Classifications

• • 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
• • 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
• • 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
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/48—After-treatment of electroplated surfaces

Definitions

• the present invention relates to metal members.
• the dielectric and conductor When the dielectric and conductor are pressed, they are pressed at a high temperature, so if the heat resistance of the conductor is insufficient, the conductor surface will deteriorate and adhesion to the dielectric cannot be obtained. In addition, since the soldered portion in the substrate manufacturing process becomes hot, the soldering may peel off the surface of the conductor. Furthermore, electronic parts for automobiles and the like are sometimes used at high temperatures, and long-term heat-resistant adhesion is required. In this way, when a conductor is required to have heat resistance, various surface treatments are applied to the metal parts used for the conductor.
• Japanese Patent Application Laid-Open No. 2021-147701 discloses a technique for forming a film made of quaternary metal oxides of chromium, molybdenum, zinc, and nickel and their compounds as a heat-resistant layer on the surface of a conductor so as to suppress the occurrence of blisters even when a heat load is applied by high-temperature press working.
• WO2019/093494 reports a technique for obtaining high heat resistance with low roughness and high adhesion by forming a metal layer on copper oxide.
• heat resistance of the conductor can be improved by bringing the metal foil surface of the inner layer circuit into contact with an acidic treatment liquid containing noble metal ions and copper ions as surface treatment of the inner layer conductor.
• WO2017/138338 discloses that forming an appropriate amount of coupling layer on the surface of a conductor is effective in improving the heat resistance of the conductor.
• Thermoplastic resins are known as dielectrics with excellent electrical properties.
• Thermoplastic resins have excellent electrical properties, but require high-temperature pressing. For example, when laminating with PTFE, it is pressed at a high temperature of 300° C. or higher.
• high-temperature pressing For example, when laminating with PTFE, it is pressed at a high temperature of 300° C. or higher.
• SiC silicon carbide
• the present invention provides a novel metal member.
• One embodiment of the present invention is a metal member containing a first metal, wherein N and Si are detected by elemental analysis of the surface of the metal member by X-ray Photoelectron Spectroscopy (XPS), the value of the atomic number ratio (N/Si) of N and Si is 0.04 or more and 0.8 or less or 0.05 or more and 0.8 or less, and the metal member satisfies any of the following:
• the color difference ⁇ E * ab before and after the alkali metal elution test for the surface is 15 or less.
• It has a second metal layer on the surface, and the area percentage of the hydroxide peak area of the second metal with respect to the total peak area derived from the second metal is 70 Area% or less or 63 Area% or less in waveform separation of the spectrum of the surface by XPS.
• the second metal may be nickel.
• Another embodiment of the present invention is a metal member containing a first metal, wherein the hydroxide and SiOx of the first metal are detected by elemental analysis of the surface of the metal member by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS), and the peak value of SiOx is greater than the peak value of the hydroxide of the first metal. Elemental analysis of the surface by TOF-SIMS may further detect Si and alkali metal, and the Si peak value may be greater than the alkali metal peak value.
• TOF-SIMS Time-of-Flight Secondary Ion Mass Spectrometry
• N and Si are detected by elemental analysis of the surface by X-ray photoelectron spectroscopy (XPS), and the ratio of the number of atoms of N and Si (N/Si) may be 0.04 or more and 0.8 or less, or 0.05 or more and 0.8 or less.
• XPS X-ray photoelectron spectroscopy
• a further embodiment of the present invention is a metal member containing a first metal, having a second metal layer on the surface, wherein SiOx is detected by elemental analysis of the surface of the metal member by TOF-SIMS, and in waveform separation of the spectrum of the surface by X-ray Photoelectron Spectroscopy (XPS), the area percentage of the hydroxide peak area of the second metal with respect to the total peak area derived from the second metal is 70 Area% or less or 6. It is a metal member having a content of 3 Area % or less.
• the second metal may be nickel.
• the amount of alkali metal eluted from the surface may be 0.2 ppm or less.
• a further embodiment of the present invention is a method for manufacturing a metal member using a metal material, the method comprising a first step of treating the metal material with a coupling agent and a second step of treating the metal material with water glass.
• the first step may occur before, after, or before or after the second step.
