JP2020117797A - Eutectoid plating solution - Google Patents

Abstract

To provide a novel eutectoid plating solution which allows formation of a plating layer in which carbonization silicon particles are favorably dispersed.SOLUTION: An eutectoid plating solution includes at least a titanium coupling agent including water and an amino group, carbonization silicon particles, and a metal source.SELECTED DRAWING: None

Description

The present invention relates to a eutectoid plating solution.

In the production 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.

Further, in recent years, eutectoid plating is known in which a plating reaction is performed with a plating solution containing insoluble particles such as silicon carbide particles. 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 particles contained therein. It is often used for substrates that require abrasion resistance and hardness, such as connectors that frequently slide, and various means for such eutectoid plating have been proposed.

Patent Document 1 includes a step of adsorbing a cationic surfactant to the silicon carbide particles, and a step of dispersing the silicon carbide particles adsorbing the cationic surfactant to a plating solution. A method of making a liquid is disclosed.

In Patent Document 2, a water-insoluble inorganic or organic fine 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. A composite plating method characterized by forming a composite plating metal film of the fine powder and a metal has been proposed.

JP, 2013-241649, A JP 2001-247998 A

Even by the means according to Patent Documents 1 and 2, sufficient dispersibility of the silicon carbide particles cannot be obtained, 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.

Therefore, there is a need to provide a novel eutectoid plating solution capable of forming a plating layer in which silicon carbide particles are well dispersed.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by the following means, and have completed the present invention. That is, the present invention is as follows:
<1> A eutectoid plating solution containing at least water, a titanium coupling agent having an amino group, silicon carbide 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 carbide particles.
<4> For producing a eutectoid plating solution, which includes an aqueous dispersion containing at least water, a titanium coupling agent having an amino group, and silicon carbide 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 carbide, and a metal.

According to the present invention, it is possible to provide a novel eutectoid plating solution capable of forming a plating layer in which silicon carbide particles are well dispersed.

<Eutectoid plating solution>
The eutectoid plating solution of the present invention contains at least water, a titanium coupling agent having an amino group, silicon carbide 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 carbide in the eutectoid plating solution is 0.001 mass% or more, 0.003 mass% or more, 0.005 mass% or more, 0.01 mass% based on the total mass of the eutectoid plating solution. The above may be 0.03 mass% or more, 0.05 mass% or more, or 0.07 mass% or more, and 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.5 mass% or less. , 0.3 mass% or less, or 0.2 mass% or less.

The content of the titanium coupling agent in the eutectoid plating solution is 0.001 mass% or more, 0.003 mass% or more, 0.005 mass% or more, 0.01 based on the total mass of the eutectoid plating solution. It may be mass% or more, 0.03 mass% or more, 0.05 mass% or more, or 0.07 mass% or more, and 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.5 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 the silicon carbide is 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 50% or more, 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.

Further, the eutectoid plating solution may contain other particles.

Below, each component of this invention is demonstrated.

<water>
The water may be ion-exchanged water, distilled water or the like.

<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, and is thereby obtained by hydrolysis of the hydrolyzable group. It refers to a compound in which a hydroxyl group chemically bonds to an inorganic material and a hydrophilic organic functional group imparts hydrophilicity.

The present inventors have found that the above titanium coupling agent is adsorbed on the surface of silicon carbide particles to act as a dispersant, whereby these are dispersed in a plating solution and the silicon carbide particles are well dispersed. It has been found that layers can be formed.

By dispersing the above titanium coupling agent in the plating solution, it is possible to favorably disperse silicon carbide particles having an arbitrary average particle diameter, particularly silicon carbide particles having an average particle diameter of 150 nm or less, and thereby a plating layer. A sufficient amount of silicon carbide particles can be evenly distributed in the plating layer when forming.

The titanium coupling agent may have an alkoxy group as a hydrolysis group and an aminoalkoxy group as a hydrophilic organic functional group. In this case, the titanium coupling agent has one alkoxy group and three aminoalkoxy groups, two alkoxy groups and two aminoalkoxy groups, or three alkoxy groups and one aminoalkoxy group. However, it is preferable to have two or more aminoalkoxy groups from the viewpoint of improving the dispersibility of the silicon carbide particles.

