KR20180047897A - Electrodeposited copper foil with its surfaceprepared, process for producing the same and usethereof - Google Patents

Abstract

The present invention relates to a surface treatment electrolysis copper foil produced by a foil manufacturing process and a surface treatment process. Wherein the surface treatment electrolysis copper foil comprises a base material and a surface protrusion unit formed on one surface of the base material. A ratio of thickness (Y=a/b) of a protrusion unit to thickness of the base material (b) and thickness of the surface protrusion unit (a) is equal to or larger than 0.15 and equal to or less than 0.69.

Description

TECHNICAL FIELD [0001] The present invention relates to an electrolytic copper foil for surface treatment, a method for producing the same,

The present invention relates to a surface treated electrolytic copper foil having an improved dielectric constant, a method for producing the same, and a use such as a surface treatment electrolytic copper foil for use in, for example, a printed wiring board.

BACKGROUND ART [0002] In recent years, electronic devices such as a notebook personal computer have become increasingly smaller and lighter. Also, the wiring of the IC is being refined. In the wiring pattern formed on the substrate used for such an electronic device, the lead width is reduced to a few tens of microns (mu m), and the metal foil forming the wiring pattern is also becoming thinner. Particularly, although the thickness of the metal foil used for forming the wiring pattern having the lead width of about 100 mu m is about 15 to 35 mu m corresponding to the width of the wiring pattern in the past, the thickness of the metal foil used for forming the wiring pattern of about 10 mu m It needs to be thinned correspondingly.

As the metal foil for forming such a wiring pattern, for example, aluminum foil, copper foil and the like are used. Among such metal foils, copper foil is preferable, and electrolytic copper foil is preferably used.

The electrolytic copper foil used for forming such a wiring pattern is usually stripped by an electrolytic electrification and emulsification apparatus as shown in Fig. 1, and the surface treatment apparatus shown in Fig. 2 conducts harmonization treatment and anti-rust treatment for improving adhesion.

1 comprises a rotating drum-shaped cathode 2 (surface made of SUS or titanium) and an anode 1 (zinc or noble metal oxide-coated titanium electrode) arranged concentrically with respect to the cathode And a current is flowed between the positive and negative electrodes while flowing the electrolytic solution 3. The copper is deposited on the surface of the cathode to a predetermined thickness and then copper is peeled off from the surface of the cathode. The copper foil 4 at this stage is an untreated copper foil. The surface of the untreated copper foil in contact with the electrolyte is a matte side and the surface in contact with the rotating drum-shaped cathode 2 is a shiny side.

The untreated untreated copper foil 4 needs to be laminated with an insulating substrate to increase the adhesive strength (peel strength) in order to produce the copper clad laminate. In this regard, electrochemical or chemical surface treatment is continuously performed by the surface treatment apparatus as shown in Fig. 2 shows an apparatus for continuously performing surface treatment electrochemically. An untreated copper foil 4 is continuously passed through an electrolytic bath filled with an electrolytic solution 5 and an electrolytic bath filled with an electrolytic solution 5, ) Is used as an anode and the copper foil itself is used as a cathode to perform surface treatment. In order to improve the adhesion with the insulating substrate (resin film), copper in the form of particles is precipitated on the surface of the untreated copper foil 4. This step is a roughening treatment step, and the roughening treatment is usually carried out on the matte surface or the shiny surface of the untreated copper foil 4. The copper foil after the surface treatment is a surface-treated copper foil 8, which is laminated with an insulating substrate to form a circuit board.

The surface state of the shiny side of the untreated copper foil 4 is substantially the same as the drum surface state. That is, the 10-point average surface roughness (Rz) of the drum is about 1.2 to 2.5 mu m, and the 10-point average surface roughness (Rz) of the shiny surface is also about the same.

