WO2014061983A9

WO2014061983A9 - Electrolytic copper foil, electric part and battery including same, and method for manufacturing same

Info

Publication number: WO2014061983A9
Application number: PCT/KR2013/009231
Authority: WO
Inventors: 이선형; 조태진; 박슬기; 송기덕
Original assignee: 일진머티리얼즈 주식회사
Priority date: 2012-10-18
Filing date: 2013-10-16
Publication date: 2015-02-05
Also published as: WO2014061983A1

Abstract

An electrolytic copper foil of which the surface roughness of a precipitation surface, Rz, is less than 1.4 μm, the tensile strength after heat treatment is at least 40 kgf/mm², and the elongation percentage is at least 4% is suggested. The electrolytic copper foil maintains low roughness and high strength while having a high elongation percentage, and may be used in a current collector of a lithium ion secondary battery having a medium to large size, and in a packing for tape automated bonding (TAB) used in a tape carrier package (TCP).

Description

【Specification】

[Name of invention]

Electrolytic copper foil, electric parts and battery including the same, and electrolytic copper foil manufacturing method

The present invention relates to an electrolytic copper foil, an electric component and a battery including an electrolytic copper foil, and a method for manufacturing an electrolytic copper foil, and more particularly, to a low roughness, high strength and high elongated electrolytic copper foil having high tensile strength and elongation even after high temperature heat treatment.

Background Art

Copper foil is generally used as an electrical power collector of a secondary battery. The copper foil is mainly used as a rolled copper foil rolled, but the manufacturing cost is expensive and it is difficult to manufacture a wide copper foil. In addition, since the rolled copper foil must use lubricating oil during rolling, adhesion to the active material may be degraded by contamination of the lubricating oil, and thus, the layer discharge cycle characteristics of the battery may be reduced.

Lithium batteries are accompanied by volume change during layer discharge and exothermic phenomenon due to overcharge. In addition, the copper foil is effective to improve adhesion to the electrode active material and to prevent the occurrence of wrinkles, breaks, etc. in the copper foil as a current collector by being less affected by the copper base material in relation to the expansion and contraction of the active material layer according to the layer discharge cycle. Should have a low surface roughness. Therefore, high-strength, high-strength and low-light copper foils capable of withstanding volumetric changes and exothermic phenomena of lithium batteries and excellent adhesion to active materials are required.

In addition, due to the demand for thin and small electronic devices, In smaller areas: In order to increase the degree of integration of circuits, there is an increasing demand for fine wiring of a semiconductor mounting board or a main board. When a thick copper foil is used for the production of a printed wiring board having such a fine pattern, the etching time for forming the wiring circuit becomes long and the sidewall verticality of the wiring pattern is lowered. In particular, when the wiring line width of the wiring pattern formed by etching is narrow, the wiring may be disconnected. Therefore, in order to obtain fine pitch white, a thinner copper foil is required. However, the thin copper foil is limited in the thickness of the copper foil, so the mechanical strength is weak, the occurrence frequency of defects such as wrinkles and bending during the manufacture of the printed wiring board.

And in semiconductor packing substrates for tape automated bonding (TAB) used in TCP Tape Carrier Package (TAB): ICs for inner leads disposed in device halls located in the center of the product A plurality of terminals of the chip are directly bonded, and at this time, a current is instantaneously heated by using a bonding device and a constant pressure is applied. Therefore, the inner lead formed by the etching of the electrolytic copper foil is pulled out by the bonding pressure and stretched. ―

Therefore, the low roughness copper foil which is thin, high mechanical strength, and high drawability is calculated | required.

[Detailed Description of the Invention]

[Technical problem]

One aspect of the present invention is to provide a new electrolytic copper foil.

Another aspect of the invention provides an electrical component comprising the electrolytic copper foil. Will be.

Another aspect of the invention is to provide a battery comprising the electrolytic copper foil.

Another aspect of the present invention is to provide a method for producing the electrolytic copper foil.

Technical Solution

According to one aspect of the present invention, the surface roughness Rz of the precipitated surface is less than lA, and after heat treatment, an electrolytic copper foil having a tensile strength of 40 kgf / rmn 2 or more and an elongation of 4% or more is presented.

According to another aspect of the invention, an insulating substrate; And the electrolytic copper foil attached to one surface of the insulating substrate, and an electric component including a circuit formed by etching the electrolytic copper foil is provided.

According to another aspect of the present invention, a battery including the electrolytic copper foil is provided. According to another aspect of the invention, additive A; Additive B; Electrolyzing a copper electrolyte comprising the additive C and the additive D; wherein the additive A is at least one selected from the group consisting of thiourea-based compound and a compound in which a thiol group is connected to a heterocyclic ring containing nitrogen, Additive B is a sulfonic acid or metal salt thereof of a compound containing a sulfur atom, and additive C is a nonionic water soluble polymer; The method for producing an electrolytic copper foil, wherein the additive D is a phenazinium compound. Advantageous Effects

According to an aspect of the present invention, by using a copper electrolyte solution containing an additive of a new composition, an electrolytic copper foil having low surface roughness and high strength and having high stretch can be obtained.