• a further embodiment of the present invention is a method for manufacturing a metal member using a metal material, comprising a third step of treating the metal material with water glass containing a coupling agent.
• a fourth step of treating the metal material with a coupling agent may be included. The third step may occur before, after, or before or after the fourth step.
• the coupling agent may be one or more selected from the group consisting of 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, and 3-acryloxypropyltrimethoxysilane. .
• a fifth step of oxidizing the metal material and/or a sixth step of plating the metal material may be included before the first step and the second step.
• a fifth step of oxidizing the metal material and/or a sixth step of plating the metal material may be included before the third step and the fourth step.
• FIG. 4 is a diagram showing analysis results of each test piece by TOF-SIMS in an example of the present invention
• FIG. 4 is a diagram showing analysis results of each test piece by TOF-SIMS in a comparative example of the present invention
• the metal material may have metal on the surface, and the portion inside the metal surface may be other than metal, but the inner portion may also be metal and the entire metal material may be made of metal.
• the surface and inner portion of the metal member may be of the same metal or different metals.
• the inside of the metal material is made of the same metal as the metal on the surface, the metal may be uniform throughout as a metal lump.
• the thickness of the metal on the surface is more than 1 nm, but may be 10 nm or more, or 100 nm or more.
• Elemental analysis of the surface of the metal member by Time-of-Flight Secondary Ion Mass Spectrometry preferably detects hydroxides of metals of the same type as the metal on the surface (referred to herein as metal hydroxides) and SiOx.
• metal hydroxides hydroxides of metals of the same type as the metal on the surface
• SiOx hydroxides of metals of the same type as the metal on the surface
• the presence of SiOx improves heat resistance and water resistance when metal is adhered to resin. It is believed that this is because SiOx functions as a protective film against heat and water.
• Metal hydroxides and SiOx can also be detected and analyzed by elemental analysis of metal surfaces by X-ray Photoelectron Spectroscopy (XPS).
• XPS X-ray Photoelectron Spectroscopy
• TOF-SIMS targets molecules within 1 nm from the surface
• XPS targets molecules within several nm to several tens of nm (for example, within 2 nm, 10 nm, or 20 nm) from the surface.
• the analysis conditions are not particularly limited and can be determined appropriately by those skilled in the art.
• the peak value of SiOx is preferably larger than the peak value of metal hydroxide.
• SiOx has the effect of a protective film, and when the metal member is adhered to the resin, the heat resistance and water resistance are improved, and the transmission loss is reduced.
• the metal hydroxide and SiOx are strongly bonded by dehydration condensation, and when the metal hydroxide is greater than the SiOx, a large amount of the metal hydroxide that is not bonded to SiOx remains on the metal surface, and when the metal is adhered to the resin, the adhesive strength is weakened, or when the SiOx and the metal member surface are used as a conductor due to the formation of a minute space between the SiOx and the metal member surface, the transmission loss is deteriorated.
• Si and alkali metals are further detected, and the peak value of Si is preferably larger than the peak value of alkali metals. This reduces the transmission loss when the metal member is used as the conductor.
• the Si adhesion amount on the surface of the metal member is preferably 30 ⁇ g/dm 2 or more, more preferably 35 ⁇ g/dm 2 or more. If the Si adhesion amount is small, SiOx is not formed, or even if it is formed, the amount is small, and the effect as a protective film cannot be obtained.
• the portion where Si exists on the surface of the metal member or the entire metal member is dissolved in an acidic solution, the mass of silicon is measured by high frequency inductively coupled plasma emission spectrometry (ICP emission spectrometry), and the volume is calculated from the density.
• the average thickness and the adhesion amount per unit area can be calculated.
• the total mass of silicon may be measured by dissolving the metal itself having the silicon layer and detecting only the amount of silicon forming the silicon layer.
• the amount of alkali metal ions eluted from the surface of the metal member including the SiOx layer is preferably 0.2 ppm or less, more preferably 0.18 ppm or less, and further preferably 0.10 ppm or less.
• the amount of eluted alkali metal is obtained by measuring the mass of Na, K ions, Li ions, etc. in the eluate by ICP emission spectrometry, and obtaining the total amount.
