WO2020217738A1 - Solution de placage eutectoïde - Google Patents

Solution de placage eutectoïde Download PDF

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Publication number
WO2020217738A1
WO2020217738A1 PCT/JP2020/009843 JP2020009843W WO2020217738A1 WO 2020217738 A1 WO2020217738 A1 WO 2020217738A1 JP 2020009843 W JP2020009843 W JP 2020009843W WO 2020217738 A1 WO2020217738 A1 WO 2020217738A1
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WO
WIPO (PCT)
Prior art keywords
mass
less
plating solution
silicon oxide
group
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PCT/JP2020/009843
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English (en)
Japanese (ja)
Inventor
直裕 加藤
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三菱鉛筆株式会社
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Publication of WO2020217738A1 publication Critical patent/WO2020217738A1/fr

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Classifications

    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • 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

Definitions

  • the present invention relates to an eutectoid plating solution.
  • plating techniques such as electrolytic plating and electroless plating are widely used as techniques for forming a film on the surface of a member.
  • eutectoid plating in which a plating reaction is performed with a plating solution containing wear-resistant particles such as silicon carbide particles is known.
  • wear-resistant particles such as silicon carbide particles
  • corrosion resistance it is possible to impart new functions such as wear resistance, lubricity, and corrosion resistance to the plating film depending on the properties of the contained particles. Therefore, especially for engine parts such as automobiles and aircraft. It is often used for substrates that require wear resistance and hardness, such as connectors that slide frequently, and various means for such eutectoid plating have been proposed.
  • Patent Document 1 is characterized by comprising a step of adsorbing a cationic surfactant on silicon carbide particles and a step of dispersing the silicon carbide particles adsorbing the cationic surfactant in a plating solution.
  • a method for producing a liquid is disclosed.
  • Patent Document 2 water-insoluble inorganic or organic fine particle powder is dispersed in an aqueous medium together with an azo surfactant having an aromatic azo compound residue, added to a metal plating bath, and electrolyzed.
  • Composite plating of the fine powder and metal A composite plating method characterized by forming a metal film has been proposed.
  • the present invention is as follows: ⁇ 1> An eutectoid plating solution containing at least water, a titanium coupling agent having an amino group, silicon oxide particles, and a metal source. ⁇ 2> The eutectoid plating solution according to item 1, wherein the titanium coupling agent has an alkoxy group and an aminoalkoxy group. ⁇ 3> An aqueous dispersion containing at least water, a titanium coupling agent having an amino group, and silicon oxide particles.
  • kit. ⁇ 5> A plated product coated with a plating layer containing at least a titanium coupling agent having an amino group, silicon oxide, and a metal.
  • the eutectoid plating solution of the present invention contains at least water, a titanium coupling agent having an amino group, silicon oxide particles, and a metal source.
  • the eutectoid plating solution of the present invention may be an electrolytic plating solution or an electroless plating solution.
  • the content of silicon oxide in the eutectoid plating solution is 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.01% by mass based on the entire mass of the eutectoid plating solution.
  • the above may be 0.03% by mass or more, 0.05% by mass or more, or 0.07% by mass or more, and 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.5% by mass or less. , 0.3% by mass or less, or 0.2% by mass or less.
  • the content of the titanium coupling agent in the eutectoid plating solution is 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.01 based on the total mass of the eutectoid plating solution. It may be 5% by mass or more, 0.03% by mass or more, 0.05% by mass or more, or 0.07% by mass or more, and 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.5% by mass. % Or less, 0.3% by mass or less, or 0.2% by mass or less.
  • the ratio of the mass of the titanium coupling agent in the eutectoid plating solution to the mass of silicon oxide is 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 50% or more. It may be 70% or more, 100% or more, 130% or more, 150% or more, 200% or more, 250% or more, or 280% or more, and 1000% or less, 900% or less, 800% or less, 700% or less, It may be 600% or less, 500% or less, 400% or less, 350% or less, or 330% or less.
  • the eutectoid plating solution may contain other particles.
  • the water may be ion-exchanged water, distilled water, or the like.
  • the titanium coupling agent is a titanium coupling agent having an amino group.
  • the "titanium coupling agent” has a hydrolyzable group and a hydrophilic organic functional group bonded to a titanium atom, whereby the hydrolyzable group is obtained by hydrolysis. It refers to a compound in which a hydroxyl group chemically bonds with an inorganic material and a hydrophilic organic functional group imparts hydrophilicity.
  • the present inventors adsorb the titanium coupling agent on the surface of the silicon oxide particles and act as a dispersant, so that these are dispersed in the plating solution and the silicon oxide particles are well dispersed in the plating. We have found that layers can be formed.
  • silicon oxide particles having an arbitrary average particle size particularly silicon oxide particles having an average particle size of 150 nm or less, can be satisfactorily dispersed, whereby the plating layer can be dispersed.