On the other hand, the surface roughness of the mat surface differs depending on the copper deposition state and thickness, but the surface roughness of the mat surface is larger than the surface roughness of the shiny surface. Generally, the 10 point average surface roughness Rz is about 2.5 to 10 mu m. In the electrolytic copper foil having an average thickness of about 35 탆, the surface roughness of such a mat surface is rarely a problem. However, in an electrolytic copper foil having a thickness of several tens of 탆, the surface roughness of such a mat surface corresponds to several tens% Such a state of the mat surface has a great influence on the electrical characteristics of the wiring pattern to be formed, particularly the board itself.

Particularly, the surface roughness, color and gloss of the electrolytic copper foil differ depending on the size and shape of the protrusions deposited on the mat surface of the surface-treated copper foil, and the tensile strength, elongation, peel strength and the like of the electrolytic copper foil are changed. Conventionally, the size and shape of the mat surface protrusions are expressed by physical parameters of surface roughness (for example, Rz, Ra, Rmax, Rpc, etc.) (see Patent Document 1, Patent Document 2 and Patent Document 3) As shown in FIG. 3B, there are many areas which are not measured by a conventional contact type illuminometer or a non-contact type illuminometer. As a result, the surface roughness value of the existing mat surface has a limit to sufficiently express the physical and chemical characteristics of the mat surface of the surface-treated copper foil.

4, even when the electrolytic copper foil 10 having the same electrodeposition amount and having the same thickness, the electrolytic copper foil 10 of the electrolytic copper foil is formed in accordance with the relative proportion of the pattern of the protruding portions 12 formed on the surface of the base portion 11 of the electrolytic copper foil. Electrical properties such as tensile strength, flexural resistance, peel strength, and dielectric constant can be greatly changed.

KR 10-1129471 B1 KR 10-2015-0014850 A KR 10-1090199 B1

The present inventors have found that the physical properties and permittivity of the electrolytic copper foil, such as the tensile strength, the bending resistance and the peel strength, of the electrolytic copper foil produced through the surface treatment process are varied according to the relative ratio of the protruding portion 12 of the mat surface to the base portion 11 of the electrolytic copper foil The same electrical characteristics have been found to vary greatly.

Accordingly, it is an object of the present invention to provide an electrolytic copper foil excellent in electrical characteristics such as physical properties such as tensile strength, bending resistance and peel strength and permittivity, and a copper clad laminate and a printed wiring board using the electrolytic copper foil.

It is another object of the present invention to provide an electrolytic copper foil in which the relative ratio (Y = a / b) of the matte surface protruding portion 12 to the substrate portion 11 of the surface treated electrolytic copper foil is optimized and a method for manufacturing such electrolytic copper foil do.

The present invention also provides an electrolytic copper foil in which the relative ratio (Y = a / b) of the matte surface protruding portion 12 to the substrate portion 11 of the surface treated electrolytic copper foil is optimized and a copper clad laminate and a printed wiring board using the electrolytic copper foil For another purpose.

The technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other technical problems not mentioned above can be clearly understood by those skilled in the art from the description of the invention described below.

According to one aspect of the present invention, there is provided a surface treated electrolytic copper foil produced by a stripping process and a surface treatment process comprising a substrate and a surface protruding portion formed on one surface of the substrate, (Y = a / b), which represents the relative ratio of the thickness (b) to the thickness (a) of the surface protrusions, is 0.15 or more and 0.69 or less.

The surface projecting portion includes a surface projecting layer formed on one surface of the substrate by a lapping process and a surface treatment layer formed on the surface projecting layer by a surface treatment process.

The thickness a of the surface protruding portion is 2 to 8 占 퐉 (more preferably 2.1 to 7.8 占 퐉) and the thickness of the base portion b is 10 to 14 占 퐉 (more preferably 10.4 to 13.8 占 퐉) .

One surface of the substrate is a mat surface, and the surface roughness of the mat surface is 1.8 to 4.6 탆 at a 10-point average roughness Rz.

The surface treatment step includes a roughening treatment step for forming a surface treatment layer on the surface projecting layer.

