WO2014126193A1 - 表面処理銅箔及び表面処理銅箔を用いて得られる銅張積層板 - Google Patents
表面処理銅箔及び表面処理銅箔を用いて得られる銅張積層板 Download PDFInfo
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- WO2014126193A1 WO2014126193A1 PCT/JP2014/053450 JP2014053450W WO2014126193A1 WO 2014126193 A1 WO2014126193 A1 WO 2014126193A1 JP 2014053450 W JP2014053450 W JP 2014053450W WO 2014126193 A1 WO2014126193 A1 WO 2014126193A1
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- copper foil
- copper
- roughened
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- composite compound
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1157—Using means for chemical reduction
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Definitions
- This application relates to a surface-treated copper foil and a copper-clad laminate obtained using the surface-treated copper foil.
- the present invention relates to a surface-treated copper foil obtained by roughening the surface of a copper foil with needle-like or plate-like fine irregularities made of a copper composite compound.
- This Patent Document 3 provides a copper-clad laminate for a printed circuit in which a copper foil and a laminated substrate are firmly bonded with a tough and reactive adhesive. Or, in a copper clad laminate having copper foil laminated and bonded on both sides, a.
- a general formula QRSiXYZ ... [1] (wherein Q is a functional group that reacts with the following resin composition, R is Or a silane coupling agent represented by the general formula T (SH) n, a bonding group for linking Q and Si atoms, and X, Y, and Z are hydrolyzable groups or hydroxyl groups bonded to Si atoms). ..
- T is an aromatic ring, aliphatic ring, heterocyclic ring, aliphatic chain, and n is an integer of 2 or more
- b Acrylic monomer, methacrylic monomer, their polymer or oleic Copolymer with fin, (2) peroxide curable resin composition of diallyl phthalate, epoxy acrylate or epoxy methacrylate and oligomer thereof, (3) ethylene butylene copolymer and styrene copolymer in the molecule
- a thermoplastic elastomer peroxide curable resin composition (4) an olefin copolymer resin composition containing a glycidyl group, and (5) a polyvinyl butyral resin resin composition having a side chain containing an unsaturated group.
- an adhesive composed of a polyvinyl butyral resin and a resin composition of an amino resin having a spiroacetal ring and an epoxy resin, or an adhesive of the resin composition. Adopting a copper-clad laminate for printed circuits characterized by being directly bonded to the laminated substrate. It has been disclosed.
- Patent Document 4 discloses a surface-treated copper that does not contain chromium in the surface treatment layer and is excellent in the peel strength of the circuit after processing into a printed wiring board and the chemical resistance deterioration rate of the peel strength.
- a surface-treated copper foil in which a surface-treated layer is provided on a laminated surface of a copper foil used when a copper-clad laminate is produced by laminating with an insulating resin base material Adopting a surface-treated copper foil obtained by adhering a zinc component to a bonding surface of a copper foil, attaching a high melting point metal component having a melting point of 1400 ° C. or higher, and further adhering a carbon component ”.
- the bonding surface of the copper foil preferably has a surface roughness (Rzjis) of 2.0 ⁇ m or less without being subjected to roughening treatment”. Yes.
- Such a non-roughened copper foil does not have irregularities used for roughening on the surface bonded to the insulating resin substrate. For this reason, it is not necessary to provide an over-etching time for removing the anchor shape (uneven shape) embedded in the insulating resin base material when the circuit is formed by etching the copper foil. Therefore, it is very useful in forming a fine pitch circuit having a good etching factor.
- this non-roughened copper foil does not have an anchor shape (uneven shape) embedded in the insulating resin substrate side, the adhesion of the non-roughened copper foil to the insulating resin substrate is roughened. It tends to be lower than copper foil.
- the non-roughened copper foil has good adhesiveness with the insulating resin base material and has no irregularities used for roughening. There was a need for a copper foil with good etching performance equivalent to.
- the surface-treated copper foil according to the present application is a surface-treated copper foil obtained by roughening the surface of the copper foil.
- the surface of the copper foil has a needle shape made of a copper composite compound having a maximum length of 500 nm or less.
- a roughening treatment layer formed of plate-like fine irregularities is provided.
