WO2024116580A1 - Feuille de cuivre traitée en surface, plaque stratifiée plaquée de cuivre et carte de circuit imprimé - Google Patents

Feuille de cuivre traitée en surface, plaque stratifiée plaquée de cuivre et carte de circuit imprimé Download PDF

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WO2024116580A1
WO2024116580A1 PCT/JP2023/035030 JP2023035030W WO2024116580A1 WO 2024116580 A1 WO2024116580 A1 WO 2024116580A1 JP 2023035030 W JP2023035030 W JP 2023035030W WO 2024116580 A1 WO2024116580 A1 WO 2024116580A1
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copper foil
heteroaromatic compound
treated copper
compound layer
layer
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PCT/JP2023/035030
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English (en)
Japanese (ja)
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翔平 岩沢
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Ｊｘ金属株式会社
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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
    • 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

Definitions

  • This disclosure relates to surface-treated copper foil, copper-clad laminates, and printed wiring boards.
  • Copper-clad laminates are widely used in a variety of applications, including flexible printed wiring boards.
  • Flexible printed wiring boards are manufactured by etching the copper foil of a copper-clad laminate to form a conductor pattern (also called a "wiring pattern"), and then mounting electronic components on the conductor pattern by connecting them with solder.
  • the causes of signal power loss (transmission loss) in electronic circuits can be roughly divided into two categories: the first is conductor loss, i.e., loss due to copper foil, and the second is dielectric loss, i.e., loss due to resin substrate.
  • Conductor loss is characterized by the skin effect in the high frequency range, in which current flows along the surface of the conductor, so if the copper foil surface is rough, the current will flow along a complex path. Therefore, in order to reduce the conductor loss of high frequency signals, it is desirable to reduce the surface roughness of the copper foil.
  • transmission loss and “conductor loss” are used simply, they mainly mean “transmission loss of high frequency signals” and “conductor loss of high frequency signals.”
  • Patent Document 1 proposes a method of providing a roughening treatment layer formed from roughening particles on the copper foil, and forming a rust-proofing treatment layer thereon.
  • the rust-proofing treatment layer is composed of a nickel-cobalt alloy plating layer, a zinc plating layer, a chromate treatment layer, and a silane coupling treatment layer.
  • the surface-treated copper foil described in Patent Document 1 has the problem that many layers must be formed on the copper foil, increasing the time and cost required for its manufacture.
  • the anchor effect of the roughening particles may not be enough to ensure sufficient adhesion.
  • an object of the present invention is to provide a surface-treated copper foil that can enhance adhesion to a resin substrate, particularly a resin substrate suitable for high frequency applications, while reducing the time and cost required for production.
  • Another object of the present invention is to provide a copper-clad laminate having excellent adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and a surface-treated copper foil, while reducing the time and cost required for production.
  • an object of the present invention is to provide a printed wiring board having excellent adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and a circuit pattern while reducing the time and cost required for production.
  • the inventors conducted intensive research to solve the above problems, and surprisingly discovered that a specific heteroaromatic compound has the function of improving adhesion to a resin substrate. Based on this discovery, they found that the above problems can be solved by forming a heteroaromatic compound layer containing a specific heteroaromatic compound on at least one side of a copper foil and controlling the Sp of the surface within a predetermined range, and thus completed an embodiment of the present invention.
  • one embodiment of the present invention relates to a surface-treated copper foil having a copper foil and a heteroaromatic compound layer formed on at least one surface of the copper foil, the heteroaromatic compound layer containing a heteroaromatic compound having a heterocycle containing a nitrogen atom as a heteroatom, and Sp being 0.10 to 1.00 ⁇ m.
  • an embodiment of the present invention relates to a copper-clad laminate comprising the above-mentioned surface-treated copper foil and a resin substrate adhered to the heteroaromatic compound layer of the surface-treated copper foil.
  • an embodiment of the present invention relates to a printed wiring board having a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate.
  • a surface-treated copper foil can be provided that can enhance adhesion to a resin substrate, particularly a resin substrate suitable for high frequency applications, while reducing the time and cost required for production.
  • a copper-clad laminate having excellent adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and a surface-treated copper foil can be provided while reducing the time and cost required for production.
  • a printed wiring board can be provided that has excellent adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and a circuit pattern while reducing the time and cost required for production.
  • 1 is an example of a load curve for a heteroaromatic layer.
  • the surface-treated copper foil according to the embodiment of the present invention has a copper foil and a heteroaromatic compound layer formed on at least one surface of the copper foil.
  • the heteroaromatic compound layer may be formed on only one side of the copper foil, or on both sides of the copper foil.
  • the types of the heteroaromatic compound layers may be the same or different.
  • the copper foil is not particularly limited, and may be either an electrolytic copper foil or a rolled copper foil.
  • high purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011) which are usually used as circuit patterns of printed wiring boards can be used.
  • copper alloys such as copper containing Sn, copper containing Ag, copper alloys containing Cr, Zr, Mg, etc., and Corson copper alloys containing Ni and Si can also be used.
  • the term "copper foil” is a concept that includes copper alloy foil.
  • the thickness of the copper foil is not particularly limited, but can be, for example, 1 to 1000 ⁇ m, or 1 to 500 ⁇ m, or 1 to 300 ⁇ m, or 3 to 100 ⁇ m, or 5 to 70 ⁇ m, or 6 to 35 ⁇ m, or 9 to 18 ⁇ m.
  • the heteroaromatic compound layer includes a heteroaromatic compound having a heterocycle containing a nitrogen atom as a heteroatom.
  • the number of ring members of the heterocycle is not particularly limited, but is, for example, 3 to 9, preferably 4 to 6, and more preferably 5.
  • the heteroatom contained in the heterocycle may consist of only a nitrogen atom, or may consist of a nitrogen atom and other atoms (for example, an oxygen atom, a sulfur atom, etc.).
  • the number of heteroatoms contained in the heterocycle is determined depending on the number of ring members, and is, for example, 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
  • the heterocycle may be either a saturated ring or an unsaturated ring.
  • the term "unsaturated ring" includes a partially unsaturated ring.
  • heterocycles include aridine (unsaturated three-membered ring containing one nitrogen atom), diazirine (unsaturated three-membered ring containing two nitrogen atoms), azeto (unsaturated four-membered ring containing one nitrogen atom), diazeto (unsaturated four-membered ring containing two nitrogen atoms), pyrrole (unsaturated five-membered ring containing one nitrogen atom), pyrrolidine (saturated five-membered ring containing one nitrogen atom), imidazole and pyrazole (unsaturated five-membered ring containing two nitrogen atoms), imidazolidine and pyrazolidine (saturated five-membered ring containing two nitrogen atoms), oxazole and isoxazole (unsaturated five-membered ring containing one nitrogen atom and one oxygen atom), oxazolidine and isoxazolidine (saturated saturated five
  • the heterocycle is preferably a 5-membered ring containing 1 to 3 nitrogen atoms, and more preferably an unsaturated 5-membered ring containing 1 to 3 nitrogen atoms (pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole).
  • the heteroaromatic compound having a heterocycle may be a condensed ring compound of a benzene ring and a heterocycle, a condensed ring compound of two or more heterocycles, or a monocyclic compound of a heterocycle.
  • the condensed ring compound of a benzene ring and a heterocycle is not particularly limited, but examples thereof include indole, indazole, isoindole, benzimidazole, benzotriazole, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, acridine, and carbazole.
  • the condensed ring compound of two or more heterocycles is not particularly limited, but examples thereof include triazolopyridine, purine, and pteridine.
  • the monocyclic heterocyclic compound is not particularly limited, and examples thereof include the compounds exemplified above as the heterocyclic ring.
  • the condensed ring compound and the monocyclic compound may have a substituent.
  • the substituent is not particularly limited. Examples of the substituent include an alkyl group such as a methyl group or an ethyl group, a vinyl group, and a nitro group.
  • the heteroaromatic compound layer is a layer containing the above-mentioned heteroaromatic compound.
  • the heteroaromatic compound contained in the heteroaromatic compound layer may be of a single type or of two or more different types.
  • the heteroaromatic compound layer may contain components other than the heteroaromatic compound, as long as the components do not impair the effects of the embodiment of the present invention. Examples of such components include solvents and additives that are mixed in when the heteroaromatic compound layer is formed.
  • the heteroaromatic compound layer has lower peaks (protrusions) than conventional surface treatment layers including roughened layers.
  • the heteroaromatic compound layer has high smoothness. This is because the conventional surface treatment layers including roughened layers improve the adhesion between the surface treatment layer and the resin substrate by the anchor effect, whereas the heteroaromatic compound layer does not aim to obtain the effect of improving adhesion by the anchor effect.
  • the heteroaromatic compound layer improves the adhesion between the surface-treated copper foil and the resin substrate by the adhesive properties of the heteroaromatic compound, so that even if the peaks on the surface are low, the desired effect of improving adhesion can be obtained.
  • the heteroaromatic compound layer has a higher surface smoothness than conventional surface treatment layers including roughened layers, so that the transmission loss due to the skin effect can be reduced.
  • Sp maximum peak height
  • Sp represents the maximum height of the surface from the mean plane.
  • Sp is a peak height parameter defined in ISO 25178-2:2012, and a surface with a small Sp can be said to be a smooth surface.
  • the heteroaromatic compound layer has an Sp of 0.10 to 1.00 ⁇ m.
  • the heteroaromatic compound layer having an Sp controlled within such a range is smooth, and therefore the adhesive properties of the heteroaromatic compound can improve the adhesiveness between the surface-treated copper foil and the resin substrate. In addition, the transmission loss can be reduced.
  • the heteroaromatic compound layer has a thickness Sp of preferably 0.10 to 0.85 ⁇ m, more preferably 0.10 to 0.78 ⁇ m, and further preferably 0.30 to 0.78 ⁇ m.
  • the Sp of the heteroaromatic compound layer can be measured in accordance with ISO 25178-2:2012.
  • the heteroaromatic compound layer has fewer peaks on its surface than conventional surface-treated layers including a roughening treatment layer because of the absence of roughening particles.
  • Vmp solid volume of peaks
  • Vmp is a functional (volume) parameter defined in ISO 25178-2:2012 and represents the solid volume of the peaks of the heteroaromatic compound layer.
  • Vmp can be determined in accordance with ISO 25178-2:2012 by measuring the surface roughness and analyzing the load curve calculated from the measurement data. In explaining the load curve, first, the load area ratio will be explained.
  • the area ratio is a ratio obtained by dividing the area corresponding to the cross section of a three-dimensional object to be measured when the object is cut at a certain height by the area of the measurement field.
  • the object to be measured is assumed to be a copper foil or a heteroaromatic compound layer of a surface-treated copper foil.
  • the load curve is a curve that represents the area ratio at each height.
  • the area ratio near 0% represents the height of the highest part of the object to be measured, and the height near 100% represents the height of the lowest part of the object to be measured.
  • the load curve can be used to express the volume of the solid part and the volume of the space part of the heteroaromatic compound layer.
  • the volume of the solid part corresponds to the volume of the part occupied by the substance of the object to be measured in the measurement field of view
  • the volume of the space part corresponds to the volume occupied by the space between the solid parts in the measurement field of view.
  • the load curve is divided into a valley part, a core part, and a peak part with the positions of the areal load ratio of 10% and 80% as the boundaries.
  • Vvv means the volume of the space part in the valley part of the heteroaromatic compound layer
  • Vvc means the volume of the space part in the core part of the heteroaromatic compound layer
  • Vmp means the volume of the solid part in the peak part of the heteroaromatic compound layer
  • Vmc means the volume of the solid part in the core part of the heteroaromatic compound layer.
  • the volume Vmp of the solid part in the peak portion is the volume of the solid part in the peak portion, i.e., the part where the height of the object to be measured is high, and means the volume of the solid part in the part where the height is particularly high in the heteroaromatic compound layer.
  • the Vmp of the heteroaromatic compound layer is preferably 0.001 to 0.010 ⁇ m 3 / ⁇ m 2 , more preferably 0.001 to 0.006 ⁇ m 3 / ⁇ m 2 .
  • the range of Vmp, which is the solid volume in the particularly high part, means that the heteroaromatic compound layer is smooth.
  • Vmp By controlling Vmp in this range, it is possible to obtain an effect of improving the adhesion between the surface-treated copper foil and the resin substrate due to the adhesive properties of the heteroaromatic compound. In addition, it is also possible to obtain an effect of reducing transmission loss.
  • the Vmp of the heteroaromatic compound layer can be measured in accordance with ISO 25178-2:2012.
  • the heteroaromatic compound layer is smoother than conventional surface treatment layers including a roughening treatment layer because of the absence of roughening particles.
  • Such a heteroaromatic compound layer also has shallow valleys on the surface.
  • Sv maximum valley depth of the valley
  • Sv is a height parameter defined in ISO 25178-2:2012 and represents the minimum height from the average plane of the surface of the heteroaromatic compound layer.
  • the Sv of the heteroaromatic compound layer is preferably 1.50 ⁇ m or less, more preferably 0.10 to 1.25 ⁇ m, and even more preferably 0.50 to 1.20 ⁇ m.
  • the Sv of the heteroaromatic compound layer can be measured in accordance with ISO 25178-2:2012.
  • the copper foil and the heteroaromatic compound layer are in direct contact with each other, but a functional layer may be provided between the copper foil and the heteroaromatic compound layer as long as it does not impair the effects of the embodiment of the present invention.
  • a functional layer include a heat-resistant treatment layer, a rust-prevention treatment layer, and a chromate treatment layer.
  • the method for producing the surface-treated copper foil according to the embodiment of the present invention is not particularly limited, but it can be produced, for example, by the following method.
  • the copper foil is produced by a method known in the art.
  • an electrolytic copper foil when used as the copper foil, it can be generally produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath.
  • a rolled copper foil When a rolled copper foil is used as the copper foil, it can be generally produced by sequentially subjecting a copper ingot to homogenization annealing, hot rolling, cold rolling, annealing, etc.
  • a commercially available product may be used.
  • a coating solution of a heteroaromatic compound is prepared.
  • the coating solution may contain a solvent such as water, additives, etc.
  • the concentration of the heteroaromatic compound in the coating solution may be adjusted depending on the type of the heteroaromatic compound used, and is not particularly limited, but is, for example, 0.1 to 10 mass %.
  • the coating solution of the heteroaromatic compound is applied to the surface of the copper foil and dried to form a heteroaromatic compound layer.
  • the coating method is not particularly limited, and various methods such as immersion, spray coating, curtain flow coater coating, roll coater coating, brush coating, and roller brush coating can be used.
  • the drying method is also not particularly limited, and room temperature drying or heat drying can be selected depending on the type of solvent used.
  • the coating solution of the heteroaromatic compound may be applied and dried once, but may be applied and dried multiple times to form a heteroaromatic compound layer of a desired thickness.
  • the Sp, Vmp and Sv of the heteroaromatic compound layer can be controlled mainly by adjusting the surface roughness of the copper foil on which the heteroaromatic compound layer is formed.
  • the roughness of the copper foil can be controlled by adjusting the manufacturing conditions of the copper foil, the degreasing conditions before the formation of the heteroaromatic compound layer, the pickling conditions, etc.
  • the surface-treated copper foil according to an embodiment of the present invention has a heteroaromatic compound layer that contains a specific heteroaromatic compound, and the Sp of the heteroaromatic compound layer is controlled to 0.10 to 1.00 ⁇ m, which reduces the time and cost required for production while improving adhesion to resin substrates, particularly resin substrates suitable for high-frequency applications.
  • a copper-clad laminate according to an embodiment of the present invention comprises the above-mentioned surface-treated copper foil and a resin substrate adhered to the heteroaromatic compound layer of the surface-treated copper foil.
  • This copper-clad laminate can be produced by adhering a resin substrate to the heteroaromatic compound layer of the above-mentioned surface-treated copper foil.
  • the resin substrate is not particularly limited, and may be one known in the art. Examples of the resin substrate include paper-based phenolic resin, paper-based epoxy resin, synthetic fiber cloth-based epoxy resin, glass cloth/paper composite substrate epoxy resin, glass cloth/glass nonwoven fabric composite substrate epoxy resin, glass cloth-based epoxy resin, polyester film, polyimide resin, liquid crystal polymer, fluororesin, etc. Among these, the resin substrate is preferably polyimide resin.
  • the resin substrate may be made of a low dielectric material. Examples of the low dielectric material include liquid crystal polymer, low dielectric polyimide, etc.
  • the method for bonding the surface-treated copper foil to the resin substrate is not particularly limited and may be any method known in the art.
  • the surface-treated copper foil and the resin substrate may be laminated and then thermocompressed.
  • the copper-clad laminate produced as described above can be used in the production of printed wiring boards.
  • the copper-clad laminate according to an embodiment of the present invention uses the above-mentioned surface-treated copper foil, and therefore can enhance adhesion between a resin substrate, particularly a resin substrate suitable for high-frequency applications, and the surface-treated copper foil while reducing the time and cost required for production.
  • a printed wiring board includes a circuit pattern formed by etching the surface-treated copper foil of the above-mentioned copper-clad laminate.
  • This printed wiring board can be manufactured by etching the surface-treated copper foil of the copper-clad laminate to form a circuit pattern.
  • the method for forming the circuit pattern is not particularly limited, and known methods such as the subtractive method and the semi-additive method can be used. Among them, the subtractive method is preferable as the method for forming the circuit pattern.
  • a printed wiring board is manufactured by the subtractive method, it is preferably carried out as follows. First, a resist is applied to the surface of the surface-treated copper foil of a copper-clad laminate, and a predetermined resist pattern is formed by exposing and developing it. Next, the surface-treated copper foil in the portion where the resist pattern is not formed (unnecessary portion) is removed by etching to form a circuit pattern. Finally, the resist pattern on the surface-treated copper foil is removed.
  • the conditions for this subtractive method are not particularly limited, and the method can be carried out according to the conditions known in the art.
  • the printed wiring board according to the embodiment of the present invention uses the above-mentioned copper-clad laminate, which reduces the time and cost required for production while improving adhesion between the resin substrate, particularly a resin substrate suitable for high-frequency applications, and the circuit pattern.
  • Example 1 A commercially available rolled copper foil (HA-V2 manufactured by JX Metals Corporation; thickness 12 ⁇ m) was prepared as the copper foil, and both sides of the copper foil were degreased and pickled.
  • the degreasing was performed by electrolyzing the surface of the rolled copper foil in a 20 g/L aqueous solution of GN Cleaner 87 (JX Metals Trading Corporation) under conditions of a current density of 11.3 A/ dm2 and a time of 8.6 seconds.
  • the pickling was performed by immersing the foil in a 20 g/L aqueous solution of sulfuric acid for 30 seconds.
  • an aqueous solution of benzotriazole (coating liquid) was prepared using benzotriazole represented by the following formula (1) as a heteroaromatic compound: The concentration of benzotriazole in the aqueous solution was 1% by mass.
  • the copper foil was immersed in an aqueous solution of benzotriazole for 30 seconds, rinsed with water, and dried with a dryer. In this way, a surface-treated copper foil was obtained in which a benzotriazole layer (heteroaromatic compound layer) was formed on the surface of the copper foil.
  • Example 2 A surface-treated copper foil having an indazole layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that an indazole represented by the following formula (2) was used as the heteroaromatic compound.
  • Example 3 A surface-treated copper foil having a benzimidazole layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that benzimidazole represented by the following formula (3) was used as the heteroaromatic compound.
  • Example 4 A surface-treated copper foil having an indole layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that indole represented by the following formula (4) was used as the heteroaromatic compound.
  • Example 5 A surface-treated copper foil having a triazolopyridine layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that a triazolopyridine represented by the following formula (5) was used as the heteroaromatic compound.
  • Example 6 A surface-treated copper foil having a 1-methylbenzotriazole layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that 1-methylbenzotriazole represented by the following formula (6) was used as the heteroaromatic compound.
  • Example 7 A surface-treated copper foil having a 5-methylbenzotriazole layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that 5-methylbenzotriazole represented by the following formula (7) was used as the heteroaromatic compound.
  • Example 8 A surface-treated copper foil having a 1,2,3-triazole layer (heteroaromatic compound layer) formed on the surface of the copper foil was obtained under the same conditions as in Example 1, except that 1,2,3-triazole represented by the following formula (8) was used as the heteroaromatic compound.
  • Comparative Example 1 A comparative sample was prepared by degreasing and pickling both sides of a commercially available rolled copper foil (HA-V2 manufactured by JX Nippon Mining & Metals Corporation; thickness 12 ⁇ m) (copper foil without a heteroaromatic compound layer). The degreasing and pickling were carried out under the same conditions as in Example 1.
  • the roughened layer was formed by electroplating.
  • the electroplating was performed in three stages.
  • the plating solution composition and current density were basically rounded off to the first decimal place.
  • Electroplating conditions current density 40 A/ dm2 , time 1.4 seconds
  • Plating solution composition 20 g/L Cu, 100 g/L sulfuric acid Plating solution temperature: 50°C
  • Electroplating conditions current density 5 A/ dm2 , time 2.0 seconds
  • Plating solution composition 16 g/L Cu, 8 g/L Co, 10 g/L Ni Plating solution pH: 2.4 Plating solution temperature: 36°C
  • Electroplating conditions current density 32 A/dm 2 , time 0.2 seconds
  • the anti-corrosive layer was formed by electroplating, which was carried out in three stages.
  • ⁇ Silane coupling treatment layer> A 4.0% by volume aqueous solution (pH: 10.4) of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and dried to form a silane coupling treatment layer.
  • the roughened layer was formed by electroplating, which was carried out in two stages.
  • First stage conditions Plating solution composition: 11 g/L Cu, 50 g/L sulfuric acid Plating solution temperature: 25°C Electroplating conditions: current density 42.7 A/ dm2 , time 1.4 seconds
  • second stage conditions Plating solution composition: 20 g/L Cu, 100 g/L sulfuric acid Plating solution temperature: 50°C Electroplating conditions: current density 3.8 A/dm 2 , time 2.8 seconds
  • Heat-resistant layer was formed by electroplating.
  • Plating solution composition 23.5 g/L Ni, 4.5 g/L Zn Plating solution pH: 3.6
  • Plating solution temperature 40°C
  • Electroplating conditions current density 1.1 A/dm 2 , time 0.7 seconds
  • Plating solution composition 3.0 g/L K2Cr2O7 , 0.33 g/L Zn Plating solution pH: 3.6 Plating solution temperature: 50°C Electroplating conditions: current density 2.1 A/dm 2 , time 1.4 seconds
  • the surface-treated copper foils or copper foils obtained in the above Examples and Comparative Examples were subjected to the following property evaluations.
  • ⁇ Sp, Vmp and Sv> Images were taken using a laser microscope (LEXT OLS4000) manufactured by Olympus Corporation. The captured images were analyzed using analysis software for a laser microscope (LEXT OLS4100) manufactured by Olympus Corporation. Measurements of Sp, Vmp and Sv were performed in accordance with ISO 25178-2:2012. The measurement results were the average values measured at any three locations. The temperature during measurement was 23 to 25°C.
  • the main settings of the laser microscope and analysis software were as follows.
  • the measurement was performed using a MiniScan (registered trademark) EZ Model 4000L manufactured by HunterLab Co., Ltd., in accordance with JIS Z8730:2009 to measure L*, a*, and b* of the CIE L*a*b* color system.
  • the surface-treated copper foil or copper foil to be measured obtained in the above examples and comparative examples was pressed against the photosensitive part of the measurement device, and measurements were performed while preventing light from entering from the outside.
  • the measurements of L*, a*, and b* were performed based on the geometric condition C of JIS Z8722:2009.
  • the main conditions of the measurement device are as follows.
  • Optical system d/8°, integrating sphere size: 63.5 mm, observation light source: D65 Measurement method: Reflection Lighting diameter: 25.4 mm Measurement diameter: 20.0 mm Measurement wavelength/interval: 400-700 nm/10 nm Light source: Pulsed xenon lamp, 1 emission/measurement Traceability standard: National Institute of Standards and Technology (NIST) calibration based on CIE 44 and ASTM E259 Standard observer: 10°
  • the white tiles used as the measurement standards were the following object colors: When measured at D65/10°, the CIE XYZ color system values are X: 81.90, Y: 87.02, and Z: 93.76.
  • ⁇ Peel strength> After laminating the surface-treated copper foil with a resin substrate made of a low dielectric material, a circuit with a width of 3 mm was formed in the MD direction (the longitudinal direction of the rolled copper foil). The formation of the circuit was carried out according to a normal method. Next, the strength (MD 90° peel strength) when the circuit (surface-treated copper foil) was peeled off from the surface of the resin substrate at a speed of 50 mm/min in a 90° direction, i.e., vertically upward from the surface of the LCP substrate, was measured in accordance with JIS C6471:1995. The measurement was carried out three times, and the average value was taken as the peel strength result. If the peel strength is 0.50 kgf/cm or more, it can be said that the adhesion between the circuit (surface-treated copper foil) and the LCP substrate is good.
  • the surface-treated copper foils of Examples 1 to 8 which had a heteroaromatic compound layer and an Sp in the range of 0.10 to 1.00 ⁇ m, had peel strengths comparable to those of the surface-treated copper foil of Comparative Example 2, which had a surface treatment layer such as a roughening layer, and had good adhesion between the LCP substrate and the surface-treated copper foil.
  • the copper foil of Comparative Example 1 which did not have a heteroaromatic compound layer, had a low peel strength.
  • the copper foil of Comparative Example 3 had a smaller roughening than that of Comparative Example 2, which is thought to be the reason for the low peel strength. The above results are surprising.
  • the adhesion between copper foil and a resin substrate such as an LCP substrate is generally improved by forming a surface treatment layer containing roughening particles.
  • the presence of a heteroaromatic compound layer having a smooth surface sufficiently ensures the adhesion to the resin substrate such as an LCP substrate.
  • a surface-treated copper foil that can enhance adhesion to a resin substrate, particularly a resin substrate suitable for high frequency applications, while reducing the time and cost required for production.
  • a copper-clad laminate that has excellent adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and the surface-treated copper foil, while reducing the time and cost required for production.
  • a printed wiring board that has excellent adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and a circuit pattern, while reducing the time and cost required for production.
  • the embodiment of the present invention may take the following aspects.
  • the heteroaromatic compound layer contains a heteroaromatic compound having a heterocycle containing a nitrogen atom as a heteroatom, and the surface-treated copper foil has an Sp of 0.10 to 1.00 ⁇ m.
  • the heteroaromatic compound is at least one selected from the group consisting of benzotriazole, indazole, benzimidazole, indole, triazolopyridine, 1-methylbenzotriazole, 5-methylbenzotriazole, and 1,2,3-triazole.
  • ⁇ 5> The surface-treated copper foil according to any one of the above ⁇ 1> to ⁇ 4>, wherein the Sp is 0.10 to 0.85 ⁇ m.
  • ⁇ 6> The surface-treated copper foil according to the above item ⁇ 5>, wherein the Sp is 0.10 to 0.78 ⁇ m.
  • ⁇ 7> The surface-treated copper foil according to the above ⁇ 5>, wherein the Sp is 0.30 to 0.78 ⁇ m.
  • ⁇ 8> The surface-treated copper foil according to any one of the above ⁇ 1> to ⁇ 7>, wherein the heteroaromatic compound layer has a Vmp of 0.001 to 0.010 ⁇ m 3 / ⁇ m 2 .
  • ⁇ 9> The surface-treated copper foil according to the above item ⁇ 8>, wherein the Vmp is 0.001 to 0.006 ⁇ m 3 / ⁇ m 2 .
  • ⁇ 10> A copper-clad laminate comprising the surface-treated copper foil according to any one of ⁇ 1> to ⁇ 9> above and a resin substrate bonded to the heteroaromatic compound layer of the surface-treated copper foil.
  • ⁇ 11> A printed wiring board comprising a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate according to ⁇ 10> above.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de cuivre traitée en surface qui comprend une feuille de cuivre et une couche de composé hétéroaromatique formée sur au moins une surface de la feuille de cuivre. La couche de composé hétéroaromatique contient un composé hétéroaromatique ayant un cycle hétérocyclique contenant un atome d'azote en tant qu'hétéroatome et ayant un Sp de 0,10 à 1,00 µm.
PCT/JP2023/035030 2022-11-29 2023-09-26 Feuille de cuivre traitée en surface, plaque stratifiée plaquée de cuivre et carte de circuit imprimé WO2024116580A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61266241A (ja) * 1985-05-21 1986-11-25 株式会社日立製作所 銅の表面処理法
JPS6453495A (en) * 1987-08-25 1989-03-01 Toshiba Chem Corp Substrate for multilayer printed wiring
JPH08311658A (ja) * 1995-05-17 1996-11-26 Nippon Parkerizing Co Ltd 銅系金属材料の表面処理用組成物
JP2006253424A (ja) * 2005-03-10 2006-09-21 Nikko Kinzoku Kk プリント配線板の製造方法
JP2011108848A (ja) * 2009-11-17 2011-06-02 Ube Nitto Kasei Co Ltd 絶縁性機能膜付き金属箔、フレキシブル金属張り積層板、電子部品実装モジュールおよびその製造方法
WO2014017183A1 (fr) * 2012-07-24 2014-01-30 三井金属鉱業株式会社 Film d'électrode et élément électroluminescent organique
JP2016151046A (ja) * 2015-02-17 2016-08-22 四国化成工業株式会社 表面処理剤、樹脂組成物及びそれらの利用
WO2017130721A1 (fr) * 2016-01-27 2017-08-03 株式会社新技術研究所 Article en cuivre ou alliage de cuivre contenant une résine polyester à surface modifiée, et procédé de fabrication de celui-ci

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61266241A (ja) * 1985-05-21 1986-11-25 株式会社日立製作所 銅の表面処理法
JPS6453495A (en) * 1987-08-25 1989-03-01 Toshiba Chem Corp Substrate for multilayer printed wiring
JPH08311658A (ja) * 1995-05-17 1996-11-26 Nippon Parkerizing Co Ltd 銅系金属材料の表面処理用組成物
JP2006253424A (ja) * 2005-03-10 2006-09-21 Nikko Kinzoku Kk プリント配線板の製造方法
JP2011108848A (ja) * 2009-11-17 2011-06-02 Ube Nitto Kasei Co Ltd 絶縁性機能膜付き金属箔、フレキシブル金属張り積層板、電子部品実装モジュールおよびその製造方法
WO2014017183A1 (fr) * 2012-07-24 2014-01-30 三井金属鉱業株式会社 Film d'électrode et élément électroluminescent organique
JP2016151046A (ja) * 2015-02-17 2016-08-22 四国化成工業株式会社 表面処理剤、樹脂組成物及びそれらの利用
WO2017130721A1 (fr) * 2016-01-27 2017-08-03 株式会社新技術研究所 Article en cuivre ou alliage de cuivre contenant une résine polyester à surface modifiée, et procédé de fabrication de celui-ci

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