconds, carry out pretreatment with bright 11 to Copper Foil 10 and dark face 12.
Then, to use identical electroplating bath to electroplate after washing; The current density of wherein electroplating is between 1.74A/dm
2to 2.89A/dm
2between and the time be 9.7 seconds, to form respectively the alligatoring structure being formed by copper in bright 11 and dark face 12 of Copper Foil 10.Similarly, after cleaning with water, use identical electroplating bath and condition to electroplate, use and form complete roughened layer 20 in bright 11 and dark face 12 of Copper Foil 10, thus the bond strength of lifting composite type double sided black Copper Foil 1 and an outside base material.
In more detail, embodiment 2 has changed composition and the plating condition of electroplating bath.Each property list of the composite type double sided melanism Copper Foil obtaining through above-mentioned steps is shown in table 2.
Embodiment 3
Embodiment 3 is step S13 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, the Copper Foil 10 that is formed with complete roughened layer 20 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 55g/L, nickel sulfate hexahydrate compound that concentration is 12g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 20g/L, magnesium sulfate 7 hydrate that concentration is 35g/L and concentration are 95g/L electroplates.
In more detail, embodiment 3 has reduced the concentration of copper sulfate pentahydrate in electroplating bath, and increases the concentration of nickel sulfate hexahydrate compound in electroplating bath.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Embodiment 4
Embodiment 4 is step S13 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, the Copper Foil 10 that is formed with complete roughened layer 20 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 27g/L, magnesium sulfate 7 hydrate that concentration is 48g/L and concentration are 95g/L electroplates.
In more detail, embodiment 4 has increased the concentration of manganese sulfate monohydrate and magnesium sulfate 7 hydrate in electroplating bath simultaneously.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Embodiment 5
Embodiment 5 is step S13 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, the Copper Foil 10 that is formed with complete roughened layer 20 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 20g/L, magnesium sulfate 7 hydrate that concentration is 35g/L and concentration are 115g/L electroplates.
In more detail, embodiment 5 has increased the concentration of Trisodium citrate dihydrate in electroplating bath.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Embodiment 6
Embodiment 6 is step S13 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, the Copper Foil 10 that is formed with complete roughened layer 20 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 38g/L, manganese sulfate monohydrate that concentration is 20g/L, magnesium sulfate 7 hydrate that concentration is 48g/L and concentration are 95g/L electroplates.
In more detail, embodiment 6 has reduced the concentration of cobaltous sulfate heptahydrate in electroplating bath.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Embodiment 7
Refer to Fig. 4, embodiment 7 is not perform step S12 with the difference of embodiment 1.Particularly, Copper Foil 10 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 70g/L, nickel sulfate hexahydrate compound that concentration is 12g/L, cobaltous sulfate heptahydrate that concentration is 50g/L, manganese sulfate monohydrate that concentration is 25g/L, magnesium sulfate 7 hydrate that concentration is 40g/L and concentration are 135g/L electroplates.
Therefore, the composite type double sided melanism Copper Foil 1 of embodiment 7 is not formed with the first roughened layer 21 and the second roughened layer 22, and the first Darkening process layer 31 is formed at bright 11 of Copper Foil 10, the second 32, Darkening process layer is formed at the dark face 12 of Copper Foil 10, and described the first Darkening process layer 31 and the second Darkening process layer 32 have respectively more strong degree of blackness.
Comparative example 1
Comparative example 1 is that with the difference of embodiment 1 step S12 will not implement, and is not formed with roughened layer 20, and all the other steps are all identical with embodiment 1.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Comparative example 2
Comparative example 2 is step S13 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, the Copper Foil 10 that is formed with complete roughened layer 20 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 20g/L, magnesium sulfate 7 hydrate that concentration is 35g/L and concentration are 70g/L electroplates.
In more detail, comparative example 2 has reduced the concentration of Trisodium citrate dihydrate in electroplating bath.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Comparative example 3
Comparative example 3 is step S13 with the difference of embodiment 1, and all the other steps are all identical with embodiment 1.Particularly, the Copper Foil 10 that is formed with complete roughened layer 20 being inserted to the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 20g/L and concentration are 95g/L electroplates.
In more detail, the electroplating bath of comparative example 3 does not comprise magnesium sulfate 7 hydrate.Each property list of the composite type double sided melanism Copper Foil 1 obtaining through above-mentioned steps is shown in table 2.
