WO2021220524A1 - Élément de cuivre composite - Google Patents

Élément de cuivre composite Download PDF

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Publication number
WO2021220524A1
WO2021220524A1 PCT/JP2020/027739 JP2020027739W WO2021220524A1 WO 2021220524 A1 WO2021220524 A1 WO 2021220524A1 JP 2020027739 W JP2020027739 W JP 2020027739W WO 2021220524 A1 WO2021220524 A1 WO 2021220524A1
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Prior art keywords
copper
group
composite
copper member
member according
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PCT/JP2020/027739
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English (en)
Japanese (ja)
Inventor
牧子 佐藤
慎 寺木
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ナミックス株式会社
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Priority to KR1020227039993A priority Critical patent/KR20230007390A/ko
Priority to CN202080100179.1A priority patent/CN115461495A/zh
Priority to JP2020539869A priority patent/JP6806405B1/ja
Publication of WO2021220524A1 publication Critical patent/WO2021220524A1/fr

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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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • 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

Definitions

  • the present invention relates to a composite copper member.
  • Copper foil used for printed wiring boards is required to have good adhesion to resin.
  • a method has been used in which the surface of the copper foil is roughened by etching or the like to increase the mechanical adhesive force by the so-called anchor effect.
  • flattening of the copper foil surface has been required.
  • a copper surface treatment method Japanese Patent Laid-Open No. 2018-145519
  • a copper surface treatment method such as performing an oxidation step and a reduction step.
  • An object of the present invention is to provide a composite copper member and a method for manufacturing a composite copper member having good adhesion to a resin substrate and excellent high frequency characteristics with little transmission loss when used in a high frequency circuit board. And.
  • the inventors of the present application suppressed the surface roughness of the conductor portion by adding a copper corrosion inhibitor during the roughening treatment with an aqueous oxidizing agent, and in particular, the surface roughness was high. Succeeded in producing a composite copper member with improved adhesion to a resin substrate while suppressing transmission loss of high-frequency current by making the maximum height roughness, which is a directional parameter, smaller than the skin depth with respect to high-frequency current. bottom.
  • the present invention has the following embodiments: [1] A composite copper member in which a layer containing a copper oxide is formed on the surface of at least a part of the copper member. A composite copper member having an Rz on the surface of at least a part of the copper member of 0.20 ⁇ m or more and 0.70 ⁇ m or less. [2] Inside the layer containing the copper oxide, Copper corrosion inhibitor, A conjugate molecule of the copper corrosion inhibitor and a copper atom, copper ion, copper hydroxide or copper oxide, The composite copper member according to [1], which contains an atom contained in a copper corrosion inhibitor.
  • the composite copper member [3] By immersing the copper member in an aqueous solution of an oxidizing agent having a pH of 11.5 to 14 containing the copper corrosion inhibitor, a layer containing a copper oxide is formed on the surface of at least a part of the copper member.
  • the composite copper member according to [2].
  • the copper corrosion inhibitor has an -OH group, an ether group (-O-), or an N atom that binds to a copper atom, a copper ion, copper hydroxide or copper oxide, in [2] or [3].
  • the copper corrosion inhibitor is an inorganic inhibitor or an organic inhibitor.
  • the organic inhibitor is selected from the group consisting of polyepoxy ether, polyglycidyl ether, water-soluble silane coupling agent, quinoline, amine, amide and tetrazole.
  • the polyglycidyl ether is selected from the group consisting of glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaeryth little polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and salts thereof [7]. ]
  • the water-soluble silane coupling agent has a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, or a succinic acid anhydride functional group, according to [7].
  • the water-soluble silane coupling agent Vinyl trimethoxysilane, vinyl trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane; p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; 3-Acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethy
  • the inorganic inhibitor is selected from the group consisting of polyphosphates, phosphonates, orthophosphates, silicates, metasilicates, chromates, nitrites, molybtensates and iron or iron ions [6]. ]
  • the composite copper member described in. [12] The composite copper member according to [11], wherein the silicate and the metasilicate are sodium silicate.
  • the organic inhibitor is benzotriazole (BTA) and its derivative; diocalpamic acid and its derivative; thiourea, thioacetamide, thiosemicarbamide, thiophenol, P-thiocresol, thiobenzoic acid, ⁇ mercaptocarboxylic acid derivative (RS).