- “acicular or plate-like fine irregularities made of a copper composite compound” will be simply referred to as “fine irregularities made of a copper composite compound”.
- the fine irregularities made of the copper composite compound of the roughened layer of the surface-treated copper foil according to the present application are obtained by using a scanning electron microscope at a surface angle of the roughened layer at a tilt angle of 45 ° and a magnification of 50000 times or more.
- the maximum length when observed from is 150 nm or less.
- the fine irregularities made of the copper composite compound of the surface-treated copper foil according to the present application are Cu (I) when the total area of each peak area of Cu (I) and Cu (II) when analyzed by XPS is 100%. ) It is preferable that the peak occupation area ratio is 50% or more.
- the fine irregularities made of the copper composite compound of the surface-treated copper foil according to the present application contain copper oxide and cuprous oxide.
- corrugation which consists of a copper complex compound of the surface treatment copper foil which concerns on this application has a specific surface area measured by making krypton adsorb
- L * a * b * color system of the lightness L * is preferably provided with a lightness of 25 or less.
- Copper-clad laminate The copper-clad laminate according to the present application is obtained using the above-mentioned surface-treated copper foil.
- the surface-treated copper foil according to the present application forms a roughened surface with “fine irregularities made of a copper composite compound having a maximum length of 500 nm or less”. And although this roughening process surface exists in the outermost surface of copper foil, the macro uneven
- the surface-treated copper foil according to the present application is a surface-treated copper foil obtained by roughening the surface of the copper foil.
- the surface of the copper foil is made of a copper composite compound having a maximum length of 500 nm or less. It is characterized by comprising a roughened layer formed with fine irregularities.
- the copper foil used for the production of the surface-treated copper foil according to the present application can be either an electrolytic copper foil or a rolled copper foil. Further, the thickness of the copper foil is not particularly limited, and it is generally sufficient to recognize that the thickness is 200 ⁇ m or less. In addition, the surface-treated copper foil according to the present application covers both cases where one side is roughened and both sides are roughened.
- the roughened surface of the surface-treated copper foil according to the present application forms a “fine unevenness made of a copper compound” containing copper oxide on the surface of the copper foil, and a reduction treatment is performed to convert cuprous oxide into cuprous oxide.
- the surface is roughened by “fine irregularities made of a copper composite compound having a maximum length of 500 nm or less” containing copper oxide and cuprous oxide.
- the maximum length is 500 nm or less” indicates the maximum value of “fine irregularities made of a copper composite compound” obtained by observing the roughened surface of the surface-treated copper foil with a field emission type scanning electron microscope. It is a thing. As shown in FIG.
- the maximum value of the shape of the “fine irregularities made of the copper composite compound” is the “roughening treatment layer formed by the fine irregularities made of the copper composite compound” provided on the surface of the copper foil. In the cross section, it is a needle-like or plate-like length extending from the surface of the copper foil. From the viewpoint of enhancing the adhesion between the surface-treated copper foil and the insulating layer constituting material according to the present application, the maximum length is more preferably 400 nm or less, and still more preferably 300 nm or less. Hereinafter, this maximum length may be referred to as “maximum length 1”.
- corrugation which consists of a copper composite compound which comprises the roughening process layer of the surface treatment copper foil which concerns on this application is a field emission type scanning, as shown in FIG.
- Maximum length of fine irregularities made of a copper composite compound when observed planarly with a scanning electron microscope at a magnification of 50000 times or more (inclination angle of the sample 45 ° when observed with a scanning electron microscope) 150 nm or less is preferable.
- This FIG. 1 is observed as shown in FIG. 1 (b) when the deposited surface (FIG. 1 (a)) of the double-side smooth electrolytic copper foil is roughened by “fine irregularities made of a copper composite compound” as referred to in the present application. It is shown that.
- the maximum length is more preferably 100 nm or less.
- this maximum length may be referred to as “maximum length 2”.
- FIG. 3 shows a cross section of fine irregularities made of a copper composite compound formed by roughening at this time.
- the average thickness from the surface of the copper foil is 400 nm or less.
- the roughened layer has an average thickness of 250 nm.