[Brief Description of Drawings]

1 is an X-ray diffraction (XRD) spectrum of the precipitated surface of the electrolytic copper foil prepared in Example 1. FIG.

2 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 1;

3 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 2. FIG.

4 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 3. FIG.

5 is a scanning micrograph photograph of the surface of the electrolytic copper foil prepared in Example 4.

6 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Comparative Example 1.

7 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Comparative Example 2.

8 is a scanning electron microscope of the surface of the electrolytic copper foil prepared in Comparative Example 3 Jin.

9 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Comparative Example 4.

[Form for implementation of invention]

Hereinafter, the electrolytic copper foil according to the preferred embodiments, an electric component and a battery including the electrolytic copper foil, and an electrolytic copper foil manufacturing method will be described in more detail. Electrolytic copper foil according to an exemplary embodiment of the present invention has a surface roughness Rz of the precipitated surface is Ι ΛίΜ or less, the tensile strength after heat treatment is more than 40 kgf / mm2, the elongation is more than 4%. The electrolytic copper foil has a high roughness of 40 kgi / mm 2 and a high roughness of 40 kgi / mm 2 even though the surface roughness of the low roughness Rz is less than or equal to Λμαι. At the same time, the electrolytic copper foil has a high elongation of 4% or more even after high temperature.

Therefore, the electrolytic copper foil may be used simultaneously for a printed circuit board (PCB) / FPC (flexible PCB) and a current collector for a battery.

If the surface roughness Rz of the precipitated surface of the electrolytic copper foil is greater than 1.4, the contact surface of the surface of the electrodeposited copper foil for the negative electrode current collector and the active material may be reduced, so that the lifespan of the layer discharge cycle and the initial capacity of the charge may be lowered. In addition, when the surface roughness Rz of the precipitation surface exceeds 1.4, it is not easy to form a high density circuit having a fine pitch in the printed wiring board.

The electrolytic copper foil has a high strength characteristics of 40kgf / mm 2 to 70kgf / mm 2 tensile strength. In addition, the electrolytic copper foil has a tensile strength of 40kgf / mm2 to even after heat treatment 70kgf / mm2. The heat treatment may be carried out at 15 CTC to 22 CTC, for example, and may be performed at 18 CTC in detail. The heat treatment may be carried out over 30 minutes, 1 hour, 2 hours and several hours, but may be carried out for at least 1 hour to maintain a constant tensile strength. The heat treatment is to measure the tensile strength of the electrolytic copper foil, and is a treatment to obtain a tensile strength or elongation maintained at a value which does not change to a certain level when the electrolytic copper foil is stored or put into a subsequent process.

If the electrolytic copper foil has a tensile strength of less than 40kgf / mm 2 after heat treatment, it may be difficult to handle because the mechanical strength is weak.

Preferably, the electrolytic copper foil has a tensile strength after heat treatment similar to the tensile strength before heat treatment. The tensile strength after the heat treatment of the electrolytic copper foil is preferably 85% to 99% of the anneal strength before the heat treatment. It is easy to handle in the process and the yield is high.

The electrolytic copper foil may have an elongation of 2% to 15% before heat treatment. In addition, the electrolytic copper foil may have an elongation of 4% to 15% after heat treatment, and the heat treatment may be performed at 18 CTC for 1 hour. Alternatively, the elongation after heat treatment may be 1 to 4.5 times the elongation before heat treatment.

If the elongation after heat treatment in the electrolytic copper foil is less than 4%, cracks may occur when the subsequent process is a high temperature process. For example, when the electrolytic copper foil is used as a negative electrode current collector of a secondary battery, the process of manufacturing the negative electrode current collector is a high temperature process, and cracks may occur due to a volume change of the active material layer during layer discharge. So After elongation, the specified elongation must be maintained.

The electrolytic copper foil has a ratio of the intensity of the diffraction peak (1 (200)) to the (200) crystal plane (1 (200)) and the intensity of the diffraction peak (1 (111)) to the (111) crystal plane in the XRD spectrum of the precipitation surface. / 1 (111) may be 0.5 to 1.0.

For example, as shown in FIG. 1, the diffraction angle for the (111) crystal plane is shown at the diffraction angle (2Θ) 43.0 ° 士 1.0 ° in the XRD spectrum for the precipitation surface, and the diffraction angle (2Θ) 50.5 ° 士 1.0 It shows a diffraction peak with respect to the (200) crystal plane at °, the intensity ratio 1 (200) / 1 (111) may be 0.5 to 1.0 or more.