• the metal member is a thin piece such as a metal foil
• the metal member cut into a size of 40 mm ⁇ 18 mm is used as a test piece, and only the treated surface is immersed in 20 mL of pure water at 121 ° C., 85% humidity, 2 atmospheres, and treated for 60 hours.
• the alkali metal ion is derived from the chemical agent that forms the SiOx layer, it is considered that the alkali metal ion exists in the SiOx layer.
• the more SiO2 the smaller the dielectric loss tangent.
• the dielectric constant of alkali metals is high, it is believed that less alkali metals are preferable from the viewpoint of transmission loss. Also, since alkali metals may corrode metal members, the smaller the content, the better.
• XPS X-ray Photoelectron Spectroscopy
• the amount and composition of each metal and each compound can be measured.
• the amount and composition of each metal and the compound containing the metal can be obtained by waveform separation of Cu2P3, and in the case of nickel, by waveform separation of Ni2P.
• the ratio of the number of atoms of N and Si (N/Si) is preferably 0.04 or more, more preferably 0.05 or more, more preferably 0.24 or more, further preferably 0.33 or more, further preferably 0.39 or more, preferably 0.80 or less, and more preferably 0.54 or less.
• the ratio of the number of atoms of N and Si (N/Si) is less than 0.04, the coupling layer is not formed in an amount suitable for the SiOx layer, resulting in poor adhesion, or insufficient removal of the alkali metal, resulting in poor transmission loss.
• the atomic number ratio (N/Si) of N and Si is greater than 0.80, the SiOx layer is not formed, or the SiOx layer is insufficient, resulting in poor heat resistance and moisture resistance.
• ⁇ E * ab is preferably 15 or less, 14 or less, 13 or less, 12 or less, or 11 or less.
• the standard deviation is preferably 4 or less, more preferably 2 or less, and even more preferably 1.95 or less.
• the treatment conditions are, for example, 121° C. in pure water, 85% humidity, 2 atm, and 60 hours. If SiOx is not bonded to the surface, it is considered that high-temperature and high-humidity processing oxidizes the expression and increases the color difference.
• the metal member disclosed herein may have a layer containing or consisting of a second metal (herein referred to as a second metal layer or a second metal layer) on the surface.
• the second metal is not particularly limited as long as it is different from the metal of the metal member, but is preferably at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au and Pt or an alloy thereof.
• a metal having higher heat resistance than copper such as Ni, Pd, Au and Pt, or an alloy thereof, is preferable in order to have heat resistance.
• nickel and nickel alloys include pure nickel, Ni--Cu alloys, Ni--Cr alloys, Ni--Co alloys, Ni--Zn alloys, Ni--Mn alloys, Ni--Pb alloys, and Ni--P alloys.
• the average thickness of the second metal layer in the vertical direction is not particularly limited, it is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more.
• the thickness is preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 50 nm or less.
• the amount of metal in the second metal layer is expressed as the weight of metal per unit area, it is preferably 0.5 mg/cm 2 or more, more preferably 1.0 mg/cm 2 or more, and even more preferably 1.8 mg/cm 2 or more. Also, it is preferably 100 mg/cm 2 or less, more preferably 80 mg/cm 2 or less, even more preferably 50 mg/cm 2 or less, even more preferably 10 mg/cm 2 or less, and even more preferably 5 mg/cm 2 or less.
• the average thickness of the second metal layer in the vertical direction can be calculated by dissolving the metal forming the second metal layer in an acidic solution, measuring the amount of metal by ICP analysis, and dividing the measured amount by the area of the second metal layer. Alternatively, it can be calculated by melting the metal member itself having the second metal layer and detecting and measuring only the amount of the metal forming the second metal layer.
• the area percentage of the peak area of the hydroxide of the second metal is preferably 70% or less, more preferably 67.8% or less, further preferably 65.0% or less, relative to the sum of the peak areas derived from the second metal (for example, the sum of the peak areas derived from the metal hydroxide, the metal oxide, and the single metal) obtained by waveform separation of the spectrum in elemental analysis of the surface by XPS. It is more preferably 0% or less, more preferably 62.1% or less, more preferably greater than 0%, preferably 20% or more, more preferably 56.4% or more, and 57.2% or more.
• the area percentage of the peak area of the second metal oxide is preferably 25 Area% or less, more preferably 23.7 Area% or less, and even more preferably 22.8 Area% or less with respect to the total peak area derived from the second metal.
• the metal member As the characteristics of the metal member as described above, it is particularly preferable to have any of the following combinations.
• the most important factor is that SiOx is bonded to the surface of the metal member in an appropriate amount with the metal hydroxide, and the less the metal hydroxide, the more preferable, and the less the alkali metal on the surface, the more preferable.
• Elemental analysis of the surface by TOF-SIMS detects metal hydroxides and SiOx, The peak value of SiOx is larger than the peak value of metal hydroxide, Furthermore, Si and an alkali metal are detected on the surface, and the peak value of Si is greater than the peak value of the alkali metal;
• N and SiOx are detected by surface elemental analysis by TOF-SIMS, and N and Si are detected by surface elemental analysis by XPS, and the atomic number ratio (N/Si) of N and Si is 0.04 or more and 0.8 or less or 0.05 or more and 0.8 or less;
• SiOx is detected by elemental analysis of the surface by TOF-SIMS, In waveform separation of the spectrum of the surface by XPS, for the sum of the peak areas derived from the second metal,
• the area percentage of the peak area of the hydroxide of the second metal is 70 Area% or less or 63 Ar ea% or less;
• SiOx is detected by elemental analysis of the surface by TOF-SIMS, In waveform separation of the spectrum of the surface by XPS, for the sum of the peak areas derived from the second metal, The area percentage of the peak area of the hydroxide of the second metal is 70 Area% or less, The amount of alkali metal eluted from the surface is 0.2 ppm or less;
• N and Si are detected by elemental analysis of the surface by XPS,
• the ratio of the number of atoms of N and Si (N/Si) is 0.04 or more and 0.8 or less, or 0.05 or more and 0.8 or less, and the color difference ⁇ E * ab before and after the alkali metal elution test for the surface is 15 or less;
• N and Si are detected by elemental analysis of the surface by XPS,
• the ratio of the number of atoms of N and Si (N/Si) is 0.04 or more and 0.8 or less or 0.05 or more and 0.8 or less, and in waveform separation of the spectrum of the surface by XPS, for the sum of the peak areas derived from the second metal,
• the area percentage of the peak area of the hydroxide of the second metal is 70 Area % or less or 63 Area % or less.
• the arithmetic mean roughness (Ra) of the surface of the metal member including the SiOx layer is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and 5.00 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 0.12 ⁇ m or less.
• the maximum height roughness (Rz) of the surface of the metal member containing the SiOx layer is not particularly limited, but is preferably 0.1 ⁇ m or more, more preferably 0.28 ⁇ m or more, and preferably 20.00 ⁇ m or less, more preferably 10.00 ⁇ m or less, and even more preferably 0.83 ⁇ m or less.
• Ra and Rz can be calculated by the method specified in JIS B 0601:2001 (in accordance with international standards ISO4287-1997).
• Metal material Prepare a metal material whose surface is partly or wholly covered with metal, which is the material of the metal member.
• the metal material only needs to have metal on the surface, and the portion inside the metal surface (that is, the inside of the metal material) may be other than metal, but the inside of the metal material may also be metal, and the entire metal material may consist of metal.
• the thickness of the metal on the surface is more than 1 nm, but may be 10 nm or more, or 100 nm or more.
• the surface metal may be formed by plating.
• the type of metal is not particularly limited, for example, it may be a metal such as Cu, Ni, Zn, Al, Fe, Mg, or an alloy such as a copper alloy, nickel alloy, zinc alloy, aluminum alloy, iron alloy, or magnesium alloy, or may be a binary alloy, a ternary alloy, a quaternary alloy, or the like.
• the type of metal on the metal surface and inside the metal material may be the same or different.
• the surface of the metal material is oxidized to form a metal oxide layer on the surface of the metal material.
• This oxidation treatment roughens the surface of the metal material and increases the adhesiveness to the resin when the metal member is bonded to the resin.
• a roughening treatment such as soft etching or etching may be performed before this oxidation treatment.
• degreasing treatment acid cleaning for uniformizing the surface by removing a natural oxide film, or alkali treatment for preventing acid from being brought into the oxidation process may be performed after acid cleaning.
• the alkali treatment method is not particularly limited, but preferably 0.1 to 10 g/L, more preferably 1 to 2 g/L alkaline aqueous solution, such as sodium hydroxide aqueous solution, at 30 to 50° C. for about 0.5 to 2 minutes.
• the oxidation treatment method is not particularly limited, it may be formed using an oxidizing agent, or may be formed by heat treatment or anodization.
• the oxidizing agent is not particularly limited, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, etc. can be used.
• Various additives eg, phosphates such as trisodium phosphate dodecahydrate
• surface active molecules may be added to the oxidizing agent.
• Surface active molecules include porphyrins, porphyrin macrocycles, extended porphyrins, ring contracted porphyrins, linear porphyrin polymers, porphyrin sandwich coordination complexes, porphyrin sequences, silanes, tetraorgano-silanes, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea) ((l-[3-(Trimethoxysilyl)propyl]u rea)), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)
• phosphates such as trisodium phosphate dodecahydrate
• surface active molecules include porphyrins, porphyrin macrocycles, extended porphyrins, ring-contracted porphyrins, linear porphyrin polymers, porphyrin sandwich coordination complexes, porphyrin sequences, silanes, tetraorgano-silanes, aminoethyl-aminopropyl-trimethoxysilane, 3-aminopropyl)trimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea, (3-aminopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-chlorochlorosilane).
• Examples include propyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane, amines, sugars, and the like.
• I can.
• the liquid temperature 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.
• a dissolving agent may be used to adjust the protrusions on the surface of the oxidized metal material.
• the solubilizing agent used in this dissolving step is not particularly limited, but is preferably a chelating agent, particularly a biodegradable chelating agent, such as ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-sodium iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, and sodium gluconate. etc. can be exemplified.
• the pH of the dissolving agent solution is not particularly limited, it is preferably alkaline, more preferably pH 8 to 10.5, still more preferably pH 9.0 to 10.5, and even more preferably pH
• the surface of this metal oxide layer may be reduced with a reducing agent, in which case cuprous oxide may be formed on the surface of the layer containing the metal oxide.
• a reducing agent in which case cuprous oxide may be formed on the surface of the layer containing the metal oxide.
• the reducing agent used in this reduction step include dimethylamine borane (DMAB), diborane, sodium borohydride, hydrazine and the like.
• the specific resistance value of pure copper is 1.7 ⁇ 10 ⁇ 8 ( ⁇ m)
• the specific resistance value of copper oxide is 1 to 10 ( ⁇ m)
• cuprous oxide is 1 ⁇ 10 6 to 1 ⁇ 10 7 ( ⁇ m).
• the second metal layer can be formed as a plating film by, for example, plating the surface of the metal material or the surface of the metal oxide layer.
• the plating method is not particularly limited, and examples include electrolytic plating, electroless plating, chemical conversion treatment, and vacuum deposition such as sputtering.
• an electric charge is required to partially reduce the oxide of the metal oxide layer, so in order to keep the thickness within a preferable range, it is preferable to apply an electric charge of 15 C/dm 2 or more to 90 C/dm 2 or less.
• the current density is preferably 5 A/dm 2 or less. If the current density is too high, uniform plating becomes difficult, for example, plating concentrates on convex portions.
• the intensity of the electric current may be changed between partly reducing the oxide of the metal oxide layer and coating the plating.
• the bath composition is preferably nickel sulfate (100 g/L to 350 g/L), nickel sulfamate (100 g/L to 600 g/L), nickel chloride (0 g/L to 300 g/L), or a mixture thereof, but may contain sodium citrate (0 g/L to 100 g/L) and boric acid (0 g/L to 60 g/L) as additives.
• the conditions for these plating treatments can be easily adjusted according to the metal to be coated and the desired thickness.
• a method for manufacturing a metal member includes a step of forming SiO X on a metal material.
• the method of forming SiO X is not particularly limited, but water glass treatment is preferred when treating with a liquid. By this treatment, the OH group of the hydroxide contained in the metal material and the water glass are bonded, and the acid resistance in the bond with the resin is enhanced.
• degreasing treatment acid cleaning to make the surface uniform by removing the natural oxide film, or alkali treatment to prevent acid from being brought into the next step after acid cleaning, roughening treatment such as soft etching or etching, oxidation treatment, etc. may be performed.