  • BTA benzotriazole
  • RS mercaptocarboxylic acid derivative
  • the derivatives of the benzotriazole are tortriazole (TTA); 2-mercaptobenzothiazole (MBT); 2,5-dimercaptothiazole (DMTDA); benzimidazole (BIA); benzimidazole thiol (BIT); benzoxazole thiol. (BOT); a mixture of methylbenzothiazole and indol; mercaptothiazoline; 2,2'-[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol (TT-LYK); and salts thereof
  • TTA tortriazole
  • MTT 2-mercaptobenzothiazole
  • DMTDA 2,5-dimercaptothiazole
  • BIOA benzimidazole
  • BIT benzimidazole thiol
  • BOT benzoxazole thiol.
  • the copper oxide copper member surface after removal of the layer containing, specific conductivity with respect to the alternating current of 20GHz is more than 95% of the standard copper plate (oxygen-free copper plate of specific conductivity 5.8 ⁇ 10 7 S / m)
  • the composite copper member according to any one of [1] to [19].
  • An eraser (AW FABER-Castell, N6-W825R) is loaded with 100 g, and the sliding speed is 65 mm / sec, the sliding distance is 25.4 mm, and 3 is placed on the layer containing the copper oxide.
  • the color difference ( ⁇ E * ab) between the surface of the portion before sliding and the surface of the portion after sliding is 50 or less with respect to the surface of the slid portion.
  • a method for manufacturing a composite copper member according to [1]. A method for producing a composite copper member, which comprises a step of forming a layer containing the copper oxide by oxidizing an aqueous solution of an oxidizing agent having a pH of 11.5 to 14 containing a copper corrosion inhibitor.
  • a production method according to [A1] which comprises a step of treating with an alkaline solution having a pH of 9 or higher, which is performed before the step of oxidizing with the aqueous oxidizing agent.
  • [A3] As a compound having an -OH group, an ether group (-O-), or an N atom, in which the copper corrosion inhibitor binds to a copper atom, copper ion, copper hydroxide or copper oxide in the oxidizing agent aqueous solution.
  • [A4] The production method according to [A1] or [A2], wherein the copper corrosion inhibitor is present as a compound having a silanol group, an epoxy group, a glycidyl group, a trizole ring or a thiazole ring in the oxidizing agent aqueous solution.
  • [A5] The production method according to [A1] or [A2], wherein the copper corrosion inhibitor is an inorganic inhibitor or an organic inhibitor.
  • the organic inhibitor is selected from the group consisting of polyepoxy ether; polyglycidyl ether; water-soluble silane coupling agent; and quinoline, amine, amide, tetrazole and salts thereof.
  • the polyglycidyl ether is selected from the group consisting of glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaeryth little polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and salts thereof, [A6. ] The manufacturing method described in.
  • the water-soluble silane coupling agent has a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, or a succinic acid anhydride functional group, in [A6]. The manufacturing method described.
  • the water-soluble silane coupling agent Vinyl trimethoxysilane, vinyl trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane; p-styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; 3-Acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethy
  • the inorganic inhibitor is selected from the group consisting of polyphosphates, phosphonates, orthophosphates, silicates, metasilicates, chromates, nitrites, molybtensates and iron or iron ions [A5]. ] The manufacturing method described in. [A11] The production method according to [A10], wherein the silicate and the metasilicate are sodium silicate.
  • the organic inhibitor is benzotriazole (BTA) and its derivative; diocalpamic acid and its derivative; thiourea, thioacetamide, thiosemicarbamide, thiophenol, P-thiocresol, thiobenzoic acid, ⁇ mercaptocarboxylic acid derivative (RS).
  • BTA benzotriazole
  • RS mercaptocarboxylic acid derivative
  • the derivatives of the benzotriazole are tortriazole (TTA); 2-mercaptobenzothiazole (MBT); 2,5-dimercaptothiazole (DMTDA); benzimidazole (BIA); benzimidazole thiol (BIT); benzoxazole thiol. (BOT); mixture of methylbenzothiazole and indole; mercaptothiazoline; 2,2'-[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol (TT-LYK); and salts thereof
  • TTA tortriazole
  • MTT 2-mercaptobenzothiazole
  • DMTDA 2,5-dimercaptothiazole
  • BIA benzimidazole thiol
  • BOT benzoxazole thiol.
  • FIG. 1 is an SEM cross-sectional image (magnification of 80,000 times) of Comparative Example 2 and Example 7.
  • the dotted line indicates the interface between the copper foil, which is a conductor, and the layer containing the copper oxide.
  • FIG. 2 shows the ratio of Rz to the surface before removing the layer containing copper oxide (A) and the ratio of Rz to the surface after removing the layer containing copper oxide in Examples and Comparative Examples. Indicates conductivity.
  • One embodiment of the present invention is a method for producing a composite copper member in which a layer containing a copper oxide is formed on the surface of at least a part of the copper member.
  • the copper member is a material containing Cu as a main component, which is a part of the structure, and includes copper foil such as electrolytic copper foil, rolled copper foil, and copper foil with a carrier, copper wiring, copper plate, and copper lead frame.
  • Copper is preferably pure copper having a purity of 99.9% by mass or more, more preferably containing tough pitch copper, deoxidized copper, and oxygen-free copper, and has an oxygen content of 0.001% by mass to 0.0005% by mass. It is more preferable to contain oxygen-free copper.
  • the roughness of the surface on which the layer containing the copper oxide is formed in the copper member used for manufacturing the composite copper member disclosed in the present specification is that the maximum height roughness (Rz) is 0.70 ⁇ m or less. preferable.
  • Rz can be calculated by the method specified in JIS B 0601: 2001 (based on international standard ISO13565-1).
  • the method for producing a composite copper member includes a step of forming a layer containing copper oxide on the surface of the copper member with an aqueous solution of an oxidizing agent.
  • the surface of the copper member is oxidized with an aqueous solution of an oxidizing agent to form a layer containing a copper oxide, and fine irregularities are formed on the surface.
  • the oxidation treatment may be a single-sided treatment or a double-sided treatment.
  • degreasing treatment Prior to the oxidation treatment, degreasing treatment, acid cleaning for homogenizing the surface by removing the natural oxide film, or alkali treatment for preventing the introduction of acid into the oxidation step after the acid cleaning may be performed.
  • the method of degreasing treatment is not particularly limited, but it is preferable to immerse the copper member in a sodium hydroxide aqueous solution (30 to 50 g / L) having a liquid temperature of 40 to 60 ° C. for 0.5 to 2 minutes.
  • the method of acid cleaning is not particularly limited, but it is preferable to immerse the copper member in a sulfuric acid aqueous solution (5 to 20% by weight) having a liquid temperature of 20 to 30 ° C. for 1 to 3 minutes.
  • the method of alkaline treatment is not particularly limited, but preferably 0.1 to 10 g / L, more preferably 1 to 2 g / L alkaline aqueous solution, for example, sodium hydroxide aqueous solution, at 30 to 50 ° C., 0.5. It may be processed for about 2 minutes.
  • the alkaline aqueous solution used for the alkaline treatment is preferably pH 8, pH 9, or pH 10 or higher.
  • the oxidizing agent aqueous solution is not particularly limited, and for example, sodium chlorite, potassium chlorate, sodium hypochlorite, potassium hypochlorite, sodium chlorate, potassium chlorate, sodium perchlorate, potassium perchlorate.
  • An aqueous solution containing the above can be used.
  • the oxidation reaction conditions are not particularly limited, but the liquid temperature of the aqueous solution of the oxidizing agent is preferably 40 to 95 ° C, more preferably 45 to 80 ° C.
  • the reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.
  • the pH of the oxidant aqueous solution may be alkaline, but is preferably pH 11.5 or higher, 12.0 or higher, 12.5 or higher or 13 or higher, and preferably pH 14.0 or lower or pH 13.5 or lower at 73 ° C. .. Since the preferable range of pH depends on the measurement temperature, those skilled in the art can appropriately experiment and set it.
  • the oxidant aqueous solution preferably contains a copper corrosion inhibitor.
  • Copper corrosion inhibitors are inorganic or organic compounds, their hydrolyzates, which, when added in small amounts in a corrosive environment, act on either or both of the annotate and cathode reactions to significantly reduce copper corrosion.
  • Salt including acidic salt, basic salt, and positive salt.
  • Corrosion inhibitors react with copper atoms, copper ions (I or II valence), copper hydroxide (I or II) or copper oxide (I or II) to form conjugates and act directly on the copper surface.
  • Copper corrosion inhibitors are classified into inorganic inhibitors or organic inhibitors, and are classified into oxide film type inhibitors, precipitation film type inhibitors, and adsorption film type inhibitors depending on the film formed.
  • the copper corrosion inhibitor is preferably water-soluble. For example, in the case of polyglycerol polyglycidyl ether, 0.20 g / L or more, 0.50 g / L or more, 0.75 g / L or more in an aqueous oxidizing agent solution at 73 ° C.
  • the oxide film type inhibitor can form an oxide film that functions as a blocking film on the copper surface.
  • the oxide film-type inhibitor chromates (e.g., cyclohexyl ammonium chromate ((C 6 H 11 NH 8 ) 2 ⁇ CrO 4)), nitrites (e.g., NaNO 2), molybdenum salts (e.g., Na 2 MoO 4 ⁇ 2H 2 O), and the like of iron and iron ions to form an iron oxide film.
  • chromates e.g., cyclohexyl ammonium chromate ((C 6 H 11 NH 8 ) 2 ⁇ CrO 4)
  • nitrites e.g., NaNO 2
  • molybdenum salts e.g., Na 2 MoO 4 ⁇ 2H 2 O
  • Precipitation film type inhibitors include water ion type inhibitors that can form a blocking film by forming insoluble salts with calcium ions (Ca 2+ ) and magnesium ions (Mg 2+) in water, and copper ions and insoluble. Includes metal ion-type inhibitors capable of producing salts to form a blocking film.
  • the aqueous ion type inhibitor includes phosphates (polyphosphates, phosphonates, orthophosphates), silicates, metasilicates and the like.
  • Specific examples include sodium silicate.
  • An aqueous solution of sodium silicate called water glass or sodium silicate may be added to the aqueous solution of the oxidizing agent.
  • Benzotriazole (BTA) and its derivatives eg, tortriazole (TTA); 2-mercaptobenzothiazole (MBT); 2,5-dimercaptothiazole (DMTDA); benzimidazole (BIA); benzimidazole thiol (BIT); benzoxazolethiol (BOT); mixture of methylbenzothiazole and indole; mercaptothiazoline; and 2,2'-[[(methyl-1H-benztriazole-1-yl) methyl] imino] bisethanol (TT) -LYK));
  • Diocalpamic acid and its derivatives for example, dimethyldithiocarbamate; diethyldithiocarbamate; N-methyldithiocarbamate; ethylene-bisdithiocarbamate); (3) Thiourea, thioacetamide, thiosemicarbamide, thiophenol, P-thio
  • the adsorption film type inhibitor can directly adsorb and / or bind to the copper surface to form a blocking film.
  • adsorption film type inhibitors (1) Water-soluble silane coupling agent; (2) Quinolines, amines (eg octadecialamines and dicyclohexylamines), amides, tetrazole and derivatives thereof (for example, 3-amino1,2,4triazole), and salts thereof; (3) An epoxy monomer or glycidyl monomer having a water-soluble monofunctional or polyfunctional (2, 3, 4 or 5 or more functional) epoxy group or glycidyl group per molecule (for example, polyepoxy ether or polyglycidyl ether). , And their salts.
  • the organic functional group is a functional group having a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, an isocyanate group, an acid anhydride functional group or the like (for example).
  • the "functional group having an epoxy group” includes a glycidyl group).
  • the silane coupling agent depends on the type of organic functional group.
  • Silane coupling agent having a vinyl group for example, vinyltrimethoxysilane, vinylethoxysilane
  • Silane coupling agent having an epoxy group for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxy
  • Silane coupling agent having a styryl group for example, p-styryltrimethoxysilane
  • Silane coupling agent having a methacryl group for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane
  • the water-soluble silane coupling agent is placed in an aqueous oxidant solution at 73 ° C. under alkaline conditions, for example, pH 11.5 to 14, at 0.01 g / L or more, 0.1 g / L or more, 0.5 g / L or more, or.
  • a silane coupling agent capable of dissolving 1 g / L or more is preferable.
  • the water-soluble monofunctional or polyfunctional epoxy polymer or glycidyl polymer is 0.01 g / L or more and 0.1 g / L or more in an aqueous oxidant solution at 73 ° C. under alkaline conditions, for example, pH 11.5 to 14 conditions. , 0.2 g / L or more, or 1 g / L or more soluble epoxy monomer or glycidyl polymer is preferable.
  • Water-soluble monofunctional or polyfunctional epoxy polymers or glycidyl polymers include polyglycidyl ethers (eg, glycerol polyepoxy ethers, trimethylolpropane polyepoxy ethers, pentaeryth little polyepoxy ethers, polyglycerol polyepoxy ethers, and sorbitols.
  • polyglycidyl ethers eg, glycerol polyepoxy ethers, trimethylolpropane polyepoxy ethers, pentaeryth little polyepoxy ethers, polyglycerol polyepoxy ethers, and sorbitols.
  • Polyepoxy ethers and polyglycidyl ethers (eg, glycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, pentaeryth little polyglycidyl ethers, polyglycerol polyglycidyl ethers, and sorbitol polyglycidyl ethers).