The copper clad laminate having the polyimide resin adhered to the surface treatment layer of the surface treated electrolytic copper foil according to one aspect of the present invention and the printed circuit board having the circuit pattern formed on the copper clad laminate can be used for a surface treatment electrolytic copper foil according to one aspect of the present invention .

A method for producing a surface treated electrolytic copper foil according to another aspect of the present invention comprises the steps of: (a) adding anionic additive 6 as an additive to an aqueous solution of copper sulfate having a copper concentration of 60 g / L to 120 g / L and a sulfuric acid concentration of 50 g / L to 120 g / And an electrolyte having a TOC concentration of 3 to 18 ppm is prepared by adding an electrolyte at a temperature of 40 to 60 DEG C and a current density of 50 to 80 ASD to a drum surface (Cu) is electrodeposited to produce an untreated copper foil comprising a substrate and a surface projection layer; And (b) forming a surface treatment layer on the surface projection layer of the untreated copper foil by a roughening treatment step to produce a surface treatment electrolytic copper foil; (Y = a / b), which represents the relative ratio of the thickness (b) of the substrate to the thickness (a) of the surface projection part made of the surface projection layer and the surface treatment layer, is 0.15 or more and 0.69 or less do.

The anion additive includes at least one of Cl, F, Br, I and PO4. Preferably, the anion additive is Cl and 7.3 to 16.2 ppm of Cl is added to the electrolyte solution.

Also, the leveler includes at least one of gelatin, collagen, and PEG (polyethylene glycol). Preferably, the leveler is gelatin, and 0.5 to 3.4 ppm of gelatin is added to the electrolyte solution.

Further, the surface treated electrolytic copper foil according to another aspect of the present invention is characterized in that an aqueous solution of copper sulfate having a copper concentration of 60 g / L to 120 g / L and a sulfuric acid concentration of 50 g / L to 120 g / L is added as an additive in an amount of 6 to 18 ppm, And an electrolyte solution having a TOC concentration of 3 to 18 ppm is prepared by adding 0.1 to 4.5 ppm of a leveler to an electrolyte solution having an electrolytic solution temperature of 40 to 60 캜 and a current density of 50 to 80 ASD, Cu) is electrodeposited to produce an untreated copper foil made of a substrate and a surface projection layer, and then a surface treatment layer is formed on the surface projection layer of the untreated copper foil by a roughening treatment step. The thickness (b) (Y = a / b), which represents the relative ratio of the surface protruding layer to the thickness (a) of the surface protruding portion made of the surface protruding layer, is 0.15 or more and 0.69 or less.

The surface treated electrolytic copper foil according to the present invention is excellent in physical properties such as tensile strength, bending resistance and peel strength, and has a low dielectric constant, thereby reducing electrical loss due to signal transmission. Therefore, the surface-treated electrolytic copper foil according to the present invention is suitable for use as an operating laminate for a printed wiring board of an electronic device in which miniaturization, light weight, and IC wiring are miniaturized.

Also, the surface treated electrolytic copper foil according to the present invention can be effectively applied to an anode current collector of a lithium secondary battery due to excellent physical properties and electrical characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given below, serve to further the understanding of the technical idea of the invention. And should not be construed as limiting.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of an anti-skimming device for electrodepositioning an untreated electrolytic copper foil.
2 is a schematic cross-sectional view of one embodiment of a surface treatment apparatus for surface treatment of an untreated copper foil produced by the stripping apparatus of Fig.
3A and 3B are SEM cross-sectional photographs of protrusions formed on the surface of the surface-treated electrolytic copper foil.
4 is a schematic cross-sectional view of a conventional surface treatment electrolytic copper foil.
5 is a schematic cross-sectional view of a surface treatment electrolytic copper foil according to an embodiment of the present invention.
6 is another schematic sectional view of a surface treatment electrolytic copper foil according to an embodiment of the present invention.
7 is a schematic cross-sectional view of a dielectric constant measuring apparatus.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only some of the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

First, a surface treatment electrolytic copper foil according to an embodiment of the present invention will be described with reference to FIG. 5 is a schematic cross-sectional view of a surface treated electrolytic copper foil 21 according to an embodiment of the present invention.

As shown in FIG. 5, the surface treatment electrolytic copper foil 21 according to the present invention is composed of a raw foil produced by the stripping apparatus of FIG. 1 and a surface treatment layer formed on one surface (for example, a mat surface) . The raw foil is an untreated copper foil produced by the stripping apparatus of Fig. 1, which has a matte side in contact with the electrolytic solution of the untreated copper foil and a shiny side in contact with the rotating drum-shaped cathode .

The untreated copper foil of FIG. 5 is composed of a substrate 22 formed by copper precipitation to a predetermined thickness and a surface projection layer 24 formed on one surface (for example, a mat surface) of the substrate. The surface treatment layer 25 is formed on the surface projection layer 24 through the surface treatment apparatus of FIG. 2 to complete the surface treatment electrolytic copper foil 21 according to the embodiment of the present invention.

The surface treatment electrolytic copper foil 21 according to the embodiment of the present invention includes the substrate 22 and the surface protruding portion 23 made of the surface protruding layer 24 and the surface treatment layer 25 on the substrate 22 .

5, the surface treatment electrolytic copper foil 21 according to the embodiment of the present invention has the thickness b of the substrate and the thickness of the surface protruding portion 23 as a, (Y = a / b), which is a parameter representing a relative ratio of the thickness (a) of the surface projection portion 23 to the surface projection portion 23, is 0.15 or more and 0.69 or less.

When the ratio (Y = a / b) of the protrusions is less than 0.15, the surface roughness of the surface treated electrolytic copper foil is excessively lowered, so that a base film (for example, a polyimide film The peeling strength between the substrate and the substrate is reduced. In this case, a de-lamination phenomenon may occur in the printed wiring board.

In addition, if the ratio of the protruded portions (Y = a / b) exceeds 0.69, the peeling strength of the surface treated electrolytic copper foil is improved, but the electrical characteristics such as the dielectric constant and the communication loss ratio are deteriorated.

Therefore, the surface-treated electrolytic copper foil according to one embodiment of the present invention has the physical properties (particularly, the peel strength with the base film) to be possessed by the electrolytic copper foil for a printed wiring board by optimizing the protrusion thickness ratio (Y = a / b) to 0.15 to 0.69, And electrical characteristics compared to conventional electrolytic copper foil.

In order to realize such a protrusion thickness ratio (Y = a / b), the surface treated electrolytic copper foil according to the embodiment of the present invention has a thickness a of the surface protrusion 23 of 2 to 8 탆 (more preferably 2.1 to 7.8 탆 ), And the thickness b of the base material 22 is 10 to 14 mu m (more preferably, 10.4 to 13.8 mu m).

Further, the surface roughness of the mat surface of the surface treated electrolytic copper foil according to the embodiment of the present invention shows 1.8 to 4.6 탆 at 10 point average surface roughness Rz.

In addition, the surface treatment layer 25 may be formed with a Cr and / or a chromate film to perform anti-rust treatment or, if necessary, a silane coupling treatment or an anti-rust treatment + silane coupling.

The thickness b of the base material 22 and the thickness a of the surface protruding portion 23 constituting the protrusion thickness ratio (Y = a / b) according to the present invention are more specifically defined with reference to FIG.

First, the surface-treated electrolytic copper foil 21 according to the embodiment of the present invention is cut in the MD (Machine Direction) direction by ion milling, and then the cut section is observed with an SEM at a magnification of 2 to 10K to measure its thickness as follows do.

The thickness of the surface protruding portion 23 is defined as a = a (max) - a (min).

A (max) is defined as a mean value of 5 points of the highest point of the protrusions of the surface protrusion within a measurement sample interval of 30um, and a (min) is defined as a mean value of 5 points of the lowest point of the protrusions of the surface protrusion within 30um of the measurement sample interval. do.

      The thickness b of the base material 22 is defined as a distance from the shiny surface to the a (min) of the mat surface.