For example, 1 (200) / 1 (111) may be 0.5 to 0.8 in the electrolytic copper foil. Orientation index with respect to (200) crystal plane in the XRD spectrum with respect to the precipitation surface in the electrolytic copper foil (M (2Q0)). And the Bb M (200) / M (lll) of the orientation index obtained from the orientation index (M (ηυ)) with respect to the (111) crystal plane may be 1.1 to 1.5. Is the value obtained by dividing the relative peak intensity of a specific crystal plane by the relative peak intensity of a characteristic crystal plane obtained from a standard sample that is not oriented with respect to all crystal planes, for example, M (200) / M (lll) in the electrolytic copper foil is 1.2 to May be 1.4.

The electrolytic copper foil may have an elongation of 10% or more after heat treatment at 180 ^° C. for 1 hour. That is, the electrolytic copper foil may have a high elongation of 10% or more after high temperature heat treatment. For example, the electrolytic copper foil may have an elongation of 10% to 20% after high temperature heat treatment. For example, the electrolytic copper foil has an elongation of 10% to 15% after high temperature heat treatment. Can be. For example, the electrolytic copper foil may have an elongation of 10% to 13% after high temperature heat treatment. The electrolytic copper foil may have an elongation of 1% or more before heat treatment. For example, the electrolytic copper foil may have an elongation of 2% to 20% before heat treatment. For example, the electrolytic copper foil may have an elongation of 5% to 20% before heat treatment. For example, the electrolytic copper foil has an elongation of 5% to before heat treatment. May be 15%. For example, the electrolytic copper foil may have an elongation of 5% to 10% before heat treatment. The term “before heat treatment” refers to a temperature of 25 ^° C. to 130 ^° C. before annealing at a high temperature.The elongation is a value obtained by dividing the stretched distance by the initial length of the electrolytic copper foil immediately before the electrolytic copper foil is broken. to be.

The surface roughness Rz of the electrodeposited copper foil may be less than or equal to .Tim. The total thawing foil may be used as both a copper foil for PCB / FPC and a copper foil for negative electrode current collector for secondary batteries by having a low roughness of Rz of 0.7 or less. For example, the electrolytic copper foil may have a precipitation surface and a surface roughness Rz of 0.5 or less. For example, the surface roughness Rz of the precipitation surface of the electrolytic copper foil may be 0.45 / ΛΙΙ or less.

The surface roughness Ra of the electrodeposited copper foil may be 0.15 im or less. The electrolytic copper foil may be used as both a copper foil for PCB / FPC and a copper foil for negative electrode current collector for secondary batteries by having a low roughness Ra of 0.15 zm or less. For example, the surface roughness Ra of the precipitation surface of the electrolytic copper foil may be less than or equal to O. Uim. For example, the surface roughness Ra of the deposition surface of the electrolytic copper foil may be less than or equal to O. ll im. * 33: The tensile strength of the electrolytic copper foil may be 85% or more of the tensile strength before the heat treatment. For example, the tensile strength after heat treatment for 1 hour at 18CTC of the electrolytic copper foil may be 90% or more of the tensile strength before heat treatment. The tensile strength before heat treatment is the tensile strength of the copper foil obtained without high temperature thermal treatment. Tensile strength before heat treatment of the electrolytic copper foil may be 40kgf / mm2 to 70kgf / mm2.

Glossiness (Gs (60 °)) in the width direction of the precipitation surface in the electrolytic copper foil may be 500 or more. For example, the glossiness (Gs (60 ⁰ )) of the width direction of the precipitation surface in the electrolytic copper foil may be 500 to 1000. The glossiness is a value measured according to JIS Z 871-1997.

The thickness of the electrolytic copper foil may be 35 or less. For example, the thickness of the electrolytic copper foil may be 6 to 35 m. For example, the thickness of the electrolytic copper foil may be 6 to 18 pm. In addition, for example, the thickness of the electrolytic copper foil may be 2 to 10.

When the electrolytic copper foil needs to be bonded to an insulating resin or the like, surface treatment may be additionally performed to make the adhesiveness practical or higher. Examples of the surface treatment on the copper foil include any one or a combination of heat and chemical resistance treatment, chromate treatment, silane coupling treatment, and the like. Depending on the process conditions it is carried out by a person of ordinary skill in the art selected. An electrical component according to an exemplary embodiment includes an insulating substrate; And the insulating base It includes; the above-mentioned electrolytic copper foil attached to one surface of, and includes a circuit formed by etching the electrolytic copper foil.

The electrical component is, for example, a TAB tape, a printed wiring board (PCB), a flexible printed wiring board (FPC, Flexible PCB), and the like, but not necessarily limited thereto. Anything that can be used in the field is possible.

A battery according to an exemplary embodiment includes the electrolytic copper foil. The electrolytic copper foil may be used as a negative electrode straw whole of the battery, but is not necessarily limited thereto and may be used as other components used in the battery. The battery is not particularly limited and includes a primary battery and a secondary battery, and a battery using an electrolytic copper foil as a current collector such as a lithium ion battery, a lithium polymer battery, a lithium air battery, and the like can be used in the art. All is possible.