- each peak of Cu (I) and Cu (II) can be separated and detected.
- the copper composite compound is analyzed by XPS, the Cu (0) peak may be observed in the shoulder portion of the large Cu (I) peak, so the Cu (I) peak including this shoulder portion may be observed. It is considered. Therefore, in the present invention, the copper composite compound is analyzed using XPS, and Cu (I) appearing at 932.4 eV and Cu (II) appearing at 934.3 eV corresponding to the binding energy of Cu 2p 3/2.
- Each peak obtained by detecting the photoelectrons is separated into waveforms, and the occupied area ratio of the Cu (I) peak is specified from the peak area of each component.
- the Cu (I) peak at this time is considered to be derived from “monovalent copper constituting cuprous oxide”. And it is thought that a Cu (II) peak originates in "the bivalent copper which comprises copper oxide.” Furthermore, it is considered that the Cu (0) peak is derived from “zero-valent copper constituting metallic copper”.
- Quantum 2000 (beam condition: 40 W, 200 um diameter) manufactured by ULVAC-PHI Co., Ltd. is used as the XPS analyzer, and “MultiPack ver. 6.1A” is used as the analysis software. Went.
- the total area of each peak area of Cu (I) and Cu (II) when analyzed by XPS is 100%.
- the occupied area ratio of the Cu (I) peak is preferably 50% or more.
- the occupied area ratio of the Cu (I) peak is less than 50%, the roughened surface of the surface-treated copper foil according to the present application is laminated on the insulating layer constituting material, and the resistance of the circuit obtained by forming the circuit is increased. This is not preferable because the chemical performance decreases.
- the occupied area ratio of the Cu (I) peak of the copper composite compound is more preferably 70% or more, and further preferably 80% or more.
- the occupied area ratio of the Cu (I) peak is not particularly limited, but is 99% or less by an oxidation treatment and a reduction treatment described later. However, the lower the occupied area ratio of the Cu (I) peak, the more the adhesion itself with the insulating layer constituting material tends to improve. In order to obtain good oxidation resistance, 98% or less is preferable and 95% or less is preferable. More preferred. It is.
- the occupied area ratio of the Cu (I) peak is calculated by a calculation formula of Cu (I) / ⁇ Cu (I) + Cu (II) ⁇ ⁇ 100 (%).
- corrugation which consists of a copper complex compound formed by the roughening at this time has a specific surface area (henceforth only called "specific surface area") which adsorb
- the upper limit of the specific surface area is not defined, the upper limit is about 0.3 m 2 / g, more preferably 0.2 m in order to ensure good etching performance equivalent to that of the non-roughened copper foil. 2 / g.
- the specific surface area at this time was pre-treated by heating the sample at 300 ° C. for 2 hours using a specific surface area / pore distribution measuring device 3Flex manufactured by Micromeritics. Measurement is performed using krypton (Kr) as the gas.
- the surface of the roughened layer is darkened such as blackening or browning. That is, the surface of the roughened layer of the surface-treated copper foil according to the present application has a characteristic color tone, and the lightness L * of the L * a * b * color system is 25 or less, more preferably 20 or less. is there. If the lightness L * exceeds 25 and the color tone becomes bright, sufficient roughening has not been performed, and “good adhesion more than unroughened copper foil to an insulating resin base material” can be obtained. Since it is not, it is not preferable.
- the lightness L * was measured using a spectral color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the whiteness plate attached to the measuring device was used for the lightness calibration in accordance with JIS Z8722: 2000. And the measurement of 3 times is performed regarding the same site
- This copper composite compound is formed as follows. First, the surface of the copper foil is oxidized by a wet method using a solution to form “fine irregularities made of a copper compound” containing copper oxide on the surface of the copper foil. Thereafter, the copper compound is subjected to a reduction treatment to convert a part of the copper oxide into cuprous oxide, thereby obtaining “fine irregularities made of a copper composite compound” containing copper oxide and cuprous oxide.
