WO2020217738A1 - Eutectoid plating solution - Google Patents

Eutectoid plating solution Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
mass
less
plating solution
silicon oxide
group
Prior art date
Application number
PCT/JP2020/009843
Other languages
French (fr)
Japanese (ja)
Inventor
直裕 加藤
Original Assignee
三菱鉛筆株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱鉛筆株式会社 filed Critical 三菱鉛筆株式会社
Publication of WO2020217738A1 publication Critical patent/WO2020217738A1/en

Links

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”.

Landscapes

  • 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

This eutectoid plating solution includes at least water, a titanium coupling agent having an amino group, silicon oxide particles, and a metal source.

Description

共析めっき液Eutectoid plating solution
　本発明は、共析めっき液に関する。 The present invention relates to an eutectoid plating solution.
　種々の分野の製品の製造において、部材の表面に皮膜を形成するための技術として、電解めっき及び無電解めっき等のめっき技術が広く用いられている。 In the manufacture of products in various fields, plating techniques such as electrolytic plating and electroless plating are widely used as techniques for forming a film on the surface of a member.
　また、近年では、炭化ケイ素粒子等の耐摩耗性粒子を含むめっき液でめっき反応を行う共析めっきが知られている。このような共析めっきでは、含有される粒子の性質によってめっき被膜に耐摩耗性、潤滑性、耐食性等の新たな機能を付与することが可能であるため、特に自動車や航空機等のエンジン部品や摺動頻度の高いコネクター等、耐摩耗性や硬度が求められる基材に用いられることが多く、かかる共析めっきのための種々の手段が提案されている。 Further, in recent years, eutectoid plating in which a plating reaction is performed with a plating solution containing wear-resistant particles such as silicon carbide particles is known. In such eutectoid plating, 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.
　特許文献１では、炭化ケイ素粒子にカチオン性界面活性剤を吸着させる工程と、めっき液に前記カチオン性界面活性剤を吸着した炭化ケイ素粒子を分散する工程と、を備えることを特徴とする複合めっき液の製造方法が開示されている。 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.
　特許文献２では、非水溶性の無機又は有機の微粒末を、芳香族アゾ化合物残基を有するアゾ界面活性剤とともに水媒体中に分散させて金属めっき浴に添加し、電解を行うことにより、前記微粉末と金属との複合めっき金属膜を形成することを特徴とする複合めっき方法が提案されている。 In 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.
特開２０１３－２４１６４９号公報Japanese Unexamined Patent Publication No. 2013-241649 特開２００１－２４７９９８号公報Japanese Unexamined Patent Publication No. 2001-247998
　特許文献１及び２による手段によっても、炭化ケイ素粒子の十分な分散性が得られず、その結果、得られためっき層中で炭化ケイ素粒子が偏在しているか、又はめっき層が良好に形成できないことがあった。 Sufficient dispersibility of the silicon carbide particles cannot be obtained by the means according to Patent Documents 1 and 2, and as a result, the silicon carbide particles are unevenly distributed in the obtained plating layer, or the plating layer cannot be formed well. There was something.
　そこで、良好な耐摩耗性層を形成することができ、かつ取り扱いが容易である、新規な共析めっき液を提供する必要性が存在する。 Therefore, there is a need to provide a new eutectoid plating solution that can form a good wear-resistant layer and is easy to handle.
　本発明者らは、鋭意検討したところ、以下の手段により上記課題を解決できることを見出して、本発明を完成させた。すなわち、本発明は、下記のとおりである：
　〈１〉水、アミノ基を有するチタンカップリング剤、酸化ケイ素粒子、及び金属源を少なくとも含有している、共析めっき液。
　〈２〉前記チタンカップリング剤が、アルコキシ基及びアミノアルコキシ基を有している、項目１に記載の共析めっき液。
　〈３〉水、アミノ基を有するチタンカップリング剤、及び酸化ケイ素粒子を少なくとも含有している、水分散液。
　〈４〉水、アミノ基を有するチタンカップリング剤、及び酸化ケイ素粒子を少なくとも含有している、水分散液、並びに
　金属源を少なくとも含有している金属めっき液
を含む、共析めっき液作製用キット。
　〈５〉アミノ基を有するチタンカップリング剤、酸化ケイ素、及び金属を少なくとも含有しているめっき層で被覆されている、めっき物。 As a result of diligent studies, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention. That is, 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.
<4> For producing an eutectoid plating solution containing water, a titanium coupling agent having an amino group, and an aqueous dispersion containing at least silicon oxide particles, and a metal plating solution containing at least a metal source. 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.
　本発明によれば、良好な耐摩耗性層を形成することができ、かつ取り扱いが容易である、新規な共析めっき液を提供することができる。 According to the present invention, it is possible to provide a novel eutectoid plating solution capable of forming a good wear-resistant layer and being easy to handle.
　《共析めっき液》
　本発明の共析めっき液は、水、アミノ基を有するチタンカップリング剤、酸化ケイ素粒子、及び金属源を少なくとも含有している。本発明の共析めっき液は、電解めっき液であってもよく、又は無電解めっき液であってもよい。 << Eutectoid plating solution >>
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.
　共析めっき液中の酸化ケイ素の含有率は、共析めっき液の質量全体を基準として、０．００１質量％以上、０．００３質量％以上、０．００５質量％以上、０．０１質量％以上、０．０３質量％以上、０．０５質量％以上、又は０．０７質量％以上であってよく、また５質量％以下、３質量％以下、１質量％以下、０．５質量％以下、０．３質量％以下、又は０．２質量％以下であってよい。 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.
　共析めっき液中のチタンカップリング剤の含有率は、共析めっき液の質量全体を基準として、０．００１質量％以上、０．００３質量％以上、０．００５質量％以上、０．０１質量％以上、０．０３質量％以上、０．０５質量％以上、又は０．０７質量％以上であってよく、また５質量％以下、３質量％以下、１質量％以下、０．５質量％以下、０．３質量％以下、又は０．２質量％以下であってよい。 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.
　共析めっき液中のチタンカップリング剤の質量の、酸化ケイ素の質量に対する比は、１％以上、３％以上、５％以上、１０％以上、２０％以上、３０％以上、５０％以上、７０％以上、１００％以上、１３０％以上、１５０％以上、２００％以上、２５０％以上、又は２８０％以上であってよく、また１０００％以下、９００％以下、８００％以下、７００％以下、６００％以下、５００％以下、４００％以下、３５０％以下、又は３３０％以下であってよい。 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.
　また、共析めっき液は、他の粒子を含有していてもよい。 Further, the eutectoid plating solution may contain other particles.
　以下では、本発明の各構成要素について説明する。 Hereinafter, each component of the present invention will be described.
　〈水〉
　水は、イオン交換水、蒸留水等であってよい。 <water>
The water may be ion-exchanged water, distilled water, or the like.
　〈チタンカップリング剤〉
　チタンカップリング剤は、アミノ基を有するチタンカップリング剤である。ここで、本発明において、「チタンカップリング剤」とは、チタン原子に結合している加水分解性基及び親水性有機官能基を有し、それによって加水分解性基が加水分解して得られる水酸基が無機材料と化学結合し、かつ親水性有機官能基が親水性を与える化合物に言及するものである。 <Titanium coupling agent>
The titanium coupling agent is a titanium coupling agent having an amino group. Here, in the present invention, 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.
　本発明者らは、上記のチタンカップリング剤が酸化ケイ素粒子の表面に吸着して分散剤として作用することにより、これらがめっき液中で分散し、酸化ケイ素粒子が良好に分散しているめっき層を形成することができることを見出した。 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.
　上記のチタンカップリング剤をめっき液中に分散させることによって、任意の平均粒子径の酸化ケイ素粒子、特に平均粒子径１５０ｎｍ以下の酸化ケイ素粒子を良好に分散させることができ、それによって、めっき層を形成したときに、十分な量の酸化ケイ素粒子をめっき層中に均等に分布させることができる。 By dispersing the above titanium coupling agent in the plating solution, 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. When the above is formed, a sufficient amount of silicon oxide particles can be evenly distributed in the plating layer.
　チタンカップリング剤は、加水分解基としてのアルコキシ基及び親水性有機官能基としてのアミノアルコキシ基を有していてよい。この場合、チタンカップリング剤は、１個のアルコキシ基及び３個のアミノアルコキシ基、２個のアルコキシ基及び２個のアミノアルコキシ基、又は３個のアルコキシ基及び１個のアミノアルコキシ基を有していてよいが、２個以上のアミノアルコキシ基を有していることが、酸化ケイ素粒子の分散性を良好にする観点から好ましい。 The titanium coupling agent may have an alkoxy group as a hydrolyzing group and an aminoalkoxy group as a hydrophilic organic functional group. In this case, 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. However, it is preferable to have two or more aminoalkoxy groups from the viewpoint of improving the dispersibility of the silicon oxide particles.
　アルコキシ基は、例えば炭素数１～１０の直鎖又は分枝のアルコキシ基であってよく、例えばｎ－メトキシ基、ｎ－エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ｎ－ペントキシ基、イソペントキシ基、ネオペントキシ基、ｔｅｒｔ－ペントキシ基、ヘキソキシ基、イソヘキソキシ基等であってよい。 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.
　アミノアルコキシ基は、アルコキシ基の末端にアミノ基が結合した構造、特にアルコキシ基の末端にアミノ基が結合した構造を有していてよく、このアミノ基の水素は、アルキル基等の置換基で置換されていてもよく、またこの置換基の末端には、ヒドロキシル基、別のアミン基等の置換基が存在してよい。かかるアミノアルコキシ基としては、例えばモノエタノールアミン基、ジエタノールアミン基、トリエタノールアミン基、チタンアミノエチルアミノエトキシ基等であってよい。 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.
　アルコキシ基及びアミノアルコキシ基を有するチタンカップリング剤としては、例えばチタンジイソプロポキシビス（トリエタノールアミネート）、チタンジエタノールアミネート、チタンアミノエチルアミノエタノレート、ジ－ｎ－ブトキシ・ビス（トリエタノールアミナト）チタン等を用いることができる。 Examples of the titanium coupling agent having an alkoxy group and an aminoalkoxy group include titanium diisopropoxybis (triethanolaminete), titaniumdiethanolamineate, titaniumaminoethylaminoetanolate, and di-n-butoxybis (triethanolamine). Minato) Titanium or the like can be used.
　〈酸化ケイ素粒子〉
　酸化ケイ素粒子は、商業的に入手できる酸化ケイ素粒子であってよい。ここで、本発明において、「酸化ケイ素粒子」とは、表面の少なくとも一部に酸化ケイ素を含む粒子を意味する。かかる酸化ケイ素粒子としては、例えば純粋な酸化ケイ素粒子、表面の全体又は一部に酸化ケイ素が存在している粒子等が挙げられる。 <Silicon oxide particles>
The silicon oxide particles may be commercially available silicon oxide particles. Here, in the present invention, 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.
　表面の全体又は一部に酸化ケイ素が存在している酸化ケイ素粒子は、例えば炭化ケイ素粒子を酸化することにより得られる。かかる酸化ケイ素粒子における酸化ケイ素の含有率は、０．０１質量％以上、０．１質量％以上、１質量％以上、３質量％以上、５質量％以上、７質量％以上、１０質量％以上、１５質量％以上、２０質量％以上、２５質量％以上、又は３０質量％以上であってよく、また９９質量％以下、９５質量％以下、９０質量％以下、８０質量％以下、７０質量％以下、６０質量％以下、５０質量％以下、４５質量％以下、４０質量％以下、又は３５質量％以下であってよい。この含有率は、例えば炭化ケイ素の酸化前後における質量変化を測定することにより測定することができる。 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. Hereinafter, 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.
　酸化ケイ素粒子の平均粒子径は、１０ｎｍ以上、２０ｎｍ以上、３０ｎｍ以上、４０ｎｍ以上、５０ｎｍ以上、６０ｎｍ以上、７０ｎｍ以上、８０ｎｍ以上、９０ｎｍ以上、又は１００ｎｍ以上であってよく、また１００μｍ以下、５０μｍ以下、３０μｍ以下、２０μｍ以下、１０μｍ以下、７μｍ以下、５μｍ以下、３μｍ以下、１μｍ以下、７００ｎｍ以下、５００ｎｍ以下、４００ｎｍ以下、３７０ｎｍ以下、３５０ｎｍ以下、３３０ｎｍ以下、３００ｎｍ以下、２７０ｎｍ以下、２５０ｎｍ以下、２３０ｎｍ以下、２００ｎｍ以下、又は１５０ｎｍ以下であってよい。ここでいう平均粒子径とは、対象となる酸化ケイ素粒子の大きさによって適宜選択され、概ね１μｍ未満の粒子の場合は、動的光散乱法により測定した散乱強度分布によるヒストグラム平均粒子径（Ｄ５０）の値であり、１μｍ以上の粒子の場合は、レーザー回折法において体積基準により算出されたＤ５０の値である。特に、平均粒子径が１５０ｎｍ以下である場合には、共析性がより良好になり、その結果、本発明の共析めっき液を用いて得ためっき層の耐摩耗性がより良好になる。 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 μm or less, 50 μm or less. , 30 μm or less, 20 μm or less, 10 μm or less, 7 μm or less, 5 μm or less, 3 μm or less, 1 μm 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 Hereinafter, 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 μm, 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 μm or more, it is the value of D50 calculated by the volume standard in the laser diffraction method. In particular, when the average particle size is 150 nm or less, the eutectoid property becomes better, and as a result, the wear resistance of the plating layer obtained by using the eutectoid plating solution of the present invention becomes better.
　〈金属源〉
　金属源は、めっき層とすべき金属、めっきの態様等に応じ、種々の形態であってよい。金属源は、例えば、特に限定されないが、例えばめっき層とすべき金属の金属塩、例えば硫酸塩、塩酸塩、ピロリン酸塩、スルファミン酸等の無機酸塩、シアン化塩等の有機酸塩等を用いることができる。 <Metal source>
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.
　めっき層とすべき金属としては、例えば銅、ニッケル、クロム、亜鉛、錫、銀、金等であってよい。 The metal to be used as the plating layer may be, for example, copper, nickel, chromium, zinc, tin, silver, gold or the like.
　〈他の成分〉
　他の成分としては、例えばｐＨ調整剤、ｐＨ緩衝剤、光沢剤等を用いることができる。 <Other ingredients>
As other components, for example, a pH adjuster, a pH buffer, a brightener and the like can be used.
　また、特に電解めっき液の場合、共析めっき液は、電解質を含有していてよい。 Further, particularly in the case of an electrolytic plating solution, the eutectoid plating solution may contain an electrolyte.
　また、特に無電解めっき液の場合、共析めっき液は、還元剤を含有していてよい。還元剤としては、アルカリ金属又はアルカリ土類金属の硫酸塩、塩酸塩、ピロリン酸塩、ホスフィン酸塩、スルファミン酸塩、テトラヒドロホウ酸塩等の無機酸塩、シアン化塩等の有機酸塩等を用いることができる。また、還元剤としては、例えばジメチルアミンボラン、ヒドラジン、三塩化チタン等を用いることができる。 Further, especially in the case of an electroless plating solution, the eutectoid plating solution may contain a reducing agent. Examples of 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. Can be used. Further, as the reducing agent, for example, dimethylamine borane, hydrazine, titanium trichloride and the like can be used.
　また、特に無電解めっき液の場合、共析めっき液は、錯化剤を含有していてよい。錯化剤としては、例えば酢酸、乳酸、シュウ酸、マロン酸、リンゴ酸、酒石酸等のカルボン酸、グリシン、アラニン、アスパラギン等のアミノ酸等を用いることができる。 Further, especially in the case of an electroless plating solution, the eutectoid plating solution may contain a complexing agent. As the 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.
　《水分散液》
　水分散液は、水、アミノ基を有するチタンカップリング剤、及び酸化ケイ素粒子を少なくとも含有している。この水分散液は、共析めっき液作製用水分散液であってよい。 《Water dispersion》
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.
　水分散液は、例えば水、アミノ基を有するチタンカップリング剤、及び酸化ケイ素粒子を攪拌混合し、そしてこれをビーズミル等により分散させることにより、製造することができる。 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.
　水分散液中の酸化ケイ素の含有率は、水分散液の質量全体を基準として、０．１質量％以上、０．３質量％以上、０．５質量％以上、１質量％以上、２質量％以上、３質量％以上、５質量％以上、又は７質量％以上であってよく、また５０質量％以下、４０質量％以下、３０質量％以下、２５質量％以下、２０質量％以下、１５質量％以下、又は１３質量％以下であってよい。 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.
　水分散液中のチタンカップリング剤の含有率は、水分散液の質量全体を基準として、０．１質量％以上、０．３質量％以上、０．５質量％以上、０．７質量％以上、１質量％以上、２質量％以上、３質量％以上、５質量％以上、又は７質量％以上であってよく、また５０質量％以下、４０質量％以下、３０質量％以下、２５質量％以下、２０質量％以下、１５質量％以下、又は１３質量％以下であってよい。 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.
　〈他の粒子〉
　他の粒子としては、例えば、Ａｌ２Ｏ３、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３、ＴｉＯ２、ＺｒＯ２、ＴｈＯ２、ＣｅＯ２、ＢｅＯ２、ＭｇＯ、ＣｄＯ、ダイヤモンド、ＳｉＣ、ＴｉＣ、ＷＣ、ＶＣ、ＺｒＣ、ＴａＣ、Ｃｒ３Ｃ２、Ｂ４Ｃ、ＢＮ、ＺｒＢ２、ＴｉＮ、Ｓｉ３Ｎ４、ＷＳｉ２、ＭｏＳ、ＷＳ２、ＣａＦ２、ＢａＳＯ４、ＳｒＳＯ４、ＺｎＳ、ＣｄＳ、ＴｉＨ２、ＮｂＣ、Ｃｒ３Ｂ２、ＵＯ２、ＣｅＯ２、フッ化黒鉛、黒鉛、ガラス、カオリン、コランダム、色素等を用いることができる。また、ＰＴＦＥ、ポリスチレン、ポリプロピレン、ポリカーボネート、ポリアミド、ポリアクリロニトリル、ポリピロール、ポリアニリン、アセチルセルロース、ポリビニルアセテート、ポリビニールブチラール、あるいはコポリマー（メタクリル酸メチルとメタクリル酸とのポリマー）を用いることもできる。また、これらの他の粒子は、単独で又は混合させて用いることができる。 <Other particles>
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. VC, ZrC, TaC, Cr 3 C 2 , B 4 C, BN, ZrB 2 , TiN, Si 3 N 4 , WSi 2 , MoS, WS 2 , CaF 2 , BaSO 4 , SrSO 4 , ZnS, CdS, TiH 2 , NbC, Cr 3 B 2 , UO 2 , CeO 2 , graphite fluoride, graphite, glass, kaolin, corundum, dye and the like can be used. Further, PTFE, polystyrene, polypropylene, polycarbonate, polyamide, polyacrylonitrile, polypyrrole, polyaniline, acetyl cellulose, polyvinyl acetate, polyvinyl butyral, or a copolymer (polymer of methyl methacrylate and methacrylic acid) can also be used. In addition, these other particles can be used alone or in combination.
　《共析めっき液作製用キット》
　共析めっき液作製用キットは、上記の水分散液、及び金属めっき液を含む。水分散液と金属めっき液とを混合させることにより、共析めっき液を作製することができる。この場合、水分散液の含有率は、共析めっき液全体の質量を基準として、０．１質量％以上、０．３質量％以上、０．５質量％以上、又は０．７質量％以上であってよく、また１０質量％以下、７質量％以下、５質量％以下、３質量％以下、又は２質量％以下であってよい。 << Kit for making eutectoid plating solution >>
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. In this case, 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.
　〈金属めっき液〉
　金属めっき液は、金属源を少なくとも含有している。また、金属めっき液は、共析めっき液に関して挙げた他の成分を含有していてよい。かかる金属めっき液としては、めっきの用途に応じ、市販されている金属めっき液を用いることができる。 <Metal plating solution>
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.
　《めっき物》
　めっき物は、アミノ基を有するチタンカップリング剤、酸化ケイ素、及び金属を少なくとも含有しているめっき層で被覆されている。このめっき層は、例えば上記の共析めっき液を用い、電解めっき法又は無電解めっき法により形成することができる。 《Plated material》
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.
　めっき層を構成している金属は、例えば銅、ニッケル、クロム、亜鉛、錫、銀、金等、又はこれらの合金であってよい。 The metal constituting the plating layer may be, for example, copper, nickel, chromium, zinc, tin, silver, gold, or an alloy thereof.
　実施例及び比較例により本発明を具体的に説明するが、本発明は、これらに限定されるものではない。 The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　《水分散液の作製》
　〈実施例１〉
　炭化ケイ素粒子を酸化して得られた平均粒子径１００ｎｍの酸化ケイ素粒子１０質量部、アミノ基含有チタンカップリング剤（ＴｉＣＰ）－Ａとして表１で言及しているチタントリエタノールアミネート（オルガチックスＴＣ－４００、マツモトファインケミカル株式会社、有効成分７９％）３．０質量部、及びイオン交換水８７．０質量部を攪拌混合して均一な状態にし、次いでこれを、ペイントシェーカー（０．３ｍｍ径のジルコニアビーズ）を用いて分散時間２時間で分散処理して、実施例１の水分散体を作製した。なお、炭化ケイ素粒子を酸化して得られた酸化ケイ素粒子における酸化ケイ素の含有率は、４０質量％であった。 << 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). 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.
　〈実施例２～１１、比較例１～７及び参考例〉
　表１に示す構成で、実施例１と同様にして、実施例２～１１、比較例１～７及び参考例の水分散体を作製した。 <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.
　なお、表１で言及した他の分散剤の詳細は以下のとおりである：
　アミノ基含有ＴｉＣＰ－Ｂ：チタンジエタノールアミネート（オルガチックスＴＣ－５００、マツモトファインケミカル株式会社、有効成分７０％）
　アミノ基含有ＴｉＣＰ－Ｃ：チタンアミノエチルアミノエタレート（オルガチックスＴＣ－５１０、マツモトファインケミカル株式会社、有効成分７０％）
　アミノ基含有ＴｉＣＰ－Ｄ：ジ－ｎ－ブトキシ・ビス（トリエタノールアミナト）チタン（ＴＡＴ、日本曹達株式会社、有効成分７７％）
　カチオン系界面活性剤：くし型アミン系弱カチオン（Ｈｙｐｅｒｍｅｒ　ＫＤ２、Ｃｒｏｄａ社、有効成分１００％）
　シランカップリング剤：３－アミノプロピルトリエトキシシラン（ＫＢＥ－９０３、信越化学工業、有効成分１００％）
　アミノ基非含有ＴｉＣＰ：チタンラクテートアンモニウム塩（オルガチックスＴＣ－３００、マツモトファインケミカル株式会社、有効成分４１％） The details of the other dispersants mentioned in Table 1 are as follows:
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 (Organix TC-300, Matsumoto Fine Chemical Co., Ltd., active ingredient 41%)
　また、表１に記載している酸化ケイ素粒子の形態に関し、炭化ケイ素粒子を酸化して得られた酸化ケイ素粒子を、「酸化」と言及しており、純粋な酸化ケイ素粒子を、「単体」と言及している。 Further, regarding the morphology of the silicon oxide particles shown in Table 1, 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.
　《水分散体中の酸化ケイ素粒子の平均粒子径の測定》
　得られた各水分散体中の酸化ケイ素粒子の平均粒子径を、動的光散乱法により測定した。ここで、以下の表１の「平均粒子径」において、「－」と記載しているものは、酸化ケイ素粒子の凝集が目視により確認できるため、平均粒子径を測定するまでもなく酸化ケイ素粒子が良好に分散できていないと判断できたものを示している。 << Measurement of average particle size of silicon oxide particles in an aqueous dispersion >>
The average particle size of the silicon oxide particles in each of the obtained aqueous dispersions was measured by a dynamic light scattering method. Here, in the "average particle size" of Table 1 below, those described as "-" are silicon oxide particles without having to measure the average particle size because the aggregation of silicon oxide particles can be visually confirmed. Indicates that the particles were not well dispersed.
　《めっき液及びめっき層の作製》
　作製した各分散液１質量部を、各々希釈めっき液（ＳＣ－９３－０、日本カニゼン株式会社：１９．８質量部に蒸留水７９．２質量部を加えたもの）９９質量部と混合して、共析めっき液を作製した。 << 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.
　作製した各共析めっき液を用い、無電解めっきにより厚さ５００μｍの鉄基材をめっき層で被覆した。 Using each of the prepared eutectoid plating solutions, an iron substrate with a thickness of 500 μm was coated with a plating layer by electroless plating.
　〈共析状態の評価〉
　被覆しためっき層の断面を電子顕微鏡により観察し、共析状態を評価した。評価基準は以下のとおりである：
　Ａ：十分な量の酸化ケイ素粒子が均等に存在している。
　Ｂ：十分な量の酸化ケイ素粒子が存在しているが、やや偏在している。
　Ｃ：酸化ケイ素粒子が観察されないか、又は存在しているが偏在しているか若しくはその量が十分でない。 <Evaluation of eutectoid state>
The cross section of the coated plating layer was observed with an electron microscope to evaluate the eutectoid state. The evaluation criteria are as follows:
A: A sufficient amount of silicon oxide particles are evenly present.
B: A sufficient amount of silicon oxide particles are present, but they are slightly unevenly distributed.
C: Silicon oxide particles are not observed or are present but unevenly distributed or the amount is not sufficient.
　〈耐摩耗性の評価〉
　上記の共析状態の評価がＡであっためっき層について、耐摩耗性を評価した。 <Evaluation of wear resistance>
The wear resistance of the plating layer whose eutectoid state was evaluated as A was evaluated.

　めっき層表面を、直径１０ｍｍの高炭素クロム軸受鋼（ＳＵＪ２）球体を用いて荷重２００ｇで６０回擦過した。擦過により形成された傷の深さを、表面形状測定機（タリサーフＣＣＩ）で測定した。評価基準は以下のとおりである。
Ａ：５００ｎｍ未満
Ｂ：５００ｎｍ以上２０００ｎｍ未満
Ｃ：２０００ｎｍ以上４０００ｎｍ未満
Ｄ：４０００ｎｍ以上
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
　実施例及び比較例の構成及び評価結果を表１に示す。なお、表１では、共析めっき液中のチタンカップリング剤の質量の、酸化ケイ素の質量に対する比を、「Ｄ／Ｐ」と言及している。 Table 1 shows the configurations and evaluation results of Examples and Comparative Examples. In Table 1, 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".
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から、アミノ基を含有しているチタンカップリング剤を用いた実施例１～１１の水分散体においては、平均粒子径１００μｍ及び１０００μｍの酸化ケイ素粒子のいずれを用いた場合にも、酸化ケイ素粒子が水分散液中に良好に分散しており、かつこの水分散液を市販のめっき液と混合して共析めっき液としたときに、良好な共析性を示していることが理解できよう。 From Table 1, in the aqueous dispersions of Examples 1 to 11 using the titanium coupling agent containing an amino group, oxidation occurs regardless of whether silicon oxide particles having an average particle diameter of 100 μm or 1000 μm are used. It is understood that the silicon particles are well dispersed in the aqueous dispersion, and when this aqueous dispersion is mixed with a commercially available plating solution to obtain an eutectoid plating solution, good eutectoid properties are exhibited. Let's do it.
　これに対し、カチオン系界面活性剤、シランカップリング剤、及びアミノ基を含有していないチタンカップリング剤を用いた比較例１～６の水分散体においては、平均粒子径１００ｎｍ及び１０００ｎｍの酸化ケイ素粒子のいずれを用いた場合にも、酸化ケイ素粒子が水分散液中に良好に分散しておらず、かつこの水分散液を市販のめっき液と混合して共析めっき液としたときに、共析性が良好ではなかった。 On the other hand, in the aqueous dispersions of Comparative Examples 1 to 6 using a cationic surfactant, a silane coupling agent, and a titanium coupling agent containing no amino group, oxidation with an average particle diameter of 100 nm and 1000 nm was performed. When any of the silicon particles is used, the silicon oxide particles are not well dispersed in the aqueous dispersion, and the aqueous dispersion is mixed with a commercially available plating solution to obtain an eutectoid plating solution. , The eutectoid was not good.
　また、耐摩耗性については、酸化ケイ素粒子を含有している実施例１～１１の水分散体を用いた場合には、酸化ケイ素粒子を含有していない比較例７の水分散体を用いた場合と比較して、良好な耐摩耗性が得られていることが理解できよう。 Regarding the wear resistance, when the aqueous dispersions of Examples 1 to 11 containing silicon oxide particles were used, the aqueous dispersion of Comparative Example 7 containing no silicon oxide particles was used. It can be seen that better wear resistance is obtained compared to the case.
　また、実施例１～１１を比較すると、平均粒子径がより小さい場合、及びＤ／Ｐがより大きい場合に、耐摩耗性が良好になることが理解できよう。 Further, when comparing Examples 1 to 11, it can be understood that the wear resistance becomes good when the average particle size is smaller and the D / P is larger.