  • polyglycidyl ethers eg, glycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, pentaeryth little polyglycidyl ethers, polyglycerol polyglycidyl ethers, and sorbitol polyglycidyl ethers.
  • Copper corrosion inhibitors are copper atoms, copper ions (I or II valence), copper hydroxide (I or II) or copper oxide (I or II) in an oxidant aqueous solution having a pH of 11.5-14. It may be a molecule having an -OH group, an ether group (-O-), and an N atom that can be bonded to.
  • the copper corrosion inhibitor is preferably a molecule having a silanol group, an epoxy group, a glycidyl group, a trizole ring or a thiazole ring in an aqueous oxidizing agent solution.
  • Benzotriazole (BTA) and its derivatives are polymerized by forming a coordinate bond between N atoms constituting the triazole ring, thiazole ring, and the like and copper ions.
  • the alkoxyryl group (-Si (OR) n ) is hydrolyzed in the oxidizing agent aqueous solution to become a silanol group (-Si (OH) n ), and the silanol group reacts with copper. It forms a Si—O—metal (M) bond.
  • the epoxy group or glycidyl group reacts with copper.
  • copper corrosion inhibitors Since many copper corrosion inhibitors have these functional groups, they form conjugate molecules with copper atoms, copper ions, copper hydroxide or copper oxide. It is preferable that one or more of these functional groups or atoms (2, 3, 4, 5 or 6 or more) are contained in one molecule of the copper corrosion inhibitor.
  • copper corrosion inhibitors may be contained alone in the oxidant aqueous solution, or a plurality of types may be contained in the oxidant aqueous solution.
  • a reducing agent for example, dimethylamine borane (DMAB), diborane, sodium borohydride, hydrazine, etc.
  • Dissolving agents eg ethylenediaminetetraacetic acid, diethanolglycine, L-glutamate diacetic acid / tetrasodium, ethylenediamine-N, N'-disuccinic acid, 3-hydroxy-2, 2'-sodium iminodicosuccinate, methylglycine diacetic acid
  • a layer containing a copper oxide formed by an oxidation treatment with 3 sodium, 4 sodium aspartate diacetate, a chelating agent such as N- (2-hydroxyethyl) disodium iminodiacate, sodium gluconate is partially formed.
  • Dissolving treatment to dissolve 3) Metals (for example, Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, Pt, or these Plating treatment to form a plating layer of alloy) (including electrolytic plating, electroless plating, vacuum deposition, chemical conversion treatment, etc.); 4) Coupling agent treatment or rust preventive layer (including benzotriazoles, etc.) that forms a coupling treatment layer (including silane coupling agent, etc.) on the layer containing copper oxide formed by oxidation treatment. Anti-corrosion treatment to form; Such surface treatment may be performed.
  • Metals for example, Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, Pt, or these Plating treatment to form a plating layer of alloy
  • Coupling agent treatment or rust preventive layer including benzotriazoles, etc.
  • a coupling treatment layer including silane coupling agent, etc.
  • the composite copper member according to the embodiment of the present invention can be manufactured.
  • One embodiment of the present invention is a composite copper member in which a layer containing a copper oxide is formed on the surface of at least a part of the copper member.
  • a copper corrosion inhibitor Inside the layer containing copper oxide, it is contained in a copper corrosion inhibitor; a bond molecule of a copper corrosion inhibitor and a copper atom, a copper ion, copper hydroxide or copper oxide; or a copper corrosion inhibitor. It preferably contains atoms.
  • the atoms contained in the corrosion inhibitor of copper are present as a part of the corrosion inhibitor.
  • the surface of the copper member existing under the layer containing the copper oxide (for example, exemplified by the interface shown by the dotted line in FIG. 1) has a small roughness.
  • the roughness of the surface of the copper member existing under the layer containing the copper oxide can be measured after the layer containing the copper oxide layer is dissolved and removed from the composite copper member.
  • the dilute sulfuric acid aqueous solution dissolves only the layer containing the copper oxide, but hardly dissolves in the copper of the copper member.
  • the roughness of the surface of the member can be evaluated as the roughness of the surface of the copper member existing under the layer containing the copper oxide.
  • the Rz on the surface of the copper member existing under the layer containing the copper oxide is preferably 0.10 ⁇ m or more, 0.15 ⁇ m or more, or 0.20 ⁇ m or more, preferably 0.70 ⁇ m or less, 0.65 ⁇ m or less, and 0.