The alkoxy group may be, for example, a linear or branched alkoxy group having 1 to 10 carbon atoms, and examples thereof include n-methoxy group, n-ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec. It may be -butoxy group, tert-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, tert-pentoxy group, hexoxy group, isohexoxy group and the like.

The aminoalkoxy group may have a structure in which an amino group is bonded to the end of the alkoxy group, particularly a structure in which an amino group is bonded to the end of the alkoxy group, and 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 terminal 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.

Examples of titanium coupling agents having an alkoxy group and an aminoalkoxy group include titanium diisopropoxybis(triethanolaminate), titanium diethanolaminate, titanium aminoethylaminoethanolate, di-n-butoxybis(triethanolamine). Minato) Titanium or the like can be used.

<Silicon carbide particles>
The silicon carbide particles may be commercially available silicon carbide particles. The average particle diameter of the silicon carbide 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 Hereafter, it may be 200 nm or less, or 150 nm or less. The average particle diameter as used herein is appropriately selected depending on the size of the silicon carbide particles of interest, and in the case of particles of less than approximately 1 μm, the histogram average particle diameter (D50 based on the scattering intensity distribution measured by the dynamic light scattering method). ), and in the case of particles of 1 μm or more, it is the value of D50 calculated on the volume basis 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.

<Metal source>
The metal source may have various forms depending on the metal to be the plating layer, the mode of plating, and the like. The metal source is, for example, but not particularly limited to, 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, or an organic acid salt such as cyanide salt. Can be used.

The metal to be the plated layer may be, for example, copper, nickel, chromium, zinc, tin, silver, gold or the like.

<Other ingredients>
As other components, for example, a pH adjusting agent, a pH buffering agent, a brightening agent, etc. can be used.

Further, particularly in the case of the electrolytic plating solution, the eutectoid plating solution may contain an electrolyte.

Further, particularly in the case of an electroless plating solution, the eutectoid plating solution may contain a reducing agent. As the reducing agent, alkali metal or alkaline earth metal sulfate, hydrochloride, pyrophosphate, phosphinate, sulfamate, tetrahydroborate, etc., inorganic acid salt, cyanide salt, etc., organic acid salt, etc. Can be used. As the reducing agent, for example, dimethylamine borane, hydrazine, titanium trichloride, etc. can be used.

Further, particularly in the case of 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.

<Water dispersion>
The aqueous dispersion contains at least water, a titanium coupling agent having an amino group, and silicon carbide particles. This aqueous dispersion may be an aqueous dispersion for producing a 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 carbide particles, and dispersing this with a bead mill or the like.

The content of silicon carbide 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, 2% by mass, based on the total mass of the aqueous dispersion. % 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 mass% or less, 15 It may be less than or equal to 13% by weight, or less than or equal to 13% by weight.

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 total 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>
Examples of the other particles include Al ₂ O ₃ , Cr ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , ZrO ₂ , ThO ₂ , SiO ₂ , CeO ₂ , BeO ₂ , MgO, CdO, diamond, TiC, WC. , 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 , fluorinated graphite, graphite, glass, kaolin, corundum, pigments 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. Moreover, these other particles can be used individually or in mixture.

<<Eutectoid plating solution preparation kit>>
The eutectoid plating solution preparation kit contains the above aqueous dispersion and a metal plating solution. The 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 mass of the entire eutectoid plating solution. It may be 10 mass% or less, 7 mass% or less, 5 mass% or less, 3 mass% or less, or 2 mass% or less.

<Metal plating solution>
The metal plating solution contains at least a metal source. Further, the metal plating solution may contain the other components listed for 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.

《Plated product》
The plated product is covered with a plated layer containing at least a titanium coupling agent having an amino group, silicon carbide, and a metal. This plating layer can be formed by an electrolytic plating method or an electroless plating method using, for example, the above-described eutectoid plating solution.

The metal forming the plating layer may be, for example, copper, nickel, chromium, zinc, tin, silver, gold or the like, or an alloy thereof.

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<<Preparation of aqueous dispersion>>
<Example 1>
10 parts by mass of silicon carbide particles having an average particle diameter of 100 nm, titanium triethanolaminate (Organics TC-400, Matsumoto Fine Chemical Co., