WO2006106956A1 - 電解銅箔及び電解銅箔の製造方法、その電解銅箔を用いて得られた表面処理電解銅箔、その表面処理電解銅箔を用いた銅張積層板及びプリント配線板 - Google Patents
電解銅箔及び電解銅箔の製造方法、その電解銅箔を用いて得られた表面処理電解銅箔、その表面処理電解銅箔を用いた銅張積層板及びプリント配線板 Download PDFInfo
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- WO2006106956A1 WO2006106956A1 PCT/JP2006/306920 JP2006306920W WO2006106956A1 WO 2006106956 A1 WO2006106956 A1 WO 2006106956A1 JP 2006306920 W JP2006306920 W JP 2006306920W WO 2006106956 A1 WO2006106956 A1 WO 2006106956A1
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- copper foil
- electrolytic copper
- electrolytic
- glossiness
- clad laminate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12451—Macroscopically anomalous interface between layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12472—Microscopic interfacial wave or roughness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12882—Cu-base component alternative to Ag-, Au-, or Ni-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
Definitions
- the present invention relates to an electrolytic copper foil, a surface-treated electrolytic copper foil, a method for producing the electrolytic copper foil, a copper-clad laminate using the surface-treated electrolytic copper foil, and a printed wiring board.
- the present invention relates to an electrolytic copper foil having a low profile and high gloss on the bonding surface of the electrolytic copper foil with the insulating layer constituting material.
- Copper metal foil is widely used as a basic material for printed wiring boards because metallic copper is a good electrical conductor and is relatively inexpensive and easy to handle.
- electronic and electrical devices that frequently use printed wiring boards are required to be so-called light and thin, such as miniaturization and weight reduction.
- light and thin such as miniaturization and weight reduction.
- the profile is the adhesive surface that is the bonding interface with the insulating layer forming material in the standard for copper foil for printed wiring boards (in the present application, the term “bonding surface” will be unified without using “bonding interface”. )
- the roughness Rzjis is defined by the value measured in the TD direction in accordance with JIS B 0601-2001.
- the low profile means that the surface roughness Rzjis of the bonding surface is small.
- the surface roughness Rz of the deposition surface of the untreated electrolytic copper foil is the same as the surface roughness Rz of the glossy surface of the untreated electrolytic copper foil.
- a surface-treated electrolytic copper foil is disclosed in which a roughening treatment is performed on the deposition surface of a smaller foil to form an adhesive surface.
- an electrolyte solution containing a compound having a mercapto group, a salt ion, a low molecular weight glue having a molecular weight of 10,000 or less, and a high molecular polysaccharide is used for the production of the untreated electrolytic copper foil.
- the compound having a mercapto group is 3-mercapto 1-propane sulfonate
- the molecular weight of the low molecular weight glue is 3000 or less
- the high molecular polysaccharide is hydroxyethyl cellulose.
- Patent Document 2 describes a method for producing an electrolytic copper foil by electrolysis of a sulfuric acid copper plating solution, wherein a diaryldialkyl ammonium salt and a diacid-sulfur dioxide are used.
- a method for producing an electrolytic copper foil characterized by using a sulfuric acid copper plating solution containing a copolymer.
- the sulfuric acid copper plating solution preferably contains polyethylene glycol, chlorine and 3-mercapto-1-sulfonic acid.
- the electrolytic copper foil with a small precipitation surface roughness used as the contact surface with the insulating substrate has a low profile with a 10-point average roughness Rz of about 1.0 ⁇ m ⁇ 0.5 ⁇ m. It is supposed to be done.
- Patent Document 1 Japanese Patent Laid-Open No. 9143785
- Patent Document 2 JP 2004-35918 A
- a copper foil having a smooth surface when used as a negative electrode current collector for a lithium ion battery.
- a copper foil with a smooth surface is used as a current collector in order to apply the active material-containing slurry onto the copper foil with a uniform coating thickness. It is advantageous to do.
- the negative electrode active material expands and contracts during charge and discharge. Since the shrinkage is repeated, the dimensional change of the copper foil as a current collector is large, and the expansion and contraction behavior of the copper foil cannot follow the expansion and contraction of the copper foil.
- the mechanical properties of the copper foil as a current collector require a good balance between tensile strength and elongation to withstand repeated expansion and contraction behavior. Furthermore, when forming a capacitor dielectric layer on a copper foil by a sol-gel method, it is also advantageous to use a copper foil having a smooth surface.
- the present inventors have conducted intensive research and found that they have productivity comparable to that of conventional electrolytic copper foil production technology and have a low profile with an upper limit of 450 m that can be handled. I came up with a copper electrolytic copper foil.
- Electrolytic copper foil according to the present invention In the present invention, the surface roughness (Rzjis) on the precipitation surface side is less than 1. O / zm and the glossiness of the precipitation surface [Gs (60 °;) An electrolytic copper foil is provided, characterized in that it is 400 or more.
- [MD glossiness] is preferably from 0.9 to 1.1.
- the precipitation surface side has a glossiness [Gs (20 °)].
- the glossy surface side has a surface roughness (Rzjis) of 2
- the electrolytic copper foil exhibits mechanical properties in which the tensile strength in a normal state is 33 kgfZmm 2 or more and the elongation is 5% or more.
- the electrolytic copper foil according to the present invention has a tensile strength of 30 kgfZmm 2 or more after heating (180 ° CX 60 minutes, air atmosphere), and an elongation rate after heating (180 ° CX 60 minutes, air atmosphere). Shows mechanical properties of more than 8%.
- Surface-treated electrolytic copper foil according to the present invention In the surface-treated electrolytic copper foil according to the present invention, the surface of the above-described electrolytic copper foil was subjected to at least one of antifouling treatment and silane coupling agent treatment. Is.
- the surface roughness (Rzjis) of the adhesion surface of the surface-treated electrolytic copper foil according to the present invention to the insulating layer constituting material is preferably 1.5 m or less.
- a surface treated electrolytic copper foil according to the present invention having a glossiness [Gs (60 °)] of 250 or more as an adhesive surface with the insulating layer constituting material.
- the surface-treated electrolytic copper foil according to the present invention it is also preferable to subject the surface-treated electrolytic copper foil to a surface to be bonded to the insulating layer constituting material.
- the deposited surface of the electrolytic copper foil as the adhesive surface of the surface-treated electrolytic copper foil according to the present invention with the insulating layer constituting material.
- Manufacturing method of electrolytic copper foil according to the present invention is as follows: the copper deposited on the cathode surface is peeled off by an electrolytic method using a sulfuric acid-based copper electrolytic solution.
- the sulfate-based copper electrolyte is a 3 mercapto 1-provensulphonic acid (hereinafter referred to as “MPS” in this application) or bis (3 sulfopropyl) disulfide (hereinafter referred to as “SPS” in this application).
- MPS 3 mercapto 1-provensulphonic acid
- SPS bis (3 sulfopropyl) disulfide
- quaternary ammonium salt polymer having a cyclic structure and chlorine.
- the total concentration of MPS and Z or SPS in the sulfuric acid-based copper electrolyte is preferably 0.5 ppm to 100 ppm.
- the concentration of the quaternary ammonium salt polymer having a cyclic structure in the sulfuric acid-based copper electrolyte is lppm.
- quaternary ammonium salt polymer having a cyclic structure it is particularly preferable to use a diallyldimethyl ammonium chloride polymer (hereinafter referred to as "DDAC" in the present application).
- DDAC diallyldimethyl ammonium chloride polymer
- the chlorine concentration in the sulfuric acid-based copper electrolyte is preferably 5 ppm to 120 ppm.
- the present invention provides an electrolytic copper foil produced by the production method.
- Copper-clad laminate according to the present invention The copper-clad laminate according to the present invention is obtained by laminating the surface-treated electrolytic copper foil and the insulating layer constituting material. And when the said insulating-layer constituent material which comprises the copper clad laminated board which concerns on this invention contains frame
- a copper-clad laminate can be obtained by using the surface-treated electrolytic copper foil according to the present invention, and the copper-clad laminate is subjected to an etching process to thereby achieve the present invention.
- Such a printed wiring board is obtained. That is, a rigid printed wiring board can be obtained by using the above-mentioned rigid copper clad laminate. And a flexible printed wiring board is obtained by using the above-mentioned flexible copper clad laminated board.
- the electrolytic copper foil according to the present invention has better low profile characteristics than the low profile electrolytic copper foil that has been supplied to the market. As a result, the electrolytic copper foil according to the present invention has an excellent gloss exceeding that of the conventional low profile electrolytic copper foil. However, in the electrolytic copper foil according to the present invention, as the thickness of the electrolytic copper foil is increased, the profile is significantly lowered. This tendency is opposite to the conventional electrolytic copper foil, which has a higher profile as the thickness increases.
- the insulating layer located between the conductor layers composed of the surface-treated electrolytic copper foil according to the present invention has excellent thickness uniformity. Even if a thin insulating layer is used, the insulation reliability between the layers is dramatically improved without causing a short circuit. In particular, if a uniform roughening treatment is performed, it is suitable for a copper clad laminate for high frequency.
- the copper-clad laminate according to the present invention is used to etch the resulting plate.
- the lint wiring board is suitable for forming a fine pitch circuit because the surface-treated electrolytic copper foil according to the present invention used for the copper clad laminate can be low profile.
- electrolytic copper foil is a state after any surface treatment, and is sometimes referred to as “untreated copper foil”, “deposited foil” or the like. In the present specification, this is simply referred to as “electrolytic copper foil”.
- the electrolytic copper foil is generally produced by a continuous production method. A drum-shaped rotating cathode and a lead-based anode or a dimensionally stable anode (DSA) disposed opposite to each other along the shape of the rotating cathode.
- DSA dimensionally stable anode
- the electrolytic copper foil obtained in this way is in the form of a roll wound up with a constant width, so the direction of rotation of the rotating cathode (the length direction of the web) must be set to MD ( Machinine Direction), the width direction perpendicular to MD is called TD (Transverse Direc- tion).
- the surface shape on the peeled side of the electrolytic copper foil in contact with the rotating cathode is a transfer of the shape of the surface of the rotating cathode that has been polished.
- the surface shape on the side that was the precipitation side usually shows a mountain-shaped uneven shape because the crystal growth rate of the deposited copper differs for each crystal surface, and this side is called the “deposition surface”.
- rough precipitation treatment is often performed on the precipitation surface side. It becomes the bonding surface with the insulating layer constituent material when manufacturing the copper clad laminate. Therefore, the smaller the surface roughness of the bonding surface, the better the low profile surface-treated electrolytic copper foil.
- the electrolytic copper foil is subjected to surface treatments such as roughening treatment and anti-oxidation to reinforce the adhesive strength with the insulating layer constituent material by the mechanical anchor effect, and circulates in the factory. However, depending on the application, it may be used without roughening treatment. is there.
- the electrolytic copper foil according to the present invention will be described below.
- the electrolytic copper foil according to the present invention has the characteristics that the surface roughness (Rzjis) on the deposition surface side is less than 1.0 m and the gloss [Gs (60 °;)] is 400 or more. More preferably, the surface roughness (Rzjis) is less than 0.6 m, and the glossiness [Gs (60 °;)] is 600 or more.
- the glossiness will be described.
- the glossiness of [Gs (60 °;)] is measured by irradiating the surface of the electrolytic copper foil with measurement light at an incident angle of 60 °, and measuring the intensity of light bounced at a reflection angle of 60 °. .
- the incident angle here is 0 ° in the direction perpendicular to the light irradiation surface.
- JIS Z 8741-1997 five specular gloss measurement methods with different incident angles are described, and the optimal incident angle should be selected according to the glossiness of the sample.
- 60 ° was mainly adopted for the measurement of the glossiness of the electrolytic copper foil according to the present invention.
- the surface roughness Rzjis has been used as a parameter for evaluating the smoothness of the deposited surface of the electrolytic copper foil.
- Rzjis alone, it is not possible to obtain information about unevenness in the height direction, and it is not possible to obtain information such as the period and undulation of unevenness.
- Glossiness is a parameter that reflects both types of information. By using it together with Rzjis, it is possible to comprehensively judge various parameters such as surface roughness period, waviness, and in-plane uniformity. it can.
- the surface roughness (Rzjis) on the precipitation surface side is less than 1. O / zm, and the glossiness [Gs (60 °;)] of the precipitation surface is The condition that it is 400 or more is satisfied. In other words, the electrolytic copper foil that can guarantee the quality within this range and can be supplied to the market has existed.
- the upper limit of glossiness is not defined here, the upper limit is about 780 in [Gs (60 °;)] based on empirical judgment.
- the glossiness in the present invention was measured using a gloss meter VG-2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z 8741-1997, which is a glossiness measurement method.
- the thickness of the electrolytic copper foil referred to here is not limited. This is because the thicker the thickness, the lower the roughness of the deposited surface and the higher the glossiness. Because. If the upper limit is daringly set, the target is electrolytic copper foil with a thickness of 450 / zm or less, which is the limit that can be profitable even if electrolytic copper foil is manufactured industrially.
- the lower limit of the surface roughness (Rzjis) on the precipitation surface side is limited! / Although it depends on the sensitivity of the measuring instrument, the lower limit of the surface roughness is empirically about 0 .: Lm. However, there are variations in actual measurements, and the lower limit of the measured value that can be guaranteed is about 0.
- the electrolytic copper foil according to the present invention has the above-described glossiness [Gs (60 °;)] on the precipitation surface side in terms of TD glossiness measured in the width direction and MD glossiness measured in the flow direction. If this ratio ([TD glossiness] Z [MD glossiness]) is taken, it will be in the range of 0.9 to 1.1. That is, the difference between the width direction and the flow direction is very small.
- the electrolytic copper foil has different mechanical properties in the width direction (TD) and the flow direction (MD) due to the influence of polishing stripes on the surface of the rotating drum as the cathode. It was hot.
- the electrolytic copper foil according to the present invention has a surface that is more uniform and smooth regardless of the thickness, and the glossiness [Gs (60 °;)] as its appearance is [TD glossiness] Z [ The value of MD glossiness is 0.9 to 1.1, and the variation width is as small as 10%.
- the variation in the surface shape between the TD direction and MD direction of the electrolytic copper foil according to the present invention is extremely small. I mean.
- the fact that there is no difference in appearance in the TD direction and the MD direction means that uniform electrolysis has been achieved and that the crystal structure is uniform. . That is, the difference in mechanical properties such as tensile strength and elongation in the TD direction and MD direction is also reduced.
- the mechanical property difference between the TD direction and the MD direction is small, the influence on the dimensional change rate of the board and the linearity of the circuit due to the directionality of the copper foil when manufacturing the printed wiring board is reduced.
- the mechanical properties of the TD direction and MD direction differ due to the processing method.
- the evaluation that it is unsuitable for fine pattern applications that have a large dimensional change rate, such as film carrier tape plants and thin rigid printed circuit boards that are assumed by the present invention is almost firmly established. ing.
- the precipitation surface side can have a relationship of gloss [Gs (20 °)]> gloss [Gs (60 °)]. If it is the same material, it is expected that it is sufficient to select one incident angle and evaluate the glossiness, but even with the same material, the reflectivity varies depending on the incident angle, so if the incident angle changes Depending on the unevenness of the surface of the surface to be measured, the spatial distribution of reflected light changes, resulting in a difference in glossiness.
- the surface state of the glossy surface is also important.
- the glossy surface is required to have a surface roughness (Rzjis) and a glossiness [Gs (60 °;)] close to the deposited surface of the electrolytic copper foil according to the present invention. That is, in the electrolytic copper foil according to the present invention, the glossy surface has a surface roughness (Rzjis) of less than 2. O / zm and a glossiness [Gs (60 °;)] of 70 or more. It is preferable. More preferably, the surface roughness (Rzjis) is less than 1.
- the glossiness [Gs (60 °;)] is 100 or more.
- the upper limit of glossiness [Gs (60 °;)] of the glossy surface is not specified, it is empirically about 500. That is, in order to obtain the surface state of the precipitation surface described so far, it is preferable to form the surface state described here on the glossy surface. If this condition is not met, there will be a difference in the surface condition in the TD and MD directions, and a difference in mechanical properties such as tensile strength and elongation in the TD and MD directions will also easily occur.
- the surface state of the glossy surface is a transfer of the surface state of the cathode, which is the electrodeposited surface, and is determined by the surface state of the cathode. Therefore, when manufacturing a thin electrolytic copper foil, the surface roughness (Rzjis) of less than 2.0 m is required on the cathode surface.
- the tensile strength in a normal state is 33 kg. fZmm 2 or more and the elongation is 5% or more. After heating (180 ° C ⁇ 60 minutes, atmospheric atmosphere), the tensile strength is preferably 30 kgfZmm 2 or more and the elongation is 8% or more.
- the normal tensile strength is 38 kgfZmm 2 or higher, and the tensile strength after heating (180 ° CX 60 minutes, atmospheric atmosphere) is 33 kgf Zmm 2 or higher. It can be said to have more excellent mechanical properties. Therefore, this good mechanical property not only can withstand bending use of flexible printed wiring boards, but also for current collector applications that constitute negative electrodes such as lithium ion secondary batteries that undergo expansion and contraction behavior. Is also suitable.
- the surface-treated electrolytic copper foil according to the present invention provides a surface-treated electrolytic copper foil obtained by performing at least one of an antifungal treatment and a silane coupling agent treatment on the surface of the above-described electrolytic copper foil.
- This anti-corrosion treatment layer is for preventing the surface of the electrolytic copper foil from being oxidized and corroded so as not to hinder the manufacturing process of the copper-clad laminate and the printed wiring board. It is recommended that the structure be improved if possible without impairing adhesion to the insulating layer constituent material.
- the method used for the anti-bacterial treatment is suitable for the purpose of use, either organic anti-bacterial using benzotriazole, imidazole, etc. or inorganic anti-fouling using zinc, chromate, zinc alloy, etc., or a combination of both. If so, there is no problem.
- the silane coupling agent treatment is a treatment for chemically improving the adhesion with the insulating layer constituting material after the anti-mold treatment is completed.
- the anti-bacterial treatment layer In the case of organic fouling, it is possible to form the organic fouling agent solution by employing techniques such as dip coating, showering coating, and electrodeposition. In the case of an inorganic fender, it is possible to use a method in which a fender element is electrolytically deposited on the surface of the electrolytic copper foil, or a so-called substitution deposition method. For example, a zinc pyrophosphate bath, a zinc cyanide bath, a zinc sulfate bath, or the like can be used for the zinc antibacterial treatment.
- the concentrations are 5 gZl to 30 gZl zinc, 50 gZl to 500 gZl potassium pyrophosphate, and a liquid temperature of 20. C-50. C, pH 9 to 12, current density 0.3 AZdm 2 to 10 AZdm 2 and so on.
- the silane coupling agent used in the silane coupling agent treatment is not particularly limited. Considering the properties of the insulating layer constituent material to be used and the plating solution used in the printed wiring board manufacturing process, epoxy silane coupling agent, amino silane coupling agent, mercapto silane coupling agent, etc. It is possible to select and use them arbitrarily.
- the silane coupling agent treatment can be carried out by employing a method such as dip coating, showering coating, or electrodeposition method with a solution of the silane coupling agent.
- vinyltrimethoxysilane, vinylphenyltrimethoxylane, and ⁇ -methacryloxypropyltrimethoxysilane are mainly used for coupling agents similar to those used for glass cloth of pre-preda for printed wiring boards.
- ⁇ Glycidoxypropyltrimethoxysilane
- 4 Glycidinolebutinoretrimethoxysilane
- ⁇ -Aminopropyltriethoxysilane N—j8 (aminoethinole) ⁇ aminopropyltrimethoxysilane
- ⁇ —3— 4- (3-Aminopropoxy) ptoxy) propyl-1-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, y-mercaptopropyltrimethoxysilane and the like can be used.
- the surface roughness (Rzjis) of the adhesion surface of the surface-treated electrolytic copper foil with the insulating layer constituting material is preferably a low profile of 1.5 m or less. By adjusting the surface roughness within this range, it becomes a surface-treated copper foil suitable for fine pitch circuit formation.
- the glossiness [Gs (60 °)] of the adhesion surface of the surface-treated electrolytic copper foil with the insulating layer constituting material is preferably 250 or more.
- the surface treatment forms an anti-corrosion film or a silane coupling agent film, so even if the change in surface roughness is not detected, the light reflectivity, etc., can be compared to before and after the surface treatment. It can be fluctuated. Therefore, the absolute value of the glossiness may vary after the surface treatment, but if the glossiness [Gs (60 °;)] obtained on the adhesive surface of the surface-treated electrolytic copper foil is maintained at 250 or more, the surface treatment It can be judged that the film is formed with an appropriate thickness.
- the surface of the surface-treated electrolytic copper foil is subjected to a roughening treatment on the bonding surface with the insulating layer constituting material.
- the coarse grain treatment can be applied with a known technique, and the combined force with the anti-corrosion technique is sufficient if the minimum coarse grain treatment is performed.
- the surface-treated electrolytic copper foil according to the present invention is preferably used, it is necessary that the rough etching treatment is not applied. It is preferred to increase the time setting accuracy!
- any one of a force for adhering and forming fine metal particles on the surface of the electrolytic copper foil and a force for forming a rough surface by an etching method may be employed.
- the former method for depositing and forming fine metal particles an example of the method for depositing and forming copper fine particles on the surface will be described.
- This rough wrinkle treatment step is composed of a step of depositing and adhering fine copper particles on the surface of the electrolytic copper foil and a step of covering to prevent the fine copper particles from falling off.
- a cracking condition is employed as the electrolysis condition. Therefore, the concentration of the solution used in the process of depositing and attaching fine copper particles is generally low so that it is easy to create the brown plating conditions.
- the condition of the plating is determined in consideration of the characteristics of the production line, which is not particularly limited.
- the concentration is 5 to 20 gZl copper, 50 to 200 gZl free sulfuric acid, and other additives as required ( ⁇ -naphthoquinoline, dextrin, glue, thiourea, etc.), liquid temperature 15 -40 ° C, current density 10-50 AZdm 2 and so on.
- the covering step for preventing the fine copper particles from falling off is a step for uniformly depositing copper so as to cover the fine copper particles under smooth contact conditions. Therefore, here, the same copper electrolyte as that used in the above-described electrolytic copper foil manufacturing process can be used as a source of copper ions.
- This smoothing condition is determined in consideration of the characteristics of the production line, which is not particularly limited. For example, if a copper sulfate-based solution is used, the conditions are copper 50 to 80 gZl, free sulfuric acid 50 to 150 gZl, liquid temperature 40 to 50 ° C., and current density 10 to 50 AZdm 2 .
- the adhesion surface of the surface-treated electrolytic copper foil with the insulating layer constituting material is a deposition surface side.
- the surface of the cathode drum is a transferred shape on the glossy surface side, it is difficult to eliminate the difference between the TD direction and the ZMD direction. Therefore, in order to minimize the variation in the linearity of the wiring end face that occurs when the shape of the bonding surface is TDZMD, it is preferable to use the deposition surface as the bonding surface.
- the present invention is a method for producing the electrolytic copper foil by stripping copper deposited on the cathode surface by an electrolytic method using a sulfuric acid-based copper electrolyte, wherein the sulfuric acid-based copper electrolyte is obtained from MPS or SPS.
- a method for producing an electrolytic copper foil characterized in that it contains at least one selected quaternary ammonium salt polymer having a cyclic structure and chlorine.
- the copper concentration in this sulfuric acid-based copper electrolyte is 40 gZl to 120 gZl, a more preferable range is 50 gZl to 80 gZl, a free sulfuric acid concentration is 60 g / l to 220 g / l, and a more preferable range is 80 g / l to 150 g / l. To do.
- the combined concentration of MPS and Z or SPS in the sulfuric acid-based copper electrolyte according to the present invention is preferably 0.5 ppm to 100 ppm, more preferably 0.5 ⁇ ! -50 ppm, more preferably 1 ppm-30 ppm.
- the MPS or SPS concentration is less than 0.5 ppm, the deposited surface of the electrolytic copper foil becomes rough, and it becomes difficult to obtain a low profile electrolytic copper foil.
- the concentration of MPS and Z or SPS exceeds lOOppm, the effect of smoothing the deposited surface of the obtained electrolytic copper foil is not improved, and only the cost of waste liquid treatment is increased.
- MPS and Z or SPS as used in the present invention are used to include their respective salts, and the concentration values are sodium 3-mercapto-1-propanesulfonate as sodium salt.
- MPS-Na sodium 3-mercapto-1-propanesulfonate as sodium salt.
- MPS-Na sodium 3-mercapto-1-propanesulfonate as sodium salt.
- MPS-Na sodium 3-mercapto-1-propanesulfonate as sodium salt.
- MPS-Na concentration of MPS or SPS is defined as 3 mercapto-1 propanesulfonic acid alone or MPS—
- the concentration includes those added as SPS and modified products that have been polymerized into SPS after being added to the electrolyte as MPS.
- the structural formula of MPS is shown as chemical formula 1, and the structural formula of SPS is shown as chemical formula 2 below. The comparison of these structural formulas shows that the SPS structure is a dimer of MPS.
- the quaternary ammonium salt polymer having a cyclic structure in the sulfuric acid-based copper electrolyte according to the present invention preferably has a concentration of 1 ppm to 150 ppm, more preferably 10 ppm to 12 Oppm. More preferably, it is 15 ppm to 40 ppm.
- a quaternary ammonium salt polymer having a cyclic structure it is possible to use various polymers. In view of the effect of forming a low profile profile, it is most preferable to use a DDAC polymer. DDAC forms a cyclic structure when taking a polymer structure, and part of the cyclic structure is composed of quaternary ammonium nitrogen atoms.
- DDAC polymer is considered to be any one of the above-mentioned cyclic structure force ring to 7-member ring or a mixture thereof, here, representative of the compounds having a 5-membered ring structure of these polymers. It is shown below as ⁇ 3.
- This DDAC polymer is one in which DDAC has a polymer structure of a dimer or more as apparent from Chemical Formula 3.
- the concentration of the DDAC polymer in the sulfuric acid-based copper electrolyte is preferably 1 ppm to 150 ppm, more preferably 10 ppm to 120 ppm, and even more preferably 15 ppm to 40 ppm. If the concentration of the DDAC polymer in the sulfuric acid-based copper electrolyte is less than 1 ppm, no matter how much the MPS or SPS concentration is increased, the deposited copper surface becomes rough, and a low profile electrolytic copper foil can be obtained. It becomes difficult. Even if the concentration of the DDAC polymer in the sulfuric acid-based copper electrolyte exceeds 150 ppm, the copper deposition state becomes unstable, making it difficult to obtain a low profile electrolytic copper foil.
- the chlorine concentration in the sulfuric acid-based copper electrolyte is 5 ⁇ ! It is preferably ⁇ 120 ppm, more preferably 10 ppm to 60 ppm.
- the chlorine concentration is less than 5 ppm, the deposited surface of the electrolytic copper foil becomes rough and the low profile cannot be maintained.
- the chlorine concentration force exceeds Sl20 ppm, the deposited surface of the electrolytic copper foil becomes rough, the electrodeposition state is not stable, and a deposited surface with a low profile cannot be formed.
- an electrolytic copper foil is produced using the sulfuric acid-based copper electrolyte
- electrolysis is performed using a cathode and an insoluble anode whose surface roughness is adjusted to a desired range.
- the liquid temperature is 20 ° C to 60 ° C, more preferably 40 ° C to 55 ° C
- the current density is 15AZdm 2 to 90AZdm 2 , more preferably 50AZdm 2 to 70A / dm 2 . It is recommended.
- the cathode surface state in the production should also be managed.
- JIS C 6515 which is the standard for electrolytic copper foil for printed wiring boards, specifies that the maximum surface roughness (Rzjis) of the glossy surface required for electrolytic copper foil is 2.4 m.
- the cathode used in the production of the electrolytic copper foil is a rotating cathode drum made of titanium (Ti), and changes in appearance and metal phase due to surface oxidation occur during continuous use. Therefore, it is necessary to perform mechanical processing such as polishing or cutting according to the regular surface polishing and condition.
- the precipitation surface roughness tends to increase as the thickness increases, and a cathode drum having a roughness of the upper limit level of the general standard value or higher is used.
- the obtained electrolytic copper foil is empirically understood that the surface roughness of the deposited surface tends to increase under the influence of the surface shape of the cathode.
- the use of the above-described copper sulfate-based electrolytic solution affects the influence of the cathode surface shape in the process of filling the unevenness of the cathode surface and increasing the thickness. It can be reduced to form a flat precipitation surface.
- an electrolytic copper foil having a thickness of less than 20 m if the precipitation surface roughness (Rzjis) is less than 1. ⁇ m, the glossy surface of the obtained electrolytic copper foil is rough.
- the viewpoint power to reduce the difference between the mechanical characteristics and the surface characteristics in the TD direction and the MD direction is also preferable.
- the present invention provides an electrolytic copper foil produced by the production method.
- the present invention provides a copper clad laminate obtained by laminating the surface-treated electrolytic copper foil with an insulating layer constituting material.
- flexible copper clad laminates If so, the conventional roll laminating method and casting method can be used, and the rigid copper-clad laminate can be manufactured using a hot press method or a continuous laminating method.
- the flexible copper-clad laminate and the rigid copper-clad laminate referred to in the present invention are concepts including all of a single-sided copper-clad laminate, a double-sided copper-clad laminate, and a multilayer copper-clad laminate.
- the surface-treated copper foil according to the present invention is used for the outer layer, and the inner layer includes an inner layer core material having an inner layer circuit.
- the following copper-clad laminate these are not explained separately. This is because they are duplicated.
- the present invention provides a rigid copper clad laminate in which the insulating layer constituting material contains a skeleton material.
- Most of the skeletal materials used in conventional rigid copper-clad laminates are glass woven fabrics or glass nonwoven fabrics, and the roughness of the copper foil bonding surface affects the interlayer insulation at levels above 10 m. It has been reported that migration resistance due to direct contact between the glass fiber, which is a skeleton material, and the circuit can be a problem even at 10 m or less. And it has been said that there is no need to make a problem at 5 m level. However, in recent years, a knock pattern substrate on which electronic components are directly mounted, such as BGA and CSP, has been required to have a fine pattern of a level that has not existed before.
- the copper-clad laminate according to the present invention is suitable not only for fine patterns but also for manufacturing printed wiring boards having a high-frequency signal transmission circuit.
- the present invention provides a flexible copper clad laminate in which the insulating layer constituting material is made of a flexible material having flexibility.
- the flexible copper-clad laminate has been divided into its use by the flexibility and light weight of the above-mentioned rigid copper-clad laminate, and the insulating layer constituent material is for light weight and high flexibility. Thinning has been achieved.
- the conductor layer is also required to be thin, and electrolytic copper foil has become the main material.
- the adhesive layer has a low profile of lZio or less of the insulation layer thickness.
- the flexible copper-clad laminate using the electrolytic copper foil of the present invention can ensure insulation reliability even if the film thickness is further reduced. Compared to conventional flexible copper-clad laminates using low profile filed electrolytic copper foil, it has superior flexibility.
- the copper-clad laminate has improved reliability.
- the roll laminate method or casting method as described above can be employed.
- This roll laminating method uses a roll of a surface-treated copper foil according to the present invention and a resin film roll such as a polyimide resin film or PET film, and is thermocompression bonded with the pressure of a heating roll by a roll to roll system. It is a method.
- the casting method is a method of forming a resin composition film that is converted to polyimide resin by heating such as a polyamic acid on the surface of the surface-treated copper foil according to the present invention, and heating it to cause a condensation reaction.
- a polyimide resin film is directly formed on the surface of the treated copper foil.
- this invention provides the rigid printed wiring board characterized by using the said rigid copper clad laminated board.
- the pattern plating Z flash etching method can be used as well as the subtractive method for the production of the printed wiring board using the copper-clad laminate using the electrolytic copper foil having a smooth adhesive surface according to the present invention.
- the overetching time setting can be shortened, so that the end face of the obtained circuit is more linear and the cross section is closer to a rectangle. Therefore, it has excellent insulation reliability between circuits with fine patterns, and at the same time has excellent signal transmission characteristics in the high-frequency region that flows near the circuit surface due to the skin effect, and noise such as crosstalk is less likely to occur. This is a printed wiring board with excellent reliability.
- the present invention also provides a flexible printed wiring board obtained by using the flexible copper-clad laminate.
- the subtractive method as well as the pattern plating Z flash etching method can be used as in the case of the above-mentioned rigid printed wiring board.
- the end face of the resulting circuit is more linear and the cross section is closer to a rectangle. Therefore, it is a highly reliable printed wiring board that has excellent signal transmission characteristics in the high frequency range and that does not easily generate noise such as crosstalk. At the same time, it has excellent insulation reliability and flexibility. It is the one that can demonstrate its superiority when used as a film carrier for direct mounting.
- etching resist layer is formed on the surface of the copper-clad laminate, and the etching circuit pattern is exposed and developed to form an etching resist pattern.
- a photosensitive resin such as a dry film or a liquid resist is used.
- UV exposure is generally used for exposure, and an etching resist pattern forming method based on a conventional method can be adopted.
- the electrolytic copper foil is etched into a circuit shape using a copper etching solution, and the etching resist is peeled off to form a desired circuit shape on the surface of the rigid base material or the flexible base material.
- a copper etching solution all copper etching solutions such as an acidic copper etching solution and an alkaline copper etching solution can be used.
- the copper-clad laminate referred to in the present invention is described as a concept including all of a single-sided copper-clad laminate, a double-sided copper-clad laminate, and a multilayer copper-clad laminate having an internal circuit inside.
- a conduction plating process for obtaining interlayer conduction is performed.
- the conductive plating treatment is performed by an active metal treatment with a noradium catalyst to give a copper electroless plating, and then the electrolytic copper plating is used for film thickness growth.
- the surface was polished with No. 2000 polishing paper and the surface roughness was adjusted to 0.85 ⁇ m with Rzjis. A plate electrode was used.
- Examples 1 to 8 were performed.
- SPS which is a dimer of MPS, was used as a substitute for MPS.
- a chromate layer was formed by electrolysis on the zinc barrier layer.
- the electrolysis conditions at this time were chromic acid concentration 5. Og / pH 11.5, liquid temperature 35 ° C., current density 8 A / dm 2 , and electrolysis time 5 seconds.
- the silane coupling agent was adsorbed on the antifouling treatment layer on the deposition surface immediately in the silane coupling agent treatment tank.
- the solution composition at this time was set to 5 g / 1 with ⁇ -glycidoxypropyltrimethoxysilane concentration using pure water as a solvent.
- the solution was adsorbed by spraying with a shower ring.
- the average crystal particle diameter is the average crystal particle possessed by the electrolytic copper foil having a low profile due to the fine crystallization used in the conventional film carrier tape. The existence of twins larger than the diameter was also confirmed.
- Example 10 to Example 14 as the sulfuric acid-based copper electrolyte, the copper concentration was 80 gZl, the free sulfuric acid concentration was 140 gZl, and the concentrations of SPS and DDAC polymer (Sunriki Co., Ltd. A solution adjusted to the chlorine concentration was used.
- Example 1 SPS-Na DDAC Polymer Example 1 0 5 30 25 Example 1 1 1 0 20 22 Example 1 2 100 100 100 100 Example 1 3 50 70 100 Example 14 50 100 50
- Table 5 shows the normal state of the 12 m and 70 IX m electrolytic copper foil obtained in Example 10, and the tensile strength and elongation after heating at 180 ° C X 6 Omin. And the normal tensile strength of the 12 / zm electrolytic copper foil is 35.5kgfZmm 2 , elongation is 11.5%, 180 ° CX 60min. After heating The tensile strength of 33.2kgfZmm 2 and the elongation of 11.2% are sufficiently high enough to withstand the use of flexible printed circuit boards.
- the folding resistance of the above 12 m electrolytic copper foil When evaluating the folding resistance of the above 12 m electrolytic copper foil by the MIT method, it can withstand a bending test of 12,000 to 1,350 times under normal conditions and 800 to 900 times even after heating. ing.
- the above MIT method is used as a MIT folding device using a Toyo Seiki Seisakusho-made film folding fatigue tester (Part No. 549) with a bending radius of 0.8 mm and a load of 0.5 kgf. It is implemented with 15mm XI 50mm. This figure is about 600 times under normal conditions when the general-purpose electrolytic copper foil that has been used for flexible printed wiring boards is evaluated under the same conditions, and about 500 times after heating. Therefore, the folding resistance is approximately double. This difference can be presumed to be due to the effect of cracks that are less likely to cause cracking due to the smooth surface.
- the electrolytic copper foil obtained above was immersed in a dilute sulfuric acid solution having a concentration of 150 gZl and a liquid temperature of 30 ° C for 30 seconds to remove deposits and surface oxide film, and washed with water.
- the 12 m electrolytic copper foil and the 70 ⁇ m electrolytic copper foil obtained in Example 10 were each subjected to a surface treatment electrolytic copper foil and a roughening treatment! A total of 4 types of treated electrolytic copper foils were prepared.
- the 12 m electrolytic copper foil and the 70 ⁇ m electrolytic copper foil to be subjected to the roughening treatment are subjected to a pickling treatment, and as a step of forming fine copper grains on the deposited surface of the electrolytic copper foil, A step of depositing and adhering fine copper particles on the precipitation surface and a covering plating step for preventing the fine copper particles from falling off were performed.
- a copper sulfate-based solution with a copper concentration of 15 gZl, a free sulfuric acid concentration of 100 gZl, a liquid temperature of 25 ° C, and a current density of 30 AZd Electrolysis was performed for 5 seconds under the condition of m 2 .
- both surfaces of all the obtained electrolytic copper foils were subjected to antifouling treatment.
- inorganic fenders having the conditions described below were employed.
- free sulfuric acid concentration of 7 Og / zinc concentration of 20 gZl, liquid temperature of 40 ° C, current density of 15 AZdm 2 and zinc anti-bacterial treatment were applied.