  • Rz is smaller than the skin depth (thickness at which the flowing current is reduced to about 37% as compared with the epidermis) with respect to high frequency.
  • Skin depth oxygen-free copper (specific conductivity: 5.8 ⁇ 10 7 S / m ) For about 2 ⁇ m for alternating current of 1 GHz, about 0.7 ⁇ m for 10GHz alternating current, 20 GHz It is about 0.5 ⁇ m for the alternating current of 40 GHz and about 0.35 ⁇ m for the alternating current of 40 GHz.
  • Rz the value of Rz is smaller than the skin depth, the influence of the surface shape of the conductor on the skin effect is extremely small, and the influence of the lateral parameter of the surface roughness is small.
  • the average length (RSm) of the roughness curve elements of the copper member existing under the layer containing the copper oxide is 2000 nm or less, 1500 nm or less, 750 nm or less, 700 nm or less. It may be 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, and may be 100 nm or more, 200 nm or more, or 300 nm or more.
  • RSm represents the average of the lengths (that is, the lengths of contour curve elements: Xs1 to Xsm) in which unevenness is generated for one cycle included in the roughness curve at a certain reference length (lr), and is represented by the following equation. It is calculated by.
  • 10% of the arithmetic mean roughness (Ra) is defined as the minimum height of the unevenness
  • 1% of the reference length (lr) is defined as the minimum length
  • the unevenness for one cycle is defined.
  • RSm can be measured according to "Method for measuring surface roughness of fine ceramic thin film by atomic force microscope (JIS R 1683: 2007)".
  • the surface roughness of the layer containing the copper oxide is large.
  • the Ra on the surface of the layer containing the copper oxide is preferably 0.10 ⁇ m or less, 0.09 ⁇ m or less, or 0.80 ⁇ m or less, preferably 0.01 ⁇ m or more, 0.02 ⁇ m or more, 0.03 ⁇ m or more, or 0.04 ⁇ m. The above is preferable.
  • the Rz on the surface of the layer containing the copper oxide is preferably 1.00 ⁇ m or less, 0.90 ⁇ m or less, or 0.80 ⁇ m or less, and is 0.10 ⁇ m or more, 0.15 ⁇ m or more, 0.20 ⁇ m or more, or 0.3 ⁇ m.
  • the above is preferable.
  • the RSm on the surface of the layer containing the copper oxide is preferably 1200 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, preferably 100 nm or more, 200 nm or more, or 300 nm or more.
  • the surface roughness of the copper oxide-containing layer is evaluated as the number of protrusions detected on the surface of the copper oxide-containing layer of the composite copper member in a cross-sectional image taken by a scanning electron microscope (SEM). can do.
  • the number of convex parts is not particularly limited, but in the photographed image of the cross section, 15 convex parts having a length of 50 nm or more and 1500 nm or less per 3.8 ⁇ m measured in a direction parallel to the surface of the layer containing copper oxide. As mentioned above, it is preferable that there are 20 or more, 25 or more, or 30 or more.
  • the height of the convex portion is, for example, the distance between the midpoint of the line segment connecting the minimum points of the concave portions adjacent to each other across the convex portion and the maximum point of the convex portion between the concave portions in the SEM cross-sectional image. can do.
  • the specific conductivity of the surface of the composite copper member is preferably good both before and after the removal of the layer containing the copper oxide.
  • the specific conductivity of the surface can be measured by the 1-dielectric cylindrical resonator 2-mode method (1 dielectric resonator method) in accordance with JIS R1627 (1996).
  • the layer containing copper oxide has thread resistance (also referred to as wear resistance).
  • the thread resistance is that the eraser (AW FABER-Castell, N6-W825R) is loaded with 100 g, the sliding speed is 65 mm / sec, the sliding distance is 25.4 mm, and the layer containing copper oxide is used.
  • the surface of the slid portion can be evaluated as a color difference ( ⁇ E * ab) between the surface before sliding and the surface after sliding.
  • the color difference is not particularly limited, but is preferably 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less.
  • the surface of the layer containing the copper oxide has little color unevenness.
  • the color unevenness can be evaluated as the standard deviation of the brightness between the five points when the brightness (L * ) of five points in an arbitrary 80 mm ⁇ 100 mm region is measured.
  • the standard deviation of brightness is not particularly limited, but is preferably 10 or less, 7.5 or less, 5 or less, or 2.5 or less.
  • a metal plating layer, a coupling treatment layer, a rust preventive agent layer, or the like may be formed on the copper oxide-containing layer of the composite copper member as long as the technical features of the present invention are not impaired.
  • the roughened surface of the treated VLP (Very Low Profile) copper foil (Rz 1.7 ⁇ m) was used as it was as the evaluation surface.
  • the copper foils of Examples 1 to 9 and Comparative Examples 1 to 7 and Comparative Example 10 were immersed in a sodium hydroxide aqueous solution at a liquid temperature of 50 ° C. and 40 g / L for 1 minute, and then washed with water.
  • the copper foil subjected to the alkaline degreasing treatment was immersed in a sulfuric acid aqueous solution having a liquid temperature of 25 ° C. and 10% by weight for 2 minutes, and then washed with water.
  • the copper foils of Examples 1 to 9 and Comparative Examples 2 to 7 were immersed in an aqueous solution of sodium hydroxide (1.2 g / L) (pH 10.5) at 40 ° C. for 1 minute, washed with water and dried.
  • the copper foil of Comparative Example 10 was immersed in an aqueous solution of 1.3% sulfuric acid; 0.8% hydrogen peroxide at 30 ° C. for 1 minute, etched, washed with water, and dried.
  • Example 2 Oxidation Treatment
  • the pretreated copper foil was immersed in an aqueous solution of an oxidizing agent to perform oxidation treatment on both sides.
  • Example 1 is an aqueous solution (pH 12) of sodium chlorite 58 g / L; potassium hydroxide 4 g / L; polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX Corporation; Denacol EX-521) as an oxidant aqueous solution. .3) was used.
  • Example 2 an aqueous solution (pH 13.4) of sodium chlorite 58 g / L; potassium hydroxide 20 g / L; polyglycerol polyglycidyl ether 1 g / L was used as the oxidizing agent aqueous solution.
  • Example 3 an aqueous solution (pH 13.4) of sodium chlorite 58 g / L; potassium hydroxide 20 g / L; polyglycerol polyglycidyl ether 2 g / L was used as the oxidant aqueous solution.
  • Example 4 is an aqueous solution (pH 13) of sodium chlorite 58 g / L; potassium hydroxide 20 g / L; tris- (trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Silicone Co., Ltd .; KBM9659) as an oxidant aqueous solution. .4) was used.
  • Example 5 as an oxidant aqueous solution, sodium chlorite 58 g / L; potassium hydroxide 20 g / L; water glass (sodium silicate content 52 to 57% by weight (Wako 1st grade), manufactured by Wako Pure Chemical Industries, Ltd.) A 1 g / L aqueous solution (pH 13.3) was used.
  • Example 9 as an oxidant aqueous solution, an aqueous solution of sodium chlorite 45 g / L; potassium hydroxide 12 g / L; 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd .; KBM403) 2 g / L (pH 13. 4) was used.
  • Comparative Example 7 an aqueous solution of sodium chlorite 58 g / L; potassium hydroxide 20 g / L (pH 13.4) was used as the oxidizing agent aqueous solution.
  • Examples 1 to 6, 8 and 9 and Comparative Examples 2, 3, 5 and 6 were immersed in an aqueous oxidizing agent solution at 73 ° C. for 2 minutes, and Examples 7 and 4 were immersed in an aqueous oxidizing agent solution at 73 ° C. for 4 minutes. Then, Comparative Example 7 was immersed in an aqueous oxidizing agent solution at 73 ° C. for 1 minute. Then it was washed with water and dried.
  • a copper corrosion inhibitor to the oxidant aqueous solution, the etching amount of the copper foil is controlled, and a layer containing a uniform copper oxide having scratch resistance and less color unevenness is formed on the copper foil surface. Will be possible.
  • FIG. 1 shows SEM cross-sectional images of the test pieces of Example 7 and Comparative Example 2.
  • the number of convex portions having a height of 50 nm or more and 1500 nm or less per 3.8 ⁇ m was counted, and the average value of the five pieces was calculated.
  • the length when the waviness of the original member was extended to a flat surface was measured and converted into a length per 3.8 ⁇ m.
  • the sample had a predetermined shape (diameter 40 mm, thickness 18 ⁇ m), and the resonance frequency was set to 20 GHz.
  • (5) High-frequency characteristics Four prepreg NC0207 (25 ⁇ m thick, manufactured by Namics Co., Ltd.) were laminated on the test pieces of the examples and comparative examples, pressed to 1.0 MPa using a vacuum press, and then 200 ° C. Then, by holding for 60 minutes, thermocompression bonding was performed to prepare a macro strip line having a length of 100 mm. The transmission loss in the high frequency band was measured using the produced macro stripline. The transmission characteristics were measured using a known stripline resonator method suitable for measurement in the 0-40 GHz band.