According to another aspect of the present invention, there is provided a copper clad laminate having a structure in which a polyimide resin is adhered to a surface treatment layer (25) of the surface treatment electrolytic copper foil (21). The polyimide resin is similar in thermal expansion coefficient to an electrolytic copper foil and has excellent heat resistance for stability such as IC chip bonding.

According to still another aspect of the present invention, there is provided a printed wiring board having the copper-clad laminate and a predetermined circuit pattern formed on the copper clad laminate by an etching process.

< Example  And Comparative Example >

Hereinafter, the surface-treated electrolytic copper foil of the example satisfying the characteristics of the present invention and the comparative example to be compared with the electrolytic copper foil of the present invention and the properties of the surface-treated electrolytic copper foil of this example and the comparative example are compared, .

(Untreated An electric boat  Produce)

The untreated electrolytic copper foil according to the examples and the comparative example is produced by using the negative electrode forming machine as shown in Fig. 1 of the structure including the rotating drum and the positive electrode plate positioned at a predetermined interval with respect to the drum in the electrolytic bath. At this time, the gap between the positive electrode plate and the rotary drum is adjustable in the range of about 5 to 20 mm, and the standard deviation of the gap should be controlled within 2 mm.

The electrolytic solution used in the stamping process using such a vapor deposition machine may be copper sulfate, and a copper electrolytic copper foil is manufactured by electrodepositing the copper foil on the drum by appropriately mixing a leveler, an anion additive, brightener, or the like as an additive.

In this connection, the composition of the copper sulfate electrolytic solution is 60 ~ 120g / L East, 50 ~ 120g / including L of sulfuric acid, and the anionic additive is Cl, F, Br, I, PO to any one or more of 6 ₄ ~ 18ppm ( (More preferably, from 0.5 to 3.4 ppm) by adding at least one of gelatin, collagen, and PEG (polyethylene glycol) Total Organic Carbon) concentration should be adjusted to 3 ~ 18ppm. Also, an electrolytic copper foil is manufactured under such electrolytic conditions that the current density is in the range of 50 ASD to 80 ASD and the electrolytic solution temperature is in the range of 40 to 60 占 폚 under the composition of the electrolytic solution and the additive composition, thereby producing an untreated electrolytic copper foil corresponding to the embodiment.

On the other hand, in order to produce an untreated electrolytic copper foil according to the comparative example, a method different from the manufacturing method of the above-described embodiment is applied. Specifically, copper sulfate (60 to 120 g / L copper, 50 To 120 g / L of sulfuric acid), the copper foil is electrodeposited in the manner as shown in [Table 1] below to prepare an untreated electrolytic copper foil according to the comparative example.

The compositions and electrolysis conditions of the electrolytic solution and additive for pretreating the electrolytic copper foil according to Examples and Comparative Examples are as follows.

Copper: 85 ~ 90g / L

Sulfuric acid: 75 to 90 g / L

Electrolyte temperature: 55 ° C

Current density: 70 ~ 80 ASD

Additive type: Cl, gelatin

Additive content: Refer to [Table 1]

Cu
[g / L] H2SO4
[g / L] gelatin
[ppm] Cl
[ppm] TOC
[ppm] Current density
[ ASD ] Solution temperature
[° C] Example  One 85 75 3.4 15.7 18 80 55 Example  2 87 90 0.5 7.3 4 75 55 Example  3 85 85 0.6 16.2 3 80 55 Example  4 86 77 3.2 7.7 18 75 55 Example  5 85 78 0.5 14.8 4 70 55 Example  6 89 83 3.1 7.9 17 70 55 Example  7 90 90 0.7 8.2 4 75 55 Comparative Example  One 88 87 3.3 18.3 19 70 55 Comparative Example  2 85 78 0.2 2.3 2 75 55 Comparative Example  3 85 76 5.8 15 32 80 55 Comparative Example  4 87 79 4.8 24.3 16 70 55

(Surface treatment An electric boat  Produce)

The untreated electrolytic copper foil of the above-described Examples and Comparative Examples is produced as a surface treatment electrolytic copper foil by passing through a surface treatment process through a surface treatment apparatus as shown in Fig.

In the surface treatment process, the surface of the untreated electrolytic copper foil (matte surface and shiny surface) is subjected to burning plating to form ultrafine copper particles and to prevent copper particles from falling off. So as to improve the mechanical and chemical bonding force of the electrolytic copper foil.

The surface treatment process is performed, for example, as shown in Table 2 below. However, the surface treatment process according to the present invention is not necessarily limited to this example. The surface treatment process according to the present invention is not necessarily limited to this example, and various harmonization treatments for forming fine copper nodules on the surface of the untreated electrolytic copper foil, It is needless to say that various known surface treatment processes may be adopted to improve the physical and / or chemical properties.

Surface treatment process
T1 process

electric current[ ASD ] 25 to 30 Temperature [° C] 20 ~ 30 Cu concentration  [g / L] 10-20 H ₂ SO ₄ Concentration [g / L] 80-120
T2 process

electric current[ ASD ] 5 to 15 Temperature [° C] 30 to 50 Cu concentration [g / L] 40 to 60 H ₂ SO ₄ Concentration [g / L] 80-120

T4 process

electric current[ ASD ] 1-5 Temperature [° C] 20 ~ 30 PH 10 to 11 Ni concentration [g / L] 1-2 Ni coating amount [ppm] 5 to 30

T5 process

electric current[ ASD ] 1-5 Temperature [° C] 20 ~ 30 PH 10 to 11 Zn concentration [g / L] 1-2 Amount of Zn coating [ppm] 5 to 30

T6 process

electric current[ ASD ] 1-5 Temperature [° C] 20 ~ 30 PH 10 to 11 Cr concentration [g / L] 1-2 Cr coating amount [ppm] 1-5 T7 process Silane coupling agent [g / L] 0.1 to 5 Drying process Temperature: 130 ~ 250 ℃, Time: 2 ~ 6 seconds

In the T1 step of Table 2, a current is applied at 25 to 30 ASD in an electrolytic solution having a Cu concentration of 10 to 20 g / L, a H ₂ SO ₄ concentration of 80 to 120 g / L and a temperature of 20 to 30 ° C in a burning plating bath, To form micro fine copper particles on the surface of the substrate. At this time, the sealing process for capturing the ultrafine copper particles is a T2 process. In the T2 process, an electrolytic solution having a Cu concentration of 40 to 60 g / L, a H ₂ SO ₄ concentration of 80 to 120 g / The current is applied at 5 to 15 ASD. The T4 to T6 process is a process which improves the physical properties such as chemical resistance / acid resistance / oxidation resistance of the copper foil surface by treating the surface with an inorganic substance such as Ni, Zn, Cr and the like.

The T7 process is a process for improving the chemical bonding force of an electrolytic copper foil by a silane coupling agent treatment. As the preferable silane coupling agent, ethoxy or methoxy silane of a quaternary amino type is suitable, and it is suitable to form a film having a thickness of 0.1 to 5 g / L and a thickness of 0.1 to 10 ppm. After the treatment with the silane coupling agent, the drying process is performed at 130 to 250 ° C for 2 to 6 seconds to obtain a sample of the surface treated electrolytic copper foil according to the examples and the comparative examples.

Physical properties such as unit weight, tensile strength and flexural resistance were measured for the untreated electrolytic copper foil samples prepared in Examples and Comparative Examples prepared in the lumbering process in Table 1, The peel strength and the dielectric constant of the surface treated electrolytic copper foil samples of the examples and comparative examples were measured and are shown in [Table 3] and [Table 4].

Performance evaluation of electrolytic copper foil

1) Measurement of Flexibility

Flexural resistance was measured according to JIS-P8115.

2) Peel strength measurement

A polyimide film was attached to the mat surface side of the surface treated electrolytic copper foil samples of Examples and Comparative Examples and then the peel strength was measured. The peel strength was measured in accordance with JIS C6471 in a 180 degree direction.