• Water glasses for treating metallic materials are aqueous solutions of alkali metal silicates.
• Alkali metal silicate is represented by M 2 O.nSiO 2 (wherein M is Na, Li or K), and water glass contains M 2 O and SiO 2 in various proportions.
• the water glass used for treating metal materials is not particularly limited, but n is preferably 2-4.
• the specific method of water glass treatment is not particularly limited, and water glass may be applied to the metal surface with a roller or bar coater, or may be sprayed, or the metal material may be immersed in water glass.
• concentration of M 2 O ⁇ nSiO 2 in water glass is not particularly limited, but may be 0.1% to 20%, 0.5% to 10%, or 2% to 5%.
• the reaction conditions are not particularly limited, the treatment temperature is preferably 10°C to 95°C, more preferably 20°C to 85°C. When treating a metal surface, the treatment temperature is more preferably 50° C. or higher in order to react with hydroxide.
• the treatment time is preferably 1 second to 10 minutes. The water glass treatment may be performed multiple times.
• the metal material After the metal material has been treated with water glass, it is dried. Drying after the treatment may be carried out by blowing off moisture with air or by heating.
• the temperature is preferably 30° C. to 250° C., and more preferably 50° C. or higher in order to form an SiOx layer.
• the heating time is preferably 10 seconds to 60 minutes.
• a coupling agent may be dissolved in water glass for processing metal materials (this solution is hereinafter referred to as a mixed agent).
• concentration of the coupling agent is not particularly limited, it is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9% or more, and preferably 20%, 15% or 10% or less by weight.
• Coupling agent treatment Coupling agents have two or more different functional groups, and the functional groups cause dehydration condensation with hydroxyl groups on the metal surface, chemically bond with organic materials, etc., to bond substances with different functional groups.
• the coupling agent for treating metal materials is not particularly limited, but silane coupling agents are preferred, among which those with 2 or 3 hydrolyzable groups are preferred, and those with methoxy or ethoxy groups as hydrolyzable groups are preferred.
• silane coupling agents are preferred, among which those with 2 or 3 hydrolyzable groups are preferred, and those with methoxy or ethoxy groups as hydrolyzable groups are preferred.
• the specific method of coupling agent treatment is not particularly limited, and the coupling agent solution may be applied to the metal surface with a roller or bar coater, or may be sprayed, or the metal material may be immersed in the coupling agent solution.
• the solvent used for the solution of the coupling agent may be water, an organic solvent, or a mixed solvent thereof.
• concentration of the coupling agent is not particularly limited, it is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9% or more, and preferably 20%, 15% or 10% or less by weight.
• a coupling agent may be dissolved in water glass for treating metal materials (this solution is hereinafter referred to as a mixed agent).
• concentration of the coupling agent is not particularly limited, it is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9% or more, and preferably 20%, 15% or 10% or less by weight.
• drying After treating the metal material with a silane coupling agent solution, dry it.
• the temperature and time for drying are not particularly limited as long as the solvent is completely evaporated, but drying at 70° C. for 1 minute or more is preferable, drying at 100° C. for 1 minute or more is more preferable, and drying at 110° C. for 1 minute or more is more preferable.
• This coupling treatment provides the metal member with an N compound detected by elemental analysis by XPS on the surface of the metal member as described above.
• N compounds include coupling agents and silicone resins containing amino groups, mercapto groups, isocyanurate groups, ureido groups, isocyanate groups, and the like.
• a method for manufacturing a metal member using a metal material includes a first step of treating the metal material with a coupling agent and a second step of treating the metal material with water glass.
• the order of the first step and the second step is not particularly limited as long as both steps are performed at least once. For example, any of the following may be used.
• each treatment may be performed multiple times in succession.
• the effect of enhancing moisture resistance in bonding with the resin is high, and the effect of reducing transmission loss is also high.
• the alkali metal is efficiently removed.
• the SiOx formed in the first step has better reactivity with the reactive group of the coupling agent than the metal member, it is possible to use various coupling agents, and the effect of improving the adhesive strength by the coupling agent is likely to be exhibited.
• the effect of enhancing the heat resistance in bonding with the resin is high.
• the metal hydroxide reacts with the coupling agent to efficiently reduce the amount of the metal hydroxide, and that the coupling agent and water glass are strongly bonded through dehydration condensation.