Electrolytic copper foil manufacturing method according to an exemplary embodiment is an additive A; Additive B; Electrolyzing a copper electrolyte solution comprising the additive C and an additive D; wherein the additive A is at least one selected from the group consisting of a thiourea-based compound and a compound in which a thiol group is connected to a heterocyclic ring containing nitrogen, The additive B is a sulfonic acid or a metal salt thereof of a compound containing a sulfur atom, and the additive C is a nonionic water-soluble polymer; The additive D is a phenazinium compound. The electrolytic copper foil manufacturing method may include a low thickness copper foil having a thin thickness, high mechanical strength and high stretching by including additives of a new composition. have. The copper electrolyte may include chlorine (chlorine ion) having a concentration of 1 to 40 ppm. The presence of a small amount of chlorine ions in the copper electrolyte increases the initial nucleation site during electroplating, resulting in fine grains and the precipitation of CuC12 formed at the grain boundary interface, which inhibits crystal growth when heated to high temperatures, thereby providing thermal stability at high temperatures. Can improve. When the concentration of the chlorine ion is less than 1 ppm, the concentration of chlorine ions required in the sulfuric acid-copper sulfate electrolyte may be insufficient, so that the tensile strength before heat treatment may be lowered and thermal stability at high temperature may be lowered. If the concentration of chlorine ion is more than 40 ppm, the surface roughness of the precipitated surface is increased, making it difficult to manufacture low roughness electrolytic copper foil, low tensile strength before heat treatment, and low thermal stability at high temperature.

In the copper electrolyte, the content of the additive: A is 1 to lOppm, the content of the additive B is 10 to 200ppm, the content of the additive C is 5 to 40ppm, and the content of the additive D may be 1 to 100ppm. .

In the copper electrolyte solution, the additive A may improve the production stability of the electrolytic copper foil and improve the strength of the electrolytic copper foil. If the content of the additive A is less than lppm, the tensile strength of the electrolytic copper foil may be lowered. If the content of the additive A is more than lOppm, the surface roughness of the precipitated surface may increase, making it difficult to manufacture the electrolytic copper foil of low roughness, and the tensile strength may be reduced.

Additive B in the copper electrolyte may improve the surface gloss of the electrolytic copper foil. When the content of the additive B is less than lOppm, the gloss of the electrolytic copper foil may be lowered. When the content of the additive B is more than 200 ppm, the surface roughness of the precipitated surface is increased. It is difficult to manufacture low roughness electrolytic copper foil and the tensile strength of the electrolytic copper foil may be reduced.

In the copper electrolyte, the additive C may lower the surface roughness of the electrolytic copper foil and improve surface glossiness. If the content of the additive C is less than 5ppm, the surface roughness of the precipitated surface is increased, making it difficult to manufacture low-temperature electrolytic copper foil, and the gloss of the electrolytic copper foil may be lowered. It may not be economical.

The additive D in the copper electrolyte may serve to improve the flatness of the surface of the electrolytic copper foil. If the content of the additive D is less than lppm, the surface roughness of the precipitated surface is increased, making it difficult to manufacture ¾ thawed foil of low degree, and the gloss of the electrolytic copper foil may be lowered. It may become unstable and the tensile strength of the electrolytic copper foil may be impaired.

The thiourea compound may be a compound represented by Formula 1:

In the above formula, R1, R2, R3 and R4 are independently an alkyl group having 1 to 10 carbon atoms, and R2 and R4 may be connected to each other to form a ring.

For example, the thiourea-based compound is diethylthiourea, ethylenethiourea, acetylenethiourea, dipropylthiourea, dibutylthiourea, N-trifluoro N-trifluoroacetylthiourea N-ethylthiourea, N-cyanoacetylthiourea, N-allylthiotirea, o_lrylthio Urea (o-tolylthiourea), Ν, Ν'-butylene thiourea (Ν, Ν'-butylene thiourea), thiozolidinethiol, 4-thiazolinethiol, 4-methyl-2-pyri It may be one or more selected from the group consisting of midithiol (4—methyl-2—pyrimidinethiol), 2-thiouracil, but is not necessarily limited to any of the thiourea compounds that can be used as an additive in the art. It is possible. To compound thiol group attached to the interrogating ring including the nitrogen, for example, to 2-mercapto-5-benzo imidazole sulfonic acid sodium salt ^{'(-2_mercapto} benzoimidazole-5 sulfonic acid sodium salt) represented by the general formula (II) Sodium 3- (5-mercapto-l-tetrazolyl) benzene sulfonate represented by Formula 3, Mercapto benzothiazole.