3) Measurement of dielectric constant

The dielectric constant was measured according to IPC-TM-650. That is, a micro transmission line as shown in FIG. 7 is formed to check a signal transmission state. Calculate the amount of loss that would be lost when injecting a constant frequency of Ref vs. microstrip line. The lower the dielectric constant, the better the signal is transmitted without loss of transmission. The dielectric constant of the surface treated electrolytic copper foil is preferably 4% or less, and if it exceeds 4%, it may cause problems in use.

Unit weight
[g / ㎡] The tensile strength
[ kgf / Mm &lt; 2 & Number of Flexibilities
[Number of MITs] Example  One 94 33 731 Example  2 96 33 721 Example  3 94 38 772 Example  4 93 39 731 Example  5 94 37 773 Example  6 94 34 691 Example  7 95 35 688 Comparative Example  One 93 40 798 Comparative Example  2 94 44 846 Comparative Example  3 96 26 583 Comparative Example  4 95 24 612

<Comparison of physical properties of untreated electrolytic copper foil>

Referring to Table 3, the untreated electrolytic copper foils of Examples 1 to 7 should have an electrolytic copper foil for a printed wiring board such as a unit weight, a tensile strength (30 kgf / mm 2 or more) and a bending resistance (MIT frequency: 680 times or more) Whereas the untreated electrolytic copper foils of Comparative Examples 3 and 4 had a tensile strength of less than 30 kgf / mm 2, and the number of MITs exhibiting flexural resistance was 650 or less, which was significantly lower than that of Examples have.

a
[Mu m] b
[Mu m] Y
[a / b] Unit weight
[g / ㎡] Rz
[Mu m] Peel strength
[ Kgf / mm] permittivity
[%] Example  One 7.8 11.3 0.69 104 4.6 1.38 3.80 Example  2 6.3 12.7 0.50 105 4.4 1.29 3.61 Example  3 4.5 13.5 0.33 104 3.3 1.21 3.52 Example  4 4.3 10.4 0.41 107 3.1 1.01 3.60 Example  5 2.1 13.8 0.15 108 2.8 1.09 3.08 Example  6 6.4 11.5 0.56 106 4.1 1.32 3.67 Example  7 5.5 12.9 0.43 107 3.0 1.06 3.63 Comparative Example  One 1.9 14 0.14 108 2.5 0.77 2.87 Comparative Example  2 1.3 10.3 0.13 105 2.2 0.72 2.56 Comparative Example  3 10.6 7.7 1.38 108 8.2 1.57 4.3 Comparative Example  4 10.3 9.0 1.14 108 7.5 1.75 4.15

<Comparison of physical and electrical characteristics of surface treated electrolytic copper foil>

b: the thickness of the base material 22; Y (a / b): thickness ratio of protrusions; Rz: average surface roughness of the mat surface 10 points of the surface treatment electrolytic copper foil)

The surface treated electrolytic copper foil of each of Examples 1 to 7 has a thickness a of 2 to 8 탆 (more preferably, 2.1 to 7.8 탆) of the surface protruding portion 23, (More preferably, 10.4 to 13.8 占 퐉), and the thickness ratio (Y = a / b) of the projection portions has a numerical value range of 0.15 or more and 0.69 or less. As a result, the surface treated electrolytic copper foils of Examples 1 to 7 exhibit relatively low surface roughness Rz of 1.8 to 4.6 탆, excellent peel strength (1.0 Kgf / mm or more) and dielectric constant (4% or less).

On the other hand, the surface treated electrolytic copper foils of Comparative Example 1 and Comparative Example 2 exhibited significantly lowered peel strength of 1.00 Kgf / mm or less because the projection thickness ratio (Y = a / b) was less than 0.15. In the surface treated electrolytic copper foil of Comparative Example 3 and Comparative Example 4, the dielectric constant is 4% or more because the protrusion thickness ratio (Y = a / b) exceeds 0.69, and the signal transmission loss increases.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not to be limited to the details thereof and that various changes and modifications will be apparent to those skilled in the art. And various modifications and variations are possible within the scope of the appended claims.