Claims (5)

  1. 　水、アミノ基を有するチタンカップリング剤、酸化ケイ素粒子、及び金属源を少なくとも含有している、共析めっき液。 An eutectoid plating solution containing at least water, a titanium coupling agent having an amino group, silicon oxide particles, and a metal source.
  2. 　前記チタンカップリング剤が、アルコキシ基及びアミノアルコキシ基を有している、請求項１に記載の共析めっき液。 The eutectoid plating solution according to claim 1, wherein the titanium coupling agent has an alkoxy group and an aminoalkoxy group.
  3. 　水、アミノ基を有するチタンカップリング剤、及び酸化ケイ素粒子を少なくとも含有している、水分散液。 An aqueous dispersion containing at least water, a titanium coupling agent having an amino group, and silicon oxide particles.
  4. 　水、アミノ基を有するチタンカップリング剤、及び酸化ケイ素粒子を少なくとも含有している、水分散液、並びに
    　金属源を少なくとも含有している金属めっき液
    を含む、共析めっき液作製用キット。     A kit for producing an eutectoid plating solution, which comprises water, a titanium coupling agent having an amino group, and a metal plating solution containing at least silicon oxide particles, and a metal plating solution containing at least a metal source.
  5. 　アミノ基を有するチタンカップリング剤、酸化ケイ素、及び金属を少なくとも含有しているめっき層で被覆されている、めっき物。 A plated product coated with a plating layer containing at least a titanium coupling agent having an amino group, silicon oxide, and a metal.
PCT/JP2020/009843 2019-04-24 2020-03-06 Eutectoid plating solution WO2020217738A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-083188 2019-04-24
JP2019083188A JP2020180326A (en) 2019-04-24 2019-04-24 Eutectoid plating solution