The sulfonic acid or metal salt thereof of the compound containing the sulfur atom is, for example, a bis- (3-sulfopropyl) -disulfide disodium salt (SPS) represented by the following Chemical Formula 5; 1-propanesulfonic acid (MPS), 3- (N, N-dimethylthiocarbamoyl) -thiopropanesulfonate sodium salt (DPS) represented by the following formula (7), 3- [(amino- Iminomethyl) thio] -1-propanesulfonate sodium salt (UPS), eethyldithiocarbonato-S- (3-sulfopropyl) -ester sodium salt represented by the following formula (9): (10) 3- (benzothiazolyl-2-hammercapto) -propyl-sulfonic acid sodium salt (ZPS), ethylenedithiodipropylsulfonic acid sodium salt, thioglycolic acid, thiophospho Lactic acid—o-ethyl-bis- (ω-sulfopropyl) ester disodium salt (Thiop consisting of hosphoric acid_0_ethy 卜 bis— (to ᅳ sulfopropyD'ester disodium salt), thiophosphoric acid-tris— (ω-sulfopropyl) ester trisodium salt It may be one or more selected from the group, but not necessarily limited to any sulfonic acid or metal salt thereof of a compound containing a sulfur atom that can be used as an additive in the art.

HS_CH ₂ -CH ₂ ᅳ CH ₂ -S0 ₃ —

<Formula 7> N— CSC H ₂ — CH ₂ -CH ₂ -S0 ₃ Na

The nonionic water-soluble polymer is polyethylene glycol, polyglycerol, hydroxyethyl cellulose, carboxymethyl cellulose (Carboxymethylcellulose), nonylpe Nonylphenol polyglycol ether, Octane diol-bis- (Polyalkylene glycol ether), Octane to polyalkylene glycol ether, Oleic acid poly Glycol ethers (eic acid polyglycol ether), polyethylene propylene glycol, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polyvinyl alcohol, β -Naph may be one or more selected from the group consisting of β-naphthol polyglycol ether, stearic acid polyglycol ether, stearyl alcohol polyglycol ether, but Water-soluble which can be used as a scavenger in the art without limitation Any polymer may be used, for example, the polyethylene glycol may have a molecular weight of 2000 to 20000.

The phenazinium compound may be a compound represented by Formula 11 below:

In the above formula,

R1, R2, R4, R5, R6, R7 ', R7 ", R8 and R9 are each independently hydrogen, carbon number An alkyl group of 1 to 10 or an aryl group of 6 to 20 carbon atoms, X is -N = N-C6H4-N (CH3) 2, hydrogen, an alkyl group of 1 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, and A is Halogen element. The phenazinium compound is not a polymer.

For example, the phenazinium compound may be at least one selected from the group consisting of safranin-O (Safaranine-O) represented by the following Equation 12, Janus Green BUanus Green B) represented by the following Formula 13, and the like. .

The temperature of the copper electrolyte used in the manufacturing method may be 30 to 6CTC, but is not necessarily limited to this range and may be appropriately adjusted within a range capable of achieving the object of the present invention. For example, the temperature of the copper electrolyte may be 40 to 50 ^° C. The current density used in the manufacturing method may be 20 to 500 A / dm 2, but is not necessarily limited to this range and may be appropriately adjusted within a range capable of achieving the object of the present invention. For example, the current density is 30 to 40

It may be A / dm2. The copper electrolyte may be sulfuric acid-copper sulfate copper electrolyte. The concentration of Cu 2+ ions in the sulfuric acid-copper sulfate copper electrolyte may be 60 g / L to 180 g / L, but is not necessarily limited to this range and may be appropriately adjusted within a range capable of achieving the object of the present invention. For example, the concentration of Cu 2+ may be 65 g / L to 175 g / L.

The copper electrolyte may be prepared by a known method. For example, the concentration of ᅳ Cu2 + ions can be obtained by controlling the iron content of copper ions or copper sulfate, and the concentration of S042 + ions can be obtained by adjusting the amount of sulfuric acid and copper sulfate added.

The concentration of the additives included in the copper electrolyte solution may be obtained from the amount and molecular weight of the additives added to the copper electrolyte solution, or may be obtained by analyzing the additives contained in the copper electrolyte solution by a known method such as column chromatography.

The electrolytic copper foil may be manufactured by a known method except for using the above-described copper electrolytic backing.

For example, the electrolytic copper foil may be prepared by supplying and electrolyzing the copper electrolyte between the curved negative electrode surface of the rotating titanium drum-shaped titanium and the positive electrode to precipitate the electrolytic copper foil on the negative electrode surface and winding it continuously to produce an electrolytic copper foil.

Hereinafter, the present invention will be described in more detail with reference to the following examples. It is not decided.