  • silicon oxide particles having an average particle size of 150 nm or less can be satisfactorily dispersed, whereby the plating layer can be dispersed.
  • a sufficient amount of silicon oxide particles can be evenly distributed in the plating layer.
  • the titanium coupling agent may have an alkoxy group as a hydrolyzing group and an aminoalkoxy group as a hydrophilic organic functional group.
  • the titanium coupling agent has 1 alkoxy group and 3 aminoalkoxy groups, 2 alkoxy groups and 2 aminoalkoxy groups, or 3 alkoxy groups and 1 aminoalkoxy group.
  • the alkoxy group may be, for example, a linear or branched alkoxy group having 1 to 10 carbon atoms, for example, an n-methoxy group, an n-ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, sec. -It may be a butoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a neopentoxy group, a tert-pentoxy group, a hexoxy group, an isohexoxy group and the like.
  • the aminoalkoxy group may have a structure in which an amino group is bonded to the terminal of the alkoxy group, particularly a structure in which an amino group is bonded to the terminal of the alkoxy group, and the hydrogen of this amino group is a substituent such as an alkyl group. It may be substituted, and a substituent such as a hydroxyl group or another amine group may be present at the end of this substituent.
  • the aminoalkoxy group may be, for example, a monoethanolamine group, a diethanolamine group, a triethanolamine group, a titanium aminoethylaminoethoxy group or the like.
  • titanium coupling agent having an alkoxy group and an aminoalkoxy group examples include titanium diisopropoxybis (triethanolaminete), titaniumdiethanolamineate, titaniumaminoethylaminoetanolate, and di-n-butoxybis (triethanolamine). Minato) Titanium or the like can be used.
  • the silicon oxide particles may be commercially available silicon oxide particles.
  • the "silicon oxide particles” mean particles containing silicon oxide in at least a part of the surface. Examples of such silicon oxide particles include pure silicon oxide particles, particles in which silicon oxide is present on the entire surface or a part of the surface, and the like.
  • Silicon oxide particles in which silicon oxide is present on the entire surface or a part of the surface can be obtained, for example, by oxidizing the silicon carbide particles.
  • the content of silicon oxide in such silicon oxide particles is 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more. , 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, and 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass.
  • it may be 60% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less.
  • This content can be measured, for example, by measuring the mass change before and after the oxidation of silicon carbide.
  • the average particle size of the silicon oxide particles may be 10 nm or more, 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, or 100 nm or more, and 100 ⁇ m or less, 50 ⁇ m or less.
  • ⁇ m or less 20 ⁇ m or less, 10 ⁇ m or less, 7 ⁇ m or less, 5 ⁇ m or less, 3 ⁇ m or less, 1 ⁇ m or less, 700 nm or less, 500 nm or less, 400 nm or less, 370 nm or less, 350 nm or less, 330 nm or less, 300 nm or less, 270 nm or less, 250 nm or less, 230 nm
  • it may be 200 nm or less, or 150 nm or less.
  • the average particle size referred to here is appropriately selected according to the size of the target silicon oxide particles, and in the case of particles smaller than about 1 ⁇ m, the average particle size of the histogram based on the scattering intensity distribution measured by the dynamic light scattering method (D50). ), And in the case of particles of 1 ⁇ m or more, it is the value of D50 calculated by the volume standard in the laser diffraction method.
  • D50 dynamic light scattering method
  • the metal source may be in various forms depending on the metal to be the plating layer, the mode of plating, and the like.
  • the metal source is not particularly limited, for example, a metal salt of a metal to be used as a plating layer, for example, an inorganic acid salt such as sulfate, hydrochloride, pyrophosphate, sulfamic acid, an organic acid salt such as cyanide salt, or the like. Can be used.
  • the metal to be used as the plating layer may be, for example, copper, nickel, chromium, zinc, tin, silver, gold or the like.
  • a pH adjuster for example, a pH buffer, a brightener and the like can be used.
  • the eutectoid plating solution may contain an electrolyte.
  • the eutectoid plating solution may contain a reducing agent.
  • the reducing agent include sulfates, hydrochlorides, pyrophosphates, phosphinates, sulfamates, tetrahydroborates and other inorganic acid salts, and cyanide salts and other organic acid salts of alkali metals or alkaline earth metals.
  • the reducing agent for example, dimethylamine borane, hydrazine, titanium trichloride and the like can be used.
  • the eutectoid plating solution may contain a complexing agent.
  • a complexing agent for example, carboxylic acids such as acetic acid, lactic acid, oxalic acid, malonic acid, malic acid and tartaric acid, amino acids such as glycine, alanine and asparagine can be used.
  • the aqueous dispersion contains at least water, a titanium coupling agent having an amino group, and silicon oxide particles.
  • This aqueous dispersion may be an aqueous dispersion for producing an eutectoid plating solution.
  • the aqueous dispersion can be produced, for example, by stirring and mixing water, a titanium coupling agent having an amino group, and silicon oxide particles, and dispersing this with a bead mill or the like.
  • the content of silicon oxide in the aqueous dispersion is 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, and 2% by mass based on the total mass of the aqueous dispersion. % Or more, 3% by mass or more, 5% by mass or more, or 7% by mass or more, and 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15 It may be 1% by mass or less, or 13% by mass or less.