Should be noted, if the concentration of copper sulfate pentahydrate is less than 40g/L in electroplating bath, black colourity can be not enough; If be greater than 80g/L, can produce the phenomenon of copper powder (powder falls).If the concentration of nickel sulfate hexahydrate compound is less than 5g/L, black colourity can be not enough; If be greater than 15g/L, etching can variation.If the concentration of cobaltous sulfate heptahydrate is less than 30g/L, black colourity can be not enough; If be greater than 60g/L, can produce speckle.If the concentration of manganese sulfate monohydrate is less than 15g/L, black colourity can be not enough; If be greater than 30g/L, can produce the phenomenon of copper powder (powder falls).If the concentration of magnesium sulfate 7 hydrate is less than 20g/L, black colourity can be not enough; If be greater than 50g/L, can produce speckle.If the concentration of Trisodium citrate dihydrate is less than 80g/L, black colourity can be not enough; If be greater than 150g/L, electroplating bath can produce precipitation.
Moreover, if the temperature of electroplating is greater than 20 DEG C, can produce speckle; If be greater than 60 DEG C, black colourity can be not enough.If pH value is less than 4, electroplating bath can produce precipitation; If be greater than 7, black colourity can be not enough.If current density is less than 3A/dm
2, black colourity can be not enough; If be greater than 20A/dm
2, can produce the phenomenon of copper powder (powder falls).If electroplating time is less than 10 seconds, black colourity can be not enough; If be greater than 30 seconds, can produce the phenomenon of copper powder (powder falls).
Refer to lower list 1 and 2, table 1 shows the electroplate liquid composition that various embodiments of the present invention and each comparative example use, and Fig. 2 shows the physical characteristic of various embodiments of the present invention and each comparative example.Wherein, the physical characteristic test event of various embodiments of the present invention and each comparative example comprises:
A. outward appearance speckle: about the black color spot striped of appearance surfaces with visual judgement.
B. colourity Y value: measure with colour difference meter.
C. glossiness: measure with Grossmeters.
D. powder falls: by the one side of filter paper with finger tip by bright 11 and the overall with leftward position of dark face 12 of Copper Foil 10, slide from left to right approximately 30 centimeters, the filter paper testing again with sample card comparison, judge grade.
The fall metewand > of grade of < powder
O :≤1 grade
△ :≤1-2 level
X :≤2 grade
E. etching: test film is made and become live width/line-spacing: 75/75 (μ m), be placed in containing copper chloride 265.9g/l, hydrogen peroxide 150ml/l, in the acidic etching liquid of HCl224ml/l, under 55 DEG C of conditions of temperature, flood after 5 minutes, with 3%NaOH solution striping under 48 DEG C of conditions of temperature.After washing, electroless nickel layer, then section, observes burr situation with OM (light microscope) and SEM (scanning type electron microscope).
The metewand > of < etching grade
O: after etching, the burr phenomenon of noresidue on base material.
△: after etching, have some residual burr phenomenons on base material.
X: after etching, have a lot of residual burr phenomenon on base material.
Table 1:
Table 2:
Hence one can see that, outward appearance black colourity, glossiness, the powder of the composite type double sided melanism Copper Foil 1 of the embodiment of the present invention 1 ~ 6 fall and the quality characteristic such as etching all quite good, the characteristics such as every characteristic outward appearance, black colourity and the glossiness of comparative example are all poor compared with embodiments of the invention.
Again consult Fig. 2, it shows via the made composite type double sided black Copper Foil 1 of the manufacture method of above-mentioned composite type double sided black Copper Foil, and it comprises a Copper Foil 10, two roughened layers 20, two Darkening process layers 30, two antirust coats 40 and a silane treatment layer 50.Copper Foil 10 has one bright 11 and a dark face 12; Two roughened layers 20 are arranged at respectively bright 11 and dark face 12; Two Darkening process layers 30 are arranged at respectively on two roughened layers 20, and wherein, two Darkening process layers 30 are to electroplate formed alloy-layer in the electroplating bath that comprises copper ion, cobalt ions, nickel ion, manganese ion, magnesium ion and sodium ion; Two antirust coats 40 are arranged at respectively on two Darkening process layers 30; And silane treatment layer 50 is arranged in one of them of two antirust coats 40.
Particularly, two Darkening process layers 30 are to electroplate formed alloy-layer in the electroplating bath that comprises the Trisodium citrate dihydrate that copper sulfate pentahydrate that concentration is 65g/L, nickel sulfate hexahydrate compound that concentration is 9g/L, cobaltous sulfate heptahydrate that concentration is 45g/L, manganese sulfate monohydrate that concentration is 20g/L, magnesium sulfate 7 hydrate that concentration is 35g/L and concentration are 95g/L; The bath temperature of wherein electroplating is that 20 DEG C to 60 DEG C, pH value are 4 to 7, the time is that 10 seconds to 30 seconds and current density are 3 amperes/square centimeter to 20 amperes/square centimeter.