(Manufacture of Electrolytic Copper Foil)

Implementation ^ 1 1

In order to manufacture electrolytic copper foil, a 3L electrolytic cell system capable of circulating at 20 L / min was used and the silver conductivity of the copper electrolyte was kept constant at 45 ^° C. The anode was a 5mm thick, 10 x 10 cm2 Dimentionally Stable Electrode (DSE) plate, and the cathode was a titanium plate with the same size and thickness as the anode.

In order to facilitate the movement of the Cu 2+ ions, plating was performed at a current density of 35 A / dm 2: An electrolytic copper foil having a thickness of 18 ^ was prepared.

The basic composition of the copper electrolyte is as follows:

CuS04-5H20: 250-400 g / L

H2S04: 80 ~ 150g / L

Silver chlorine and additives are added to the additive copper electrolyte, and the composition of the added additives and chloride ions is shown in Table 1 below. In Table 1 below, ppm is the same concentration as mg / L.

The scanning electron micrograph of the prepared electrolytic copper foil precipitation surface (matte surface, M surface) is shown in FIG.

Examples 2-4 and Comparative Examples 1-4

Except for changing the composition of the copper electrolyte as shown in Table 1 below An electrolytic copper foil was manufactured in the same manner as in Example 1. Scanning electron micrographs of the surface of the precipitated surfaces of the electrolytic copper foils prepared in Examples 2 to 4 and Comparative Examples 1 to 4 are shown in FIGS. 3 to 9, respectively.

Table 1

Arguments i The abbreviations in Table 1 mean the following compounds.

DET: Diethyl Thiourea

SPS: Bis- (3-Sulfopropyl) -Dosulfide

MPS: 3-mercato-1-propanesulfonic acid

PEG: polyethylene glycol (canto chemical Cas No. 25322-68-3)

ZPS: 3- (benzothiazolyl— 2-mercato) -propyl-sulfonic acid antidotes

JGB: Janus Green B

2M-SS; 2—mercapto-5'benzoimidazole sulfonic acid

DDAC: diallyldi: methylammonium chloride

PGL: Polyglycerol (KCI, PGL 104KC) Evaluation example: 1: Scanning electron microscope experiment

In Examples 1 to 4 and Comparative Examples 1 to 4, scanning electron microscopes were measured on the surfaces of the precipitated surfaces of the obtained electrolytic copper foil, and the results are shown in FIGS. 2 to 9, respectively.

As shown in FIGS. 2 to 9, the electrolytic copper foils of Examples 1 to 4 had a flat surface and a low roughness compared to those of Comparative Copper Samples 1 to 4.

Evaluation Example 2 Glossiness Measurement

Glossiness was measured about the surface of the precipitation surface of the electrolytic copper foil obtained in Examples 1-4 and Comparative Examples 1-4. The glossiness side according to JIS Z 871-1997 It is a fixed value.

Glossiness was measured by irradiating measurement light on the surface of the copper foil along the flow direction (MD direction) of the electrolytic copper foil at an incident angle of 60 °, and measuring the intensity of light reflected at a reflection angle of 60 °. It measured based on 8741-1997.

The measurement results are shown in Table 2 below.

Table 2

As described in Table 2, the electrolytic copper foils of Examples 1 to 4 exhibited improved glossiness as compared to the electrolytic copper foils of Comparative Examples 1 to 4.

Evaluation Example 3: XRD Experiment

The X-ray diffraction (XRD) spectra of the precipitated surfaces of the electrolytic copper foils obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured. XRD for Example 1 The spectrum is shown in FIG.

As shown in FIG. 1, the peak intensity of the (111) crystal plane was the highest, followed by the (200) crystal plane.

K200) / I (i n), which is the ratio of the intensity (K20Q) of the diffraction peak with respect to the (200) crystal plane and the intensity (1 (111)) of the diffraction peak with respect to the (111) crystal plane, was 0.605.

In addition, the orientation index (M) of the (111), (200), (220), (311), and (222) crystal planes in the XRD spectrum of the precipitated surface was measured and the results are shown in Table 3 below. Indicated.

Orientation indexes are S. Yoshimura, S. Yoshihara, T. Shirakashi, E. Sato, Electrochim. Measurement was performed using the orientation index (M) proposed in Acta 39, 589 (1994).

For example, for a specimen having a (111) plane, the orientation index XM is calculated as follows.

IFR (111) = IF (111) / {IF (111) + IF (200) + IF (220) + IF (311)}

IR (111) = I (111) / {I (111) + 1 (200) + 1 (220) + 1 (311) 1

M (111) = IR (111) / IFR (111)

IF (lll) is the XRD intensity on JCPDS Cards and 1 (111) is the experimental value. If M (lll) is greater than 1, it has a preferred orientation parallel to the (111) plane, and if M is less than 1, it means that the preferred orientation is reduced. Table 3

Referring to Table 3, the orientation index obtained from the orientation index (M (200)) for the (200) crystal plane and the orientation index (M (lll)) for the (111) crystal plane in the XRD spectrum for the precipitation surface. The ratio M (200) / M (lll) was 1.31.