• the first step is performed before and after the second step, both moisture resistance and heat resistance are enhanced, and transmission loss is effectively reduced.
• mixture treatment When using a mixture, it is possible to simultaneously perform coupling agent treatment and water glass treatment in one treatment (hereinafter referred to as mixture treatment). However, one or more coupling agent treatments may be performed before and/or after the admixture treatment.
• the metal material Before the first step, the metal material may be subjected to the oxidation treatment and/or the second metal layer formation treatment described above.
• the metal member according to the present invention can be suitably used as a member that requires high heat resistance, moisture resistance, and adhesion to resin when metal is adhered to resin.
• metal for example, if copper is used as the metal, copper wiring, copper pillars, and lead frames of printed circuit boards including laminates in which a resin base material is laminated on the copper surface, or positive electrode current collectors and negative electrode current collectors of lithium ion batteries. Can be suitably used.
• the degreased metal material is immersed in a 10% by weight sulfuric acid aqueous solution at a liquid temperature of 25°C for 2 minutes for acid cleaning.
• the oxide film on the metal surface was removed. After that, the metal material was washed with water.
• test pieces 1 to 3, 6 to 9, and 11 were immersed in an aqueous solution of sodium hydroxide 1.2 g/L (pH 10.5) at 40°C for 1 minute to prevent acid contamination in the subsequent oxidation treatment.
• electrolytic plating solution (10 g/L zinc oxide; 115 g/L sodium hydroxide; 5 mL/L 9500A (Nippon Surface Chemical Co., Ltd.); 0.5 mL/L 9500B (Nippon Surface Chemical Co., Ltd.); 10 mL/L Hypersoft (Nippon Surface Chemical Co., Ltd.)) was used to perform electrolytic zinc plating under the conditions described in Table 1 to form a Zn layer on the surface. After that, all test pieces were washed with water at room temperature for 1 minute and then dried.
• Coupling process I The test pieces 2 to 4, 6 and 7 were subjected to the coupling treatment after the electroplating treatment (1-4).
• test piece 5 a commercially available aluminum foil was used as it was without surface treatment such as oxidation treatment or electroplating treatment, and coupling treatment was performed.
• Coupling treatment was performed under the conditions shown in Table 1 by immersing the metal foils of test pieces 2 to 7 in 3 vol% KBE-903 (3-aminopropyltriethoxysilane) (Shin-Etsu Chemical Co., Ltd.). After that, all test pieces were washed with water and dried at 130° C. for 1 minute.
• a potassium silicate aqueous solution (potassium silicate solution (Fuji Film Wako Pure Chemical Industries, Ltd.), potassium silicate 48.5 to 52.5% by weight, SiO / K O ratio 1.8 to 2.2) was used for the test piece 6, and a sodium silicate aqueous solution (sodium silicate 52 to 57% by weight, SiO / Na O ratio 2.06 to 2.31) was used. Also, in test piece 7, water glass containing 3 vol% KBE-903 was used. After that, all test pieces were washed with water and dried at 100° C. for 1 minute.
• the surface shape of the copper foil was measured using a confocal scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.), and Ra and Rz were calculated by the method specified in JIS B 0601: 2001 (in accordance with international standards ISO4287-1997).
• the scan width was 100 ⁇ m
• the scan type was area
• the light source was Blue
• the cutoff value was 1/5.
• the object lens was set to x100
• the contact lens was set to x14
• the digital zoom was set to x1
• the Z pitch was set to 10 nm. Table 2 shows the results.
• the metal member was treated with 12% nitric acid to dissolve the metal member, and the mass of Ni and Si in the eluate was measured using an ICP emission spectrometer 5100 SVDV ICP-OES (manufactured by Agilent Technologies). Then, the volume of Ni was calculated using the density of Ni, and the average thickness of the Ni layer was calculated by dividing the obtained mass and volume by the area of the metal member in which the Ni layer was dissolved. Similarly, for Si, the mass per unit area was calculated. Table 3 shows the results.
• a metal piece was prepared by cutting a metal member into a size of 40 mm ⁇ 18 mm.
• the untreated surface was masked with a masking tape (masking tape for plating 851A: manufactured by 3M), and the elution test was performed only on the treated surface.