Publications (1)

Publication Number Publication Date
WO2020217738A1 true WO2020217738A1 (en) 2020-10-29

Family

ID=72942524

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/009843 WO2020217738A1 (en) 2019-04-24 2020-03-06 Eutectoid plating solution

Country Status (2)

Country Link
JP (1) JP2020180326A (en)
WO (1) WO2020217738A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61250179A (en) * 1985-04-26 1986-11-07 Nisshin Steel Co Ltd Highly corrosion resistant colored stainless steel
JPS6283478A (en) * 1985-10-09 1987-04-16 Sumitomo Metal Ind Ltd Chromated steel material having superior adhesion to coating
JPH10212598A (en) * 1997-01-28 1998-08-11 Osaka Gas Co Ltd Composite plating coating, composite plating solution and formation of composite plating coating
JP2000212758A (en) * 1999-01-18 2000-08-02 Inoac Corp Laminated article with metal skin by electroless plating and its production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61250179A (en) * 1985-04-26 1986-11-07 Nisshin Steel Co Ltd Highly corrosion resistant colored stainless steel
JPS6283478A (en) * 1985-10-09 1987-04-16 Sumitomo Metal Ind Ltd Chromated steel material having superior adhesion to coating
JPH10212598A (en) * 1997-01-28 1998-08-11 Osaka Gas Co Ltd Composite plating coating, composite plating solution and formation of composite plating coating
JP2000212758A (en) * 1999-01-18 2000-08-02 Inoac Corp Laminated article with metal skin by electroless plating and its production

Also Published As

Publication number Publication date
JP2020180326A (en) 2020-11-05

Similar Documents

Publication Publication Date Title
Hou et al. Preparation and wear resistance of electrodeposited Ni–W/diamond composite coatings
Karthikeyan et al. Effect of reducing agent and nano Al2O3 particles on the properties of electroless Ni–P coating
TWI453307B (en) Composite coatings for whisker reduction
TWI539034B (en) Composites of carbon black and metal
US6837923B2 (en) Polytetrafluoroethylene dispersion for electroless nickel plating applications
Luo et al. Synthesis of a duplex Ni-P-YSZ/Ni-P nanocomposite coating and investigation of its performance
JP2021179015A (en) Metallic coating and method for producing the same
EP2242873A1 (en) Electrolytic deposition of metal-based composite coatings comprising nano-particles
WO2014144180A1 (en) Electrodeposition of silver with fluoropolymer nanoparticles
Rostami et al. Tribological and corrosion behavior of electrochemically deposited Co/TiO2 micro/nano-composite coatings
Alirezaei et al. Novel investigation on tribological properties of Ni–P–Ag–Al2O3 hybrid nanocomposite coatings
WO1988006638A1 (en) Composites of metal with carbon fluoride and method of preparation
WO2009059915A2 (en) Gold-containing nickel layer
Pedrizzetti et al. Microstructural, mechanical and corrosion characterization of electroless Ni-P composite coatings modified with ZrO2 reinforcing nanoparticles
WO2020217738A1 (en) Eutectoid plating solution
KR102043505B1 (en) Electroplating solution for steel sheet and methods of electroplating steel sheet using the same
US20160010214A1 (en) Composite Electroless Nickel Plating
Gul et al. Effect of Alumina Concentration on morphology, wear, and corrosion: Electroless Ni-WP/Al2O3 composite coatings on aluminum surfaces
JP7103351B2 (en) A method for forming an electric Ni-PB plating film, the film, and a sliding member having the film.
JP2020117797A (en) Eutectoid plating solution
JP2022091384A (en) Eutectoid plating solution
KR20200127209A (en) Electroless plating of objects using carbon-based materials
RU2437967C1 (en) Procedure for sedimentation of composite coating nickel-vanadium-phosphorus-boron nitride
JP2022091366A (en) Eutectoid plating solution
Zhong et al. Enhanced mechanical properties and corrosion resistance of nickel and nickel-phosphorous coatings fabricated by electrodeposition embedding with TiB2 ceramic particles

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20796250

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20796250

Country of ref document: EP

Kind code of ref document: A1