Evaluation Example 4 Surface Roughness (Rz) Measurement

Precipitation surface and gloss surface roughness Rz and Ra of the electrolytic copper foil obtained in Examples 1-4 and Comparative Examples 1-4 were measured according to JISB 0601- 1994 standard. Surface roughness Rz and Ra obtained by the measuring method are shown in Table 4 below. The lower the value, the lower the roughness.

Evaluation Example 5: Normal Tensile Strength, Normal Elongation, High Temperature Tensile Strength, and High Temperature Elongation

Tensile tests were performed on the electrolytic copper foils obtained in Examples 1 to 4 and Comparative Examples 1 to 4 with a width of 12.7 mm X gauge length of 50 mm, followed by a tensile test at a crosshead speed of 50.8 mm / min. IPC-TM—650 2.4.18B The maximum load of the tensile strength measured and carried out according to the method was called room temperature tensile strength, and the elongation at break was called room temperature elongation. Here the room temperature is 25 ^° C.

The same electrolytic copper foil used for the measurement of tensile strength and elongation at room temperature was taken out after heat treatment at 180 ^° C for 1 hour, and the tensile strength and Elongation was measured and referred to as high temperature tensile strength and high temperature elongation.

Room temperature tensile strength, room temperature elongation, high temperature tensile strength, and high temperature elongation obtained by the measuring method are shown in Table 4 below.

Table 4

As shown in Table 4, the electrolytic copper foils of Examples 1 to 4 have a low surface roughness Rz of less than 0.5 / im, a tensile strength of 40 kgf / mm 2 or more after high temperature heat treatment, and an elongation of 10% or more after high temperature heat treatment. High. On the other hand, the electrolytic copper foils of Comparative Examples 1 to 4 have higher surface roughness and lower elongation after high temperature heat treatment than i electrolytic copper foils of Examples 1 to 4, so that they can be used as negative current collectors for secondary batteries and / or low-low copper foils for PDB / FPC. Not suitable for. The invention is not to be limited by the foregoing embodiments and the accompanying drawings, which are to be interpreted by the appended claims. In addition, it will be apparent to those skilled in the art that various forms of substitution, modification, and alteration are possible without departing from the technical spirit of the present invention described in the claims with respect to the present invention.

Claims

[Range of request]

[Claim 11

The surface roughness Rz of the precipitated surface is 1.4;

Electrolytic copper foil with tensile strength over 40kgf / mm2 and elongation over 4% after heat treatment.

[Claim 2]

The method according to claim 1,

Electrolytic copper foil, characterized in that the tensile strength before heat treatment is 40kgf / mm2 to 70kgf / mm2.

[Claim 3]

The method according to claim 1,

The tensile strength after heat treatment is 40kgf / mm2 to 70kgf / mm2 electrolytic copper foil, characterized in that.

[Claim 4]

The method according to claim 3,

Electrolytic copper foil, characterized in that the tensile strength after heat treatment at 18CTC for 1 hour 40kgf / mm2 to 70kgf / mm2.

[Claim 5]

The method according to claim 1,

The tensile strength after heat treatment is an electrolytic copper foil, characterized in that 85% to 99% of the tensile strength before heat treatment.

[Claim 6]

The method according to claim 1,

Electrolytic copper foil characterized by an elongation of 2% to 15% before heat treatment.

[Claim 7]

The method according to claim 1,

An electrolytic copper foil characterized by an elongation of 4% to 15% after heat treatment.

[Claim 8]

The method according to claim 7,

Electrolytic copper foil characterized by elongation of 4% to 15% after heat treatment at 180 ^° C for 1 hour.

[Claim 9]

The method according to claim 1,

Elongation after heat treatment is an electrolytic copper foil, characterized in that 1 to 4.5 times the elongation before heat treatment.

[Claim 10]

The method according to claim 1,

In the XRD spectrum for the precipitation surface, 1 (200) / 1 111) electrolytic copper foil with 0.5 to 1.0.

[Claim 111] The method according to claim 1 ^; ，

In the XRD spectrum of the precipitation surface, M (200) / M ( lll) electrolytic copper foil with 1.1 to 1.5.

[Claim 12]

The method according to claim 1,

Electrolytic copper foil whose surface roughness Rz of the said precipitation surface is O.lim or less.

[Claim 13]

In claim

Electrolytic copper foil whose surface roughness Ra of the said precipitation surface is 0.15;

[Claim 14]

The method according to claim 1,

Gloss to the width direction of the deposition surface (Gs (60 ⁰⁾⁾ is 500 or more electrolytic copper foil.

[Claim 15]

The method according to claim 1,

An electrolytic copper foil having a thickness of 2 zm or more.

[Claim 16]

Insulating substrates; And

Includes; the electrolytic copper foil according to any one of claims 1 to 15 attached to one surface of the insulating substrate, An electric component comprising a circuit formed by etching said ¹ electrolytic copper foil.