• Ten metal pieces were immersed in 20 mL of pure water and treated for 60 hours under the conditions of 121° C., 85% humidity and 2 atmospheres to obtain a metal treatment liquid.
• one side of the metal member not subjected to the surface treatment was soaked with a metal foil with a masking tape attached, and treated with pure water under the same conditions at the same time.
• the resulting treated liquid was subjected to ion chromatography using 940 IC Vario Two ChS/PP and 930 Compact IC Flex Oven/SeS/PP/Deg (manufactured by Metrohm) to measure the eluted amounts of sodium ions and potassium ions. From the measured masses of Na and K, the masses of Na and K detected from the eluate with masking tape applied only to one side of the metal member without surface treatment were subtracted as represented by the following formula, and the mass of Na and K eluted from the metal member and the sum thereof were calculated. Those results are shown in Table 7.
• Amount of alkali metal eluted from test pieces 1 to 11 (mass of alkali metal from test pieces 1 to 11) - (mass of metal eluted from metal members without surface treatment)
• the ratio of (initial peel strength - peel strength after heat treatment) to the initial peel strength (referred to as peel strength reduction rate after heat treatment in Table 9) was calculated.
• test piece was prepared by cutting into a size of 25 mm ⁇ 25 mm after thermocompression bonding.
• the metal member and the resin were peeled off from the test piece that had been immersed in a solder bath at a temperature of 300° C. for 5 minutes, and the peeled surface on the metal member side was observed. If the resin adhered to 50 Area% or more of the peeled surface, it was evaluated as being broken inside the resin.
• a metal member that satisfies any one of the above, it is possible to manufacture a metal member having high heat resistance in bonding with a resin.
• a specific manufacturing method for example, it can be manufactured by treating the surface of the metal material with water glass.
• test pieces 2 to 7 had a peel strength reduction rate of 15% or less after heat treatment, and had high heat resistance in adhesion to the resin. in this way,
• test pieces 1 to 7 had a peel strength reduction rate of 20% or less after wet treatment and were excellent in moisture resistance. in this way,
• N and Si are detected in surface elemental analysis by XPS, and the atomic number ratio (N/Si) of N and Si is 0.05 or more and 0.8 or less;
• the peak of the SIOX is detected (see Table 5 [1]), and in the elemental analysis of the surface by XPS, if the NI2p is separated, the peak area of the NI compound (including NI, NI oxide, NI hydroxide) is overtaken.
• the percentage of the peak area of the NI hydroxide is 70AREA % or less (see Table 6), and the elutment of alkali metals from the surface is 0.2 ppm or less (see Table 7);
• a metal member that satisfies any one of the above, it is possible to manufacture a metal member having high moisture resistance in bonding with a resin.
• a specific manufacturing method for example, it can be manufactured by subjecting the metal surface to a coupling agent treatment independently of the water glass treatment.
• test pieces 2 to 6 had a peel strength reduction rate of 10% or less after wet treatment, and had excellent moisture resistance in adhesion to the resin.
• Test pieces 1 to 3, 6 to 9, and 11 and TU-933P+ with a thickness of 100 ⁇ m were laminated and thermocompressed using a vacuum high pressure press to prepare a microstrip line with a length of 100 mm.
• the circuit width was 230 ⁇ m and the characteristic impedance was 50 ⁇ .
• N5227B Keysight Technologies Inc.
• WR12 VDI Inc.
• S 21 (dB) 20 ⁇ log (Vout/Vin)
• Test pieces 1 to 3, 6 and 7 had S 21 per 1 mm greater than -0.075, and had less transmission loss than test pieces 8, 9 and 11. In this way, by performing the coupling agent treatment on the metal surface independently of the water glass treatment and fabricating a metal member that satisfies the conditions [1] [2] [3] in Table 5, a metal member with little transmission loss can be fabricated.
• a novel metal member can be provided by the present invention.

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• 2022
  • 2022-12-26 WO PCT/JP2022/048018 patent/WO2023140062A1/ja active Application Filing
  • 2022-12-26 JP JP2023575163A patent/JPWO2023140062A1/ja active Pending
• 2023
  • 2023-01-11 TW TW112101217A patent/TW202330256A/zh unknown

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