- a chromate layer was further formed on the zinc barrier layer by electrolysis.
- the electrolysis conditions were as follows: chromic acid concentration 5. Og / U pH 11.5, liquid temperature 35 ° C, current density 8AZdm 2 , electrolysis time 5 seconds.
- the silane coupling agent was adsorbed on the antifouling treatment layer on the deposition surface in a silane coupling agent treatment tank immediately after washing with water.
- the solution composition at this time was such that the concentration of y-glycidoxypropyltrimethoxysilane was 5 gZ 1 using pure water as a solvent.
- the solution was adsorbed by spraying with a shower ring.
- water was finally diffused by an electric heater to obtain six types of surface-treated electrolytic copper foils including one type of roughened foil.
- This comparative example is a trace experiment of Example 1 described in Patent Document 2.
- sulfuric acid-based copper electrolyte copper sulfate (reagent) and sulfuric acid (reagent) were dissolved in pure water to give a copper sulfate (pentahydrate equivalent) concentration of 280 gZl and a free sulfuric acid concentration of 90 gZl.
- a copolymer of diallyl alkyl ammonium salt and diacid sulfur (manufactured by Nitto Boseki Co., Ltd., trade name PAS-A-5, weight average molecular weight 4000) concentration 4 ppm, polyethylene glycol (average molecular weight 100 00) It was adjusted to a concentration of 10 ppm and MPS-Na concentration of 1 ppm, and further, an acidic copper sulfate solution was prepared by using sodium chloride sodium salt to a chlorine concentration of 20 ppm.
- the sulfuric acid-based copper electrolyte a solution having a copper concentration of 80 gZl, a free sulfuric acid concentration of 140 gZl, a DDAC polymer (Sunriki Co., Ltd. unisense FPAIOOL) concentration of 4 ppm, and a chlorine concentration of 15 ppm was used.
- the anode was electrolyzed with a DSA electrode at a liquid temperature of 50 ° C. and a current density of 60 AZdm 2 to obtain an electrolytic copper foil having a thickness of 12 / zm.
- Table 2 shows the mechanical properties of this electrolytic copper foil
- Table 3 shows the surface roughness (Rzjis), glossiness, etc. of the deposited surface together with examples.
- This comparative example is a trace experiment of Example 4 described in Patent Document 2.
- the basic solution of the sulfuric acid-based copper electrolyte was copper sulfate (reagent) and sulfuric acid (reagent) dissolved in pure water to give a copper sulfate (pentahydrate equivalent) concentration of 280 gZl and a free sulfuric acid concentration of 90 gZl.
- Table 5 shows the normal properties of this electrolytic copper foil and the mechanical properties after heating at 180 ° CX for 60 min.
- surface roughness (Rzjis), gloss [Gs (20 °)], [Gs (60 °;)] and [Gs (85 °;)] surface roughness (Rzjis) and gloss [Gs (60 °)] of the deposited surface after surface treatment
- surface roughness of the roughened surface of the roughened foil Table 6 shows the (Rzjis).
- the electrolytic copper foil obtained in the examples has a surface roughness (Rzjis) of 1.0 / zm, gloss [Gs (60 °)] ⁇ 400, and a TDZMD ratio of 0.9 to: L 1 and [Gs (20 °)]> [Gs (60 °)]> [Gs (85 °)] t ⁇ ⁇ Satisfying the respective conditions of the present invention.
- the mechanical properties in the normal state are tensile strength of 33 kgfZmm 2 or more and elongation of 5% or more, and the mechanical properties after heating are tensile strength of 30 kgfZmm 2 or more and elongation of 8% or more.
- the conditions of the invention are satisfied.
- Example 1 When comparing the surface roughness (Rzjis) on the deposition surface side of the electrolytic copper foil, the electrolytic copper foil of Comparative Example 1 also has a good low profile. However, the surface roughness (Rzjis) of the precipitation surface of the 12 ⁇ m electrolytic copper foil according to the present invention is 0.30 ⁇ m to 0.41 ⁇ m, whereas the surface of the precipitation surface of the 12 m electrolytic copper foil of Comparative Example 1 The roughness (Rzjis) is 0. m, and the surface roughness (Rzjis) of the deposited surface of the 210 / zm electrolytic copper foil according to the present invention is 0.27 m to 0.34 / zm.
- the surface roughness (Rzjis) of the copper foil deposition surface is 0.70 m. Therefore, the tendency that a smoother precipitation surface is obtained as the copper foil thickness increases is common, but the electrolytic copper foil according to the present invention is superior in the absolute value of smoothness. Further, when the glossiness [Gs (60 °;)] is compared, the glossiness [Gs (60 °;)] of Comparative Example 1 is in the range of 221 to 283, whereas the glossiness [Gs (60 °;)] shows a completely different range of 603-759. From this, it can be said that, compared with the electrolytic copper foil of Comparative Example 1, each of the electrolytic copper foils of Examples has a flatter surface and a deposition surface close to a mirror surface.
- the 12 / zm electrolytic copper foil of Comparative Example 1 has a tensile strength of 36.2 kgfZmm 2 and an elongation of 4.0% in a normal state, and a tensile strength of 32.4 kgf / mm 2 and elongation after heating.
- the rate is 5.6%, and the only equivalent to the electrolytic copper foil of the example is the bow I tension strength in the normal state.
- Example 2 When comparing the surface roughness (Rzjis) on the deposition surface side of the electrolytic copper foil, the electrolytic copper foil of Comparative Example 2 also has a good low profile. However, the surface roughness (Rzjis) of the precipitation surface of the 12 ⁇ m electrolytic copper foil according to the present invention is 0.30 ⁇ m to 0.41 ⁇ m, whereas the surface of the precipitation surface of the 12 m electrolytic copper foil of Comparative Example 2 The roughness (Rzjis) is 0. m, and the surface roughness (Rzjis) of the deposited surface of the 210 / zm electrolytic copper foil according to the present invention is 0.27 m to 0.34 / zm.
- the surface roughness (Rzjis) of the deposited surface of the copper foil is 1.22 m. Yotsu Thus, in Comparative Example 2, it is considered difficult to obtain a stable and smooth electrolytic copper foil because the smoothness of the deposited surface is impaired by increasing the copper foil thickness.
- the 12 / zm electrolytic copper foil of Comparative Example 2 is in a normal state with a tensile strength of 31.4 kgf / mm 2 , an elongation of 3.5%, and after heating, a tensile strength of 26.8 kgfZmm 2 , The elongation is 5.8%, and the electrolytic copper foils of the examples are superior.