  • the content of the titanium coupling agent in the aqueous dispersion is 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass based on the entire mass of the aqueous dispersion. 1 mass% or more, 2 mass% or more, 3 mass% or more, 5 mass% or more, or 7 mass% or more, and 50 mass% or less, 40 mass% or less, 30 mass% or less, 25 mass % Or less, 20% by mass or less, 15% by mass or less, or 13% by mass or less.
  • ⁇ Other particles include, for example, Al 2 O 3 , Cr 2 O 3 , Fe 2 O 3 , TiO 2 , ZrO 2 , ThO 2 , CeO 2 , BeO 2 , MgO, CdO, diamond, SiC, TiC, WC, etc.
  • PTFE polystyrene
  • polypropylene polycarbonate
  • polyamide polyacrylonitrile
  • polypyrrole polyaniline
  • acetyl cellulose polyvinyl acetate, polyvinyl butyral, or a copolymer (polymer of methyl methacrylate and methacrylic acid)
  • these other particles can be used alone or in combination.
  • the kit for producing an eutectoid plating solution contains the above-mentioned aqueous dispersion and a metal plating solution.
  • An eutectoid plating solution can be prepared by mixing the aqueous dispersion and the metal plating solution.
  • the content of the aqueous dispersion is 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, or 0.7% by mass or more, based on the total mass of the eutectoid plating solution. It may be 10% by mass or less, 7% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less.
  • the metal plating solution contains at least a metal source. Further, the metal plating solution may contain other components mentioned with respect to the eutectoid plating solution. As such a metal plating solution, a commercially available metal plating solution can be used depending on the purpose of plating.
  • the plated product is coated with a plating layer containing at least a titanium coupling agent having an amino group, silicon oxide, and a metal.
  • This plating layer can be formed by an electrolytic plating method or an electroless plating method using, for example, the above-mentioned eutectoid plating solution.
  • the metal constituting the plating layer may be, for example, copper, nickel, chromium, zinc, tin, silver, gold, or an alloy thereof.
  • ⁇ Preparation of aqueous dispersion >> ⁇ Example 1> 10 parts by mass of silicon oxide particles having an average particle diameter of 100 nm obtained by oxidizing silicon carbide particles, titanium triethanol aminate (organics) referred to in Table 1 as an amino group-containing titanium coupling agent (TiCP) -A. TC-400, Matsumoto Fine Chemical Co., Ltd., active ingredient 79%) 3.0 parts by mass, and 87.0 parts by mass of ion-exchanged water were stirred and mixed to make a uniform state, and then this was put into a paint shaker (0.3 mm diameter).
  • TiCP titanium triethanol aminate
  • the aqueous dispersion of Example 1 was prepared by dispersing the particles using (Zirconia beads) for a dispersion time of 2 hours.
  • the content of silicon oxide in the silicon oxide particles obtained by oxidizing the silicon carbide particles was 40% by mass.
  • Examples 2 to 11, Comparative Examples 1 to 7 and Reference Example> Water dispersions of Examples 2 to 11, Comparative Examples 1 to 7 and Reference Examples were prepared in the same manner as in Example 1 with the configurations shown in Table 1.
  • Amino Group-Containing TiCP-B Titanium Diethanol Aminate (Organics TC-500, Matsumoto Fine Chemicals Co., Ltd., 70% Active Ingredient)
  • Amino Group-Containing TiCP-C Titanium Aminoethyl Amino Etalate (Organic TC-510, Matsumoto Fine Chemical Co., Ltd., 70% Active Ingredient)
  • Amino group-containing TiCP-D tert-butoxy-bis (triethanolamine) titanium (TAT, Nippon Soda Co., Ltd., active ingredient 77%)
  • Cationic surfactant Comb-type amine-based weak cation (Hypermer KD2, Croda, 100% active ingredient)
  • Silane coupling agent 3-aminopropyltriethoxysilane (KBE-903, Shin-Etsu Chemical, 100% active ingredient)
  • Amino group-free TiCP Titanium lactate ammonium salt (Organics TC-500, Matsumoto
  • the silicon oxide particles obtained by oxidizing the silicon carbide particles are referred to as "oxidation”, and the pure silicon oxide particles are referred to as “elemental substance”. Is mentioned.
  • Preparation of plating solution and plating layer >> 1 part by mass of each of the prepared dispersions was mixed with 99 parts by mass of a diluted plating solution (SC-93-0, Japan Kanigen Co., Ltd .: 19.8 parts by mass plus 79.2 parts by mass of distilled water). To prepare an eutectoid plating solution.
  • SC-93-0 Japan Kanigen Co., Ltd .: 19.8 parts by mass plus 79.2 parts by mass of distilled water.
  • an iron substrate with a thickness of 500 ⁇ m was coated with a plating layer by electroless plating.
  • the surface of the plating layer was rubbed 60 times with a load of 200 g using a high carbon chromium bearing steel (SUJ2) sphere having a diameter of 10 mm.
  • the depth of the scratch formed by rubbing was measured with a surface shape measuring machine (Tarisurf CCI).
  • the evaluation criteria are as follows. A: Less than 500 nm B: 500 nm or more and less than 2000 nm C: 2000 nm or more and less than 4000 nm D: 4000 nm or more
  • Table 1 shows the configurations and evaluation results of Examples and Comparative Examples.
  • the ratio of the mass of the titanium coupling agent in the eutectoid plating solution to the mass of silicon oxide is referred to as "D / P”.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Cette solution de placage eutectoïde comprend au moins de l'eau, un agent de couplage au titane ayant un groupe amino, des particules d'oxyde de silicium et une source métallique.
PCT/JP2020/009843 2019-04-24 2020-03-06 Solution de placage eutectoïde WO2020217738A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019083188A JP2020180326A (ja) 2019-04-24 2019-04-24 共析めっき液
JP2019-083188 2019-04-24