Preferably, the thickness of Copper Foil 10 is 6 to 35 μ m, and the roughness (Rz) of bright 11 of Copper Foil 10 is 1.0 to 2.0, and the roughness of the dark face 12 of Copper Foil 10 is 1.0 to 2.0.And the colourity Y value of the two Darkening process layers 30 measured of colour difference meter is 2 to 10, be wherein preferably not more than 4; The gloss value of the two Darkening process layers 30 that Grossmeters is measured is 0.1 to 10, is wherein preferably not more than 1.
Via the above, there is the electrolytic copper foil of one side black treated side (layer) compared to tradition, the present invention has following advantages: the manufacture method of composite type double sided black Copper Foil of the present invention can be by the electrolytic treatments of special electrolyte and step, allows outward appearance, homogeneous that the two sides of Copper Foil has a thick black without line spot, occur and the advantage such as etching is good without dry linting; Moreover described manufacture method is first to wash away after the two sides dirt or dirty thing that is attached to Copper Foil with acid solution, then imposes Darkening process in the two sides of Copper Foil, to form preferably Darkening process layer of color and luster and homogeneity.
As above institute is old, Darkening process layer of the present invention also has excellent shielding character, electromagnetic wave, near infrared ray, veiling glare and outer light etc. be can effectively intercept, plasma display (PDP), electromagnetic shielding (EMI), high-density printed circuit board (HDI) technique, Direct Laser bore process, inner plating technique, flexible copper clad substrate (FCCL), flexible printed circuit board (FPC) etc. are therefore applicable to.
The foregoing is only better possible embodiments of the present invention, non-ly therefore limit to the scope of the claims of the present invention, therefore such as use the equivalence techniques that description of the present invention and diagramatic content are done to change, be all contained in scope of the present invention.
Claims (11)
1. a composite type double sided black Copper Foil, is characterized in that, comprising:
One Copper Foil, has one bright and a dark face; And
Two Darkening process layers, be arranged at respectively on this bright and this dark face, and described two Darkening process layers are to electroplate formed alloy-layer in the electroplating bath that comprises copper ion, cobalt ions, nickel ion, manganese ion, magnesium ion and sodium ion.
2. composite type double sided black Copper Foil as claimed in claim 1, is characterized in that, also comprises two roughened layers, is arranged at respectively one of them of described two Darkening process layers and between this bright and between wherein another and this dark face of described two Darkening process layers.
3. composite type double sided black Copper Foil as claimed in claim 2, it is characterized in that, also comprise two antirust coats and a silane treatment layer, described two antirust coats are arranged at respectively on described two Darkening process layers, and this silane treatment layer is arranged in one of them of described two antirust coats.
4. composite type double sided black Copper Foil as claimed in claim 1, it is characterized in that, described two Darkening process layers are in comprising the copper sulfate pentahydrate that concentration is 40 ~ 80g/L, concentration is the nickel sulfate hexahydrate compound of 5 ~ 15g/L, concentration is the cobaltous sulfate heptahydrate of 30 ~ 60g/L, concentration is the manganese sulfate monohydrate of 15 ~ 30g/L, the electroplating bath of the Trisodium citrate dihydrate that the magnesium sulfate 7 hydrate that concentration is 20 ~ 50g/L and concentration are 80 ~ 150g/L is electroplated formed alloy-layer, the bath temperature of wherein electroplating is 20 DEG C to 60 DEG C, pH value is 4 to 7, time is that 10 seconds to 30 seconds and current density are 3 amperes/square centimeter to 20 amperes/square centimeter.
5. composite type double sided black Copper Foil as claimed in claim 1, is characterized in that, the thickness of this Copper Foil is 6 to 35 μ m, and this roughness of bright is 1.0 to 2.0, and the roughness of this dark face is 1.0 to 2.0.
6. composite type double sided black Copper Foil as claimed in claim 1, is characterized in that, the colourity Y value of the described two Darkening process layers of being measured by colour difference meter is 2 to 10, and the gloss value that is crossed the described two Darkening process layers that meter measures by gloss is 0.1 to 10.
7. a manufacture method for composite type double sided black Copper Foil, is characterized in that, comprises the following steps:
One Copper Foil is provided, and it has one bright and a dark face;
Clean bright and dark face of this Copper Foil with acid solution;
Form one first roughened layer in this bright, and form one second roughened layer in this dark face; And
Form one first Darkening process layer on this first roughened layer, and form one second Darkening process layer on this second roughened layer, and this first Darkening process layer and this second Darkening process layer are to electroplate formed alloy-layer in the electroplating bath that comprises copper ion, cobalt ions, nickel ion, manganese ion, magnesium ion and sodium ion.