  • the S21 parameter was measured under the following conditions without a coverlay film. Measurement conditions: Microstrip structure; Base material prepreg Adflema NC0207; Circuit length 200 mm; Conductor width 280 ⁇ m; Conductor thickness 28 ⁇ m; Base material thickness 100 ⁇ m; Characteristic impedance 50 ⁇ A high frequency characteristic of ⁇ 0.94 or higher was evaluated as ⁇ , and a high frequency characteristic of less than ⁇ 0.94 was evaluated as ⁇ .
  • Thread resistance A load of 100 g is applied to an eraser (AW FABER-Castell, N6-W825R) on the evaluation surface of the test pieces of Examples and Comparative Examples, and the sliding speed is 65 mm / sec. , Sliding 3 times with a sliding distance of 25.4 mm.
  • Comparative Example 1 the peel strength with the resin base material was small.
  • Comparative Example 2 the Rz of the layer containing the copper oxide is the same as that of Example 7, but the Rz of the copper portion which is the conductor is large, the specific conductivity of the surface is poor, the high frequency characteristics are poor, and the thread resistance. was also low.
  • Comparative Example 3 the peel strength with the resin base material was small, and the color unevenness was also large.
  • Comparative Example 4 the Rz of the copper portion was large, the specific conductivity of the surface was poor, and the thread resistance was also low.
  • RSm was large and the peel strength with the resin base material was small.
  • the Rz of the copper portion was large, the thread resistance was low, and the color unevenness was also large.
  • the peel strength with the resin base material was small, and the color unevenness was also large.
  • the Rz of the copper portion was large, the specific conductivity of the surface was poor, and the high frequency characteristics were also poor.
  • the surface of the copper portion which is a conductor, is smooth, so that it exhibits good specific conductivity and high frequency characteristics, and the formation of copper oxide provides good peel strength with the resin base material. Indicated.
  • the surface ratio is controlled by controlling the roughness of the copper portion existing under the layer containing the copper oxide, not the surface roughness of the layer containing the copper oxide. Good conductivity and high frequency characteristics.
  • the composite copper member according to the present invention is suitable for manufacturing a high frequency (for example, 1 GHz or higher, 10 GHz or higher, 20 GHz or higher, or 40 GHz or higher) alternating current circuit board.
  • a high frequency for example, 1 GHz or higher, 10 GHz or higher, 20 GHz or higher, or 40 GHz or higher

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'objet de la présente invention est de fournir un nouvel élément de cuivre composite. Plus particulièrement, un élément de cuivre composite qui comprend un élément de cuivre et une couche formée sur au moins une partie de la surface de l'élément de cuivre et contenant un oxyde de cuivre, la valeur Rz d'au moins une partie de la surface de l'élément de cuivre allant de 0,20 à 0,70 µm inclus.
PCT/JP2020/027739 2020-04-27 2020-07-16 Élément de cuivre composite WO2021220524A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013534054A (ja) * 2010-07-06 2013-08-29 イーサイオニック・スリーサウザンド・インコーポレーテッド プリント配線板において使用するために、銅表面を処理して有機基板への接着を強化する方法
JP2017048467A (ja) * 2013-09-20 2017-03-09 三井金属鉱業株式会社 銅箔、キャリア箔付銅箔及び銅張積層板
JP2018016886A (ja) * 2016-07-15 2018-02-01 ナミックス株式会社 プリント配線板に用いる銅箔の製造方法
JP2019218602A (ja) * 2018-06-20 2019-12-26 ナミックス株式会社 粗化処理銅箔、銅張積層板及びプリント配線板

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7127861B2 (ja) 2017-11-10 2022-08-30 ナミックス株式会社 複合銅箔

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013534054A (ja) * 2010-07-06 2013-08-29 イーサイオニック・スリーサウザンド・インコーポレーテッド プリント配線板において使用するために、銅表面を処理して有機基板への接着を強化する方法
JP2017048467A (ja) * 2013-09-20 2017-03-09 三井金属鉱業株式会社 銅箔、キャリア箔付銅箔及び銅張積層板
JP2018016886A (ja) * 2016-07-15 2018-02-01 ナミックス株式会社 プリント配線板に用いる銅箔の製造方法
JP2019218602A (ja) * 2018-06-20 2019-12-26 ナミックス株式会社 粗化処理銅箔、銅張積層板及びプリント配線板

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