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WO2020217738A1 true WO2020217738A1 (fr) 2020-10-29

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61250179A (ja) * 1985-04-26 1986-11-07 Nisshin Steel Co Ltd 高耐食性着色ステンレス鋼
JPS6283478A (ja) * 1985-10-09 1987-04-16 Sumitomo Metal Ind Ltd 塗装密着性に優れたクロメ−ト処理鋼材
JPH10212598A (ja) * 1997-01-28 1998-08-11 Osaka Gas Co Ltd 複合メッキ被膜、複合メッキ液および複合メッキ被膜の形成方法
JP2000212758A (ja) * 1999-01-18 2000-08-02 Inoac Corp 無電解めっき層を備える積層品及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61250179A (ja) * 1985-04-26 1986-11-07 Nisshin Steel Co Ltd 高耐食性着色ステンレス鋼
JPS6283478A (ja) * 1985-10-09 1987-04-16 Sumitomo Metal Ind Ltd 塗装密着性に優れたクロメ−ト処理鋼材
JPH10212598A (ja) * 1997-01-28 1998-08-11 Osaka Gas Co Ltd 複合メッキ被膜、複合メッキ液および複合メッキ被膜の形成方法
JP2000212758A (ja) * 1999-01-18 2000-08-02 Inoac Corp 無電解めっき層を備える積層品及びその製造方法

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