8. the manufacture method of composite type double sided black Copper Foil as claimed in claim 7, is characterized in that, after the step of this formation first Darkening process layer and the second Darkening process layer, further comprising the steps of:
Form one first antirust coat on this first Darkening process layer, and form one second antirust coat on this second Darkening process layer; And
Form a silane treatment layer in one of them of this first antirust coat and this second antirust coat.
9. the manufacture method of composite type double sided black Copper Foil as claimed in claim 7, it is characterized in that, this the first Darkening process layer and this second Darkening process layer are in comprising the copper sulfate pentahydrate that concentration is 40 ~ 80g/L, concentration is the nickel sulfate hexahydrate compound of 5 ~ 15g/L, concentration is the cobaltous sulfate heptahydrate of 30 ~ 60g/L, concentration is the manganese sulfate monohydrate of 15 ~ 30g/L, the electroplating bath of the Trisodium citrate dihydrate that the magnesium sulfate 7 hydrate that concentration is 20 ~ 50g/L and concentration are 80 ~ 150g/L is electroplated formed alloy-layer, the bath temperature of wherein electroplating is 20 DEG C to 60 DEG C, pH value is 4 to 7, time is that 10 seconds to 30 seconds and current density are 3 amperes/square centimeter to 20 amperes/square centimeter.
10. the manufacture method of composite type double sided black Copper Foil as claimed in claim 7, is characterized in that, the thickness of this Copper Foil is 6 to 35 μ m, and this roughness of bright is 1.0 to 2.0, and the roughness of this dark face is 1.0 to 2.0.
The manufacture method of 11. composite type double sided black Copper Foils as claimed in claim 7, it is characterized in that, the colourity Y value of the described two Darkening process layers that colour difference meter is measured is 2 to 10, and the gloss value that gloss crosses the described two Darkening process layers that meter measures is 0.1 to 10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105603343A (en) * | 2015-12-21 | 2016-05-25 | 北海光利彩色印刷有限公司 | Breathable copper air-conditioning foil and preparation method thereof |
| CN107801366A (en) * | 2016-09-06 | 2018-03-13 | 拓自达电线株式会社 | Electromagnetic shielding film |
| CN110029377A (en) * | 2019-05-15 | 2019-07-19 | 东南大学 | A kind of long-wave band blacker-than-black is composite porous and preparation method thereof |
| CN110344105A (en) * | 2019-08-05 | 2019-10-18 | 中色奥博特铜铝业有限公司 | A kind of two-sided surface treatment method of rolled copper foil |
| CN110571365A (en) * | 2019-07-19 | 2019-12-13 | 厦门大学 | External packing material for lithium ion battery and application thereof |
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| JPH0987889A (en) * | 1995-09-28 | 1997-03-31 | Nikko Gould Foil Kk | Treatment of copper foil for printed circuit |
| CN101809206A (en) * | 2007-09-28 | 2010-08-18 | 日矿金属株式会社 | Copper foil for printed circuit and copper clad laminate |
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| JPH0987889A (en) * | 1995-09-28 | 1997-03-31 | Nikko Gould Foil Kk | Treatment of copper foil for printed circuit |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603343A (en) * | 2015-12-21 | 2016-05-25 | 北海光利彩色印刷有限公司 | Breathable copper air-conditioning foil and preparation method thereof |
| CN107801366A (en) * | 2016-09-06 | 2018-03-13 | 拓自达电线株式会社 | Electromagnetic shielding film |
| CN107801366B (en) * | 2016-09-06 | 2020-07-17 | 拓自达电线株式会社 | Electromagnetic wave shielding film |
| CN110029377A (en) * | 2019-05-15 | 2019-07-19 | 东南大学 | A kind of long-wave band blacker-than-black is composite porous and preparation method thereof |
| CN110571365A (en) * | 2019-07-19 | 2019-12-13 | 厦门大学 | External packing material for lithium ion battery and application thereof |
| CN110344105A (en) * | 2019-08-05 | 2019-10-18 | 中色奥博特铜铝业有限公司 | A kind of two-sided surface treatment method of rolled copper foil |
| CN110344105B (en) * | 2019-08-05 | 2020-10-09 | 中色奥博特铜铝业有限公司 | Double-sided surface treatment method of rolled copper foil |
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| CN104002515B (en) | 2016-08-03 |
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