[Claim 17]

Claim 1 The ^guidelines for naeja of claim 15 including the electrolytic copper foil according to any of the preceding.

[Claim 18]

Additive A; Additive B; Electrolyzing a copper electrolyte comprising the additive C and the additive D;

The additive A is at least one selected from the group consisting of a thiol group compound and a compound in which a thiol group is connected to a heterocycle including nitrogen.

The additive B is a sulfonic acid or metal salt thereof of a compound containing a sulfur atom :，

The additive C is a nonionic water soluble polymer;

Electrolytic copper foil manufacturing method wherein the additive D is a phenazinium compound.

[Claim 19]

The method according to claim 18,

The copper electrolyte solution manufacturing method of the electrolytic copper foil containing chlorine of 1-40 ppm concentration.

[Claim 20]

The method according to claim 18,

The content of the additive A is 1 to lOppm, The content of the additive B is 10 to 200ppm,

The content of the fertilizer C is 5 to 40 ppm,

Electrolytic copper foil manufacturing method of the content of the additive D is 1 to lOppm.

[Claim 21]

The method of claim 18, wherein the thiourea-based compound is diethylthiourea, ethylenethiourea, acetylenethiourea, dipropylthiourea, dibutylthiourea, N-trifluoroacetylthiourea (N-trifluoroacetylthiourea), N-ethylthiourea, N-cyanoacetylthiourea, N-allylthiourea, o-tolylthiourea, Ν, Ν'- Butylene Thiourea (N, N "-butylene thiourea), Thiozolidinethiol, 4-thiazolinethiol, 4-Methyl-2-pyrimidinethiol (4—methyl-2-pyrimidinethiol And at least one selected from the group consisting of 2-thiouracil.

[Claim 22]

19. The method of claim 18, wherein the compound having a thi group connected to the heterocycle including nitrogen is 2-mercapto-5-benzoimidazole sulfonic acid sodium salt, sodium 3 one ( 5 one mercapto— 1—tetrazolyl) benzen sulfonate (Sodium 3— (5— mercapto— 1— tetrazolyl) benzene sulfonate), and 2— mermerto benzothiazole. One or more electrolytic copper foil manufacturing method.

[Claim 23]

The sulfonic acid of the compound comprising a sulfur atom or a metal salt thereof is bis- (3-sulfopropyl) -disulfide polyanhydride, 3-mercapto-l-propanesulfonic acid, 3— (Ν, Ν-dimethylthiocarba) Moyl) -thiopropanesulfonate sodium salt, 3- [(amino-imino methyl) thio] — 1-propanesulfonate sodium salt, 0-ethyldathiocarbonato-S— (3-sulfopropyl)- Ester sodium salt, 3- (benzothiazolyl-2-mercapto) -propyl-sulfonic acid sodium salt, ethylene dithiodipropylsulfonic acid sodium salt, thioglycolic acid, thioglycolic acid- o-Ethyl-bis- (ω-sulfopropyl) ester ^{ᅵ leodisodium} salt ^' (Thiophosphoric acid_o-ethyl— bis 一 (ω— sulfopropyDester disodium salt) and thiophosphoric acid-tris- (ω-sulfopropyl) ester tri Sodium salt (Thiophosphoric acid-tris- (o) -sulfopropyl) ester trisodium salt) The method is at least one selected from the group consisting of electrolytic copper foil.

[Claim 24]

The method according to claim 18, wherein the nonionic water-soluble polymer is polyethylene glycol, polyglycerol, hydroxyethyl salose, carboxymethyl salose

(Carboxymethylcellulose), Nonylphenol polyglycolether, Octane diol-bis- (polyalkylene glycol ether), Octane to polyalkylene glycol ether (Ocatanol polyalkylene glycol ether) , Oleic acid polyglycol ether, polyethylene propylene glycol, polyethylenyl Alkylene glycol ether ¹ (Polyethylene glycol dimethyl ether), polyoxyethylene polypropylene glycol (Polyoxypropylene glycol), polyvinyl alcohol (Polyvinyl alcohol), β- or peuteul polyglycol ether (eu β naphthol polyglycol ether), stearic acid polyglycol A method for producing an electrolytic copper foil comprising at least one selected from the group consisting of ether (Stearic acid polyglycol eter) and stearyl alcohol polyglycol ether.

[Claim 25]

The method according to claim 18, wherein the phenazinium compound is a compound represented by the formula (11):

Wherein Rl, R2, R4, R5, R6, R7 ', R7 ", R8 and R9 are independently of each other hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms,

X is -N = N-C6H4— N (CH3) 2, hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms,

A is a halogen element.

[Claim 26] The method according to claim 18,

Said phenazinium compound is at least one selected from the group consisting of safranin—O (Safaranine-O) and Janus Green BUanus Green B).