- Comparative Example 4 shows the effect when low molecular weight glue is added to the copper electrolyte instead of MPS.
- the surface roughness (Rzjis) of the deposited surface of the electrolytic copper foil is 3.59 m.
- the low profile is not achieved.
- the glossiness [Gs (60 °;)] is reached, it is almost eradicated, and thus shows a very low value of 1.0. Then, in the mechanical properties, tensile strength of the ordinary state 38.
- the electrolytic copper foil obtained in the example is 0.30 ⁇ m to 0.41 ⁇ m, and the electrolytic copper obtained in Comparative Example 5 is used.
- the surface roughness (Rzji s) of the precipitation surface is 1.00 m, and the difference is clear.
- the electrolytic copper foil obtained in Comparative Example 5 is in the range of 324 to 383,
- the electrolytic copper foils obtained in the examples are in completely different ranges of 603 to 759.
- the electrolytic copper foil of the Example has a flatter surface and a deposition surface close to a mirror surface.
- the mechanical properties of the normal state are that the tensile strength of the electrolytic copper foil of Comparative Example 5 is 37.9 kgf Zmm 2 , the elongation is 8.0%, and the tensile strength of the electrolytic copper foil of Example 10 is 35.5 kgf / mm. 2 , and the growth rate is 11.5%, which is somewhat flexible.
- the mechanical properties after heating were 180 ° CX 60min.
- the tensile strength of the electrolytic copper foil of Comparative Example 5 was 31.6 kgf / mm 2 , and the elongation rate was 7.5%.
- the strength is 33.2 kgf / mm 2 and the elongation is 11.2%, and the electrolytic copper foil according to the present invention is superior. From this result, considering the thermal history when processed into a copper-clad laminate, for example, a flexible printed wiring board using the electrolytic copper foil according to the present invention is expected to have excellent bending resistance. it can.
- FIG. 1 which is an SEM photograph of the electrolytic copper foil deposit surface obtained in Example 11 is shown in Fig. 1, and an SEM photograph of the 12 m electrolytic copper foil deposit surface obtained in Comparative Example 5 is shown in Fig. 2.
- Fig. 2 there are some abnormal precipitates on the surface of the electrolytic copper foil obtained in Comparative Example 5, which are small but have irregularities that cannot be found unless observed at high magnification.
- the irregular reflection of light at the uneven portions decreases the glossiness [Gs (20 °;)] value and increases the surface roughness (Rzjis).
- FIG. 1 which is an SEM photograph of the electrolytic copper foil according to the present invention, no obvious irregularities are observed, and no abnormally precipitated portion is observed.
- the electrolytic copper foil according to the present invention has excellent surface roughness and glossiness.
- the surface roughness (Rzjis The increase in the value of) is approximately the same, about 0.
- the unevenness seen in the deposited copper foil shape obtained in Comparative Example 5 has a pitch of around 3 ⁇ m, but is flat, and thus obtained by rough wrinkle treatment. It can be inferred that the fine particles are attached along the shape of each unevenness.
- the surface roughness (Rzjis) of the precipitation surface that is the base is large, so the surface roughness (Rzjis) of the adhesion surface with the insulating layer constituent material, which is a requirement of the present invention, is 1 . 5 m or less, and the superiority of the electrolytic copper foil according to the present invention is clear.
- the sulfuric acid-based copper electrolytic solution has a copper concentration of about 40 gZl to 120 gZl and a free sulfuric acid concentration of about 60 gZl to 220 gZl.
- the concentration range can be changed according to the intended application. And, even if the presence of additives other than the additives described in the above examples is denied, the effects of the above additives can be further emphasized, and can contribute to quality stability during continuous production. If it has been confirmed, it may be added arbitrarily.
- the deposited surface of the electrolytic copper foil according to the present invention has a lower profile than the low profile electrolytic copper foil that has been supplied to the market, and the roughness of the deposited surface is less than the roughness of the glossy surface. Both sides are glossy and smooth.
- the copper electrolyte used for the production of electrolytic foils is highly productive and adaptable to variations in manufacturing conditions and thickness variations. Therefore, it is suitable for forming a fine pitch circuit of a tape automated bonding (TAB) substrate or a chip on film (COF) substrate, and further an electromagnetic wave shielding circuit of a plasma display panel. And this electrolytic copper foil is excellent Therefore, it is also suitable for use as a current collector constituting negative electrodes such as lithium ion secondary batteries.
- FIG. 1 is an SEM photograph of a 12 m electrolytic copper foil deposited surface obtained in Example 11.
- FIG. 2 is a SEM photograph of the 12 m electrolytic copper foil deposited surface obtained in Comparative Example 5.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP06730868.4A EP1876266B1 (en) | 2005-03-31 | 2006-03-31 | Electrodeposited copper foil and process for producing electrodeposited copper foil |
KR1020097021164A KR100975491B1 (ko) | 2005-03-31 | 2006-03-31 | 전해 동박 및 전해 동박의 제조 방법 |
US11/910,050 US8722199B2 (en) | 2005-03-31 | 2006-03-31 | Electrodeposited copper foil, its manufacturing method, surface-treated electrodeposited copper foil using the electrodeposited copper foil, and copper-clad laminate and printed wiring board using the surface-treated electrodeposited copper foil |
CN2006800096811A CN101146933B (zh) | 2005-03-31 | 2006-03-31 | 电解铜箔及电解铜箔的制造方法、采用该电解铜箔得到的表面处理电解铜箔、采用该表面处理电解铜箔的覆铜层压板及印刷电路板 |
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EP (1) | EP1876266B1 (ja) |
KR (2) | KR100975491B1 (ja) |
CN (2) | CN101851769B (ja) |
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KR100975491B1 (ko) | 2010-08-11 |
KR20090110953A (ko) | 2009-10-23 |
KR20070107803A (ko) | 2007-11-07 |
EP1876266B1 (en) | 2020-06-03 |
US8722199B2 (en) | 2014-05-13 |
CN101851769B (zh) | 2012-07-04 |
US20100038115A1 (en) | 2010-02-18 |
CN101146933B (zh) | 2010-11-24 |
CN101851769A (zh) | 2010-10-06 |
TWI285686B (en) | 2007-08-21 |
KR100941219B1 (ko) | 2010-02-10 |
CN101146933A (zh) | 2008-03-19 |
TW200641186A (en) | 2006-12-01 |
EP1876266A4 (en) | 2013-06-19 |
EP1876266A1 (en) | 2008-01-09 |
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