- the solution used for the oxidation treatment in the present application is preferably an alkaline solution that hardly erodes copper oxide, and can be dissolved in the alkaline solution and can be relatively stably coexistent with an amino-based silane coupling. It is preferable to use an agent. Therefore, by adding an amino-based silane coupling agent to the solution used for the oxidation treatment, formation of “fine irregularities made of a copper compound” is facilitated. Since the amino silane coupling agent is adsorbed on the surface of the copper foil, the surface of the copper foil is finely suppressed, so that it becomes a shape of “fine irregularities made of a copper compound”.
- this amino silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. may be used. it can.
- Fine unevenness made of copper compound '' formed by the oxidation treatment on the surface of the surface-treated copper foil according to the present application while maintaining the shape of the fine unevenness made of the original copper compound even when the reduction treatment is performed, It becomes “fine irregularities made of a copper composite compound” containing copper oxide and cuprous oxide having a length of the order of nm. If the copper compound of “fine unevenness made of copper compound” obtained by the oxidation treatment is left as it is, it is easy to be eroded by the etching solution of the component and other acid solutions. Because the solution erosion at the interface is remarkable, the chemical resistance of the formed circuit is reduced.
- a reduction treatment it is preferable to carry out a reduction treatment to obtain a copper composite compound in which a part of copper oxide of “fine irregularities made of a copper compound” is converted into cuprous oxide.
- this reduction treatment by adjusting the reducing agent concentration, solution pH, solution temperature, and the like, the occupied area ratio of the Cu (I) peak of “fine irregularities made of a copper composite oxide” can be adjusted as appropriate.
- the copper composite compound containing copper oxide and cuprous oxide may contain a small amount of metallic copper.
- the surface-treated copper foil according to the present application is immersed in an oxidation treatment solution and contains copper oxide on the surface of the copper foil by a wet method. And then a reduction treatment is performed to form “fine irregularities made of a copper composite oxide” in which the occupied area ratio of the Cu (I) peak is 50% or more. Therefore, it is possible to simultaneously roughen both surfaces of the copper foil. Therefore, when this wet method is used, it is possible to easily obtain a double-side roughened copper foil suitable for forming the inner layer circuit of the multilayer printed wiring board.
- Form of copper-clad laminate The copper-clad laminate according to the present application is obtained using a surface-treated copper foil provided with the above-mentioned roughened layer. If the copper clad laminate at this time is obtained using the surface-treated copper foil according to the present application, there are no particular limitations on the constituent components, thickness, bonding method, etc. of the used insulating resin substrate. No. In addition, the concept of the copper-clad laminate referred to here includes the concept of both rigid type and flexible type.
- an electrolytic copper foil (thickness: 18 ⁇ m) manufactured by Mitsui Metal Mining Co., Ltd. having a surface roughness (Rzjis) of 0.2 ⁇ m and a glossiness [Gs (60 °)] of 600 is used.
- the surface treatment was performed according to the following procedure.
- the electrolytic copper foil was immersed in an aqueous sodium hydroxide solution, subjected to alkali degreasing treatment, and washed with water. Then, the electrolytic copper foil after the alkaline degreasing treatment was immersed in a sulfuric acid solution having a hydrogen peroxide concentration of 1 mass% and a sulfuric acid concentration of 5 mass% for 5 minutes, and then washed with water.
- a predetermined oxidation treatment time (1 minute, 2 minutes, 4 minutes, 10 minutes) was immersed in a sodium hydroxide solution containing 10 g / L to form “fine irregularities made of a copper compound” on the surface of the electrolytic copper foil. Four types of samples were obtained.
- FIG. 1 A scanning electron microscope observation image of the surface of the roughened layer of the surface-treated copper foil obtained in Example 1 is shown in FIG.
- the surface of the roughened layer was subjected to state analysis using XPS, the presence of “Cu (I)”, “Cu (II)”, and “—COO group” was confirmed.
- the occupied area ratio, specific surface area, lightness L * and peel strength of the Cu (I) peak of the surface-treated copper foil obtained in this example are summarized in Table 1 below.
- Example 2 Using the same electrolytic copper foil as used in Example 1, surface treatment was performed according to the following procedure.
- the preliminary treatment and the oxidation treatment (oxidation treatment time: 2 minutes) are the same as those in Example 1.
- the following reduction treatment is adopted in order to examine the influence of the pH of the aqueous solution used for the reduction treatment and the dimethylamine borane concentration.
- the surface-treated copper foil according to the present application was obtained by dipping for 1 minute in each of nine types of aqueous solutions (room temperature) combining these three levels, performing a reduction treatment, washing with water, and drying.
- the surface-treated copper foils obtained when the aqueous solution used for the reduction treatment has a pH of 12 are referred to as “implemented sample 12-a, implemented sample 12-b, and implemented sample 12-c”.
- the “ ⁇ a” display when indicating each of the samples is when the dimethylamine borane concentration in the aqueous solution used for the reduction treatment is 5 g / L.
- “ ⁇ b” is displayed when the dimethylamine borane concentration in the aqueous solution used for the reduction treatment is 10 g / L.
- “ ⁇ c” is indicated when the dimethylamine borane concentration in the aqueous solution used for the reduction treatment is 20 g / L.
- Blackening treatment 10% by volume of “PRO BOND 80A OXIDE SOLUTION”, which is an oxidation treatment solution manufactured by Rohm & Haas Electronic Materials Co., Ltd., and “PRO BOND 80B OXIDE SOLUTION”, which has been subjected to the preliminary treatment.
- a general blackening treatment was formed on the surface by immersing in an aqueous solution containing 20 vol% and having a liquid temperature of 85 ° C. for 5 minutes.
- Reduction treatment The oxidized copper foil after the oxidation treatment is reduced to 6.7 vol% for “CIRCUPOSIT PB OXIDE CONVERTER 60C”, which is a reduction treatment solution manufactured by Rohm & Haas Electronic Materials Co., Ltd., and 1.5 vol for “CUPOSIT Z”.
- the sample was immersed in an aqueous solution containing 35% of a liquid temperature of 35 ° C. for 5 minutes, washed with water, and dried to obtain a comparative sample having a reduced blackening treatment surface shown in FIG.
- Example 1 and Comparative Example Comparison between Example 1 and Comparative Example: With reference to Table 1 below, Example 1 and Comparative Example are compared.
- the maximum length of the “fine irregularities made of a copper composite compound” seen from the surface of the roughening treatment layer is 100 nm.
- the maximum length of the unevenness in the comparative example is 500 nm, which is about 5 times as large. That is, it can be seen that the “fine irregularities made of a copper composite compound” of the surface-treated copper foil according to the present application is extremely fine compared to the conventional blackening treatment.
- the comparative example shows a larger value than the first embodiment.
- the peel strength of the example is 0.63 kgf / cm to 0.78 kgf / cm. Even in the shortest oxidation treatment time, a practically sufficient peel strength is obtained, and a peel strength proportional to the value of the specific surface area is obtained.
- the peel strength of the comparative example having a higher specific surface area than that of Example 1 is as low as 0.33 kgf / cm. Usually, the higher the specific surface area value, the higher the peel strength, but vice versa.
- Example 1 the specific surface area becomes large in proportion to the increase in oxidation treatment time. That is, it can be determined that the oxidation treatment time employed in Example 1 is appropriate. Further, the value of the lightness L * of the roughened surface of Example 1 is 18 to 20, which is a very small value.
- FIG. 2 the scanning electron microscope observation for seeing the roughening form of the electrode surface side and precipitation surface side of the surface treatment copper foil obtained on the conditions for the immersion time of 2 minutes of the oxidation treatment in Example 1 The image is shown. From FIG. 2, on a macro basis, the surface shapes on the electrode surface side and the deposition surface side of the electrolytic copper foil before roughening are maintained after roughening, and along the surface shape before roughening, “copper composite compound” It can be seen that "fine irregularities made of" are formed.
- Example 2 and Comparative Example With reference to Table 2 below, Example 2 and Comparative Example are compared.
- the occupied area ratio of the Cu (I) peak is 83%. Therefore, it can be seen that there is no difference between the example and the comparative example in the occupied area ratio of the Cu (I) peak, but the detected components are different in the state analysis by XPS described above.
- the roughened state of the implementation sample and the comparative sample will be compared with an electron microscope observation image.
- FIG. 2 the roughening state which concerns on an implementation sample can be understood.