21: surface treatment electrolytic copper foil
22: substrate
23:
24: surface projection layer
25: Surface treatment layer

Claims (14)

As a surface treated electrolytic copper foil produced by the lapping and surface treatment processes,
Wherein the surface-treated electrolytic copper foil comprises a base material and a surface projection part formed on one surface of the base material,
Wherein a ratio (Y = a / b) of a protrusion portion (Y = a / b) indicating a relative ratio of the thickness (b) of the substrate to the thickness (a) of the surface projection portion is 0.15 or more and 0.69 or less. The method according to claim 1,
Wherein the surface projection portion comprises a surface projection layer formed on one surface of the substrate by a lapping process and a surface treatment layer formed on the surface projection layer by a surface treatment process. 3. The method of claim 2,
Wherein the surface projection portion has a thickness (a) of 2 to 8 占 퐉. The method of claim 3,
Wherein the surface projection portion has a thickness (a) of 2.1 to 7.8 占 퐉. 3. The method of claim 2,
And the thickness (b) of the substrate is 10 to 14 占 퐉. 6. The method of claim 5,
Characterized in that the thickness (b) of the substrate is 10.4 to 13.8 占 퐉. 3. The method of claim 2,
Wherein one surface of the base material is a matte surface. 8. The method of claim 7,
Wherein the surface roughness of the mat surface is 1.8 to 4.6 占 퐉 in terms of 10-point average surface roughness Rz. A copper clad laminate characterized by having a polyimide resin adhered to a surface treatment layer of a surface treated electrolytic copper foil according to any one of claims 1 to 8. The printed wiring board according to claim 9, wherein a circuit pattern is formed on the copper-clad laminate. (a) adding 6 to 18 ppm of an anionic additive and 0.1 to 4.5 ppm of a leveler as an additive to an aqueous solution of copper sulfate having a copper concentration of 60 g / L to 120 g / L and a sulfuric acid concentration of 50 g / L to 120 g / (Cu) is electrodeposited on the surface of the drum of the pre-charging step at an electrolytic temperature of 40 to 60 DEG C and a current density of 50 ASD to 80 ASD to form an untreated Producing a copper foil; And
(b) forming a surface treatment layer on the surface projection layer of the untreated copper foil by a roughening treatment step to produce a surface treatment electrolytic copper foil;
(Y = a / b), which represents the relative ratio of the thickness (b) of the substrate to the thickness (a) of the surface projection part made of the surface projection layer and the surface treatment layer, is 0.15 or more and 0.69 or less Wherein the surface treated electrolytic copper foil is produced by the method. 12. The method of claim 11,
Wherein the anionic additive comprises at least one of Cl, F, Br, I, and PO4. 12. The method of claim 11,
Wherein the leveler comprises at least one of gelatin, collagen, and polyethylene glycol (PEG). An electrolyte solution having a TOC concentration of 3 to 18 ppm by adding an anionic additive of 6 to 18 ppm and a leveler of 0.1 to 4.5 ppm as an additive to an aqueous solution of copper sulfate having a copper concentration of 60 g / L to 120 g / L and a sulfuric acid concentration of 50 g / L to 120 g / , Copper (Cu) is electrodeposited on the surface of the drum of the former stage with the electrolytic solution having an electrolytic temperature of 40 to 60 캜 and a current density of 50 ASD to 80 ASD to produce an untreated copper foil comprising a substrate and a surface projection layer In the surface treated electrolytic copper foil on which the surface treatment layer is formed by the roughening treatment step on the surface projection layer of the untreated copper foil,
(Y = a / b), which represents the relative ratio of the thickness (b) of the substrate to the thickness (a) of the surface projection part made of the surface projection layer and the surface treatment layer, is 0.15 or more and 0.69 or less Surface treatment of electrolytic copper foil.

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