- FIG. 3 the state of the cross section of the roughening process layer which concerns on an implementation sample can be understood.
- the roughened electron microscope observation image shown in FIG. 4A immediately after the blackening treatment shows a long and thick needle shape, and the tip of the blackening treatment is sharply pointed. ing.
- the thickness of the roughened layer formed by this needle shape was 500 nm to 700 nm.
- FIG. 4B it can be understood that the top of the irregularities is rounded, and the roughened shape is greatly changed by the reduction process.
- FIG. 5A shows a cross section of the roughened layer immediately after blackening in the comparative example.
- FIG. 5B shows a cross section after the reduction process and the reduction blackening process.
- the uneven shape before the reduction is considerably damaged by the reduction treatment. That is, it can be seen that the needle-like shape formed by the oxidation treatment is thinned and finely broken by the reduction treatment.
- the roughened shape of the “fine irregularities made of a copper composite compound” in the example is not damaged at all even when the reduction treatment is performed, as can be understood from the cross section of FIG. Therefore, it can be predicted that the unevenness after the reduction treatment of the comparative sample is very fragile as compared with the working sample, and the so-called problem of powder falling occurs.
- the peel strength of the surface-treated copper foil obtained in Example 2 and the comparative example will be compared.
- the peel strength of the working sample is 0.70 kgf / cm to 0.81 kgf / cm.
- the peel strength of the comparative sample is 0.33 kgf / cm, which is lower than that of the working sample.
- the surface-treated copper foil according to the present application described above is roughened with "fine irregularities made of a copper composite compound having a maximum length of 500 nm or less", and the insulating resin base material of the non-roughened copper foil Compared with the adhesiveness with respect to, good adhesiveness with the insulating resin substrate can be ensured. Moreover, the surface-treated copper foil according to the present application “because the fine irregularities made of the copper composite compound having a maximum length of 500 nm or less are very fine”, and therefore, an extremely short over-etching time is required for the etching process. Therefore, it is expected that a fine pitch circuit having a good etching factor can be formed. Therefore, it can be usefully used in all printed wiring board products.
- the surface-treated copper foil according to the present application can be made into a form in which the both surfaces of the copper foil are roughened, and the double-sided roughening suitable for forming the inner layer circuit of the multilayer printed wiring board.
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Abstract
Description
実施例1と比較例との対比: 以下の表1を参照して、実施例1と比較例との対比を行う。
Claims (7)
- 銅箔の表面を粗化した表面処理銅箔において、
当該銅箔の表面に、最大長さが500nm以下の銅複合化合物からなる針状又は板状の微細凹凸で形成した粗化処理層を備えることを特徴とする表面処理銅箔。 - 前記銅複合化合物からなる針状又は板状の微細凹凸は、走査型電子顕微鏡を用いて、試料の傾斜角45°、50000倍以上の倍率で粗化処理層の表面から観察したときの最大長さが150nm以下である請求項1に記載の表面処理銅箔。
- 前記銅複合化合物からなる針状又は板状の微細凹凸は、XPSで分析したときのCu(I)及びCu(II)の各ピーク面積の合計面積を100%としたとき、Cu(I)ピークの占有面積率が50%以上である請求項1又は請求項2に記載の表面処理銅箔。
- 前記銅複合化合物からなる針状又は板状の微細凹凸は、酸化銅及び亜酸化銅を含有するものである請求項1~請求項3のいずれかに記載の表面処理銅箔。
- 前記銅複合化合物からなる針状又は板状の微細凹凸は、クリプトンを吸着させて測定した比表面積が0.035m2/g以上である請求項1~請求項4のいずれかに記載の表面処理銅箔。
- 前記粗化処理層の表面は、L*a*b*表色系の明度L* が25以下の明度を備えるものである請求項1~請求項5のいずれかに記載の表面処理銅箔。
- 請求項1~請求項6のいずれかに記載の表面処理銅箔を用いて得られたことを特徴とする銅張積層板。
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JP5809361B2 (ja) | 2015-11-10 |
CN105102678B (zh) | 2018-06-12 |
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CN107881505A (zh) | 2018-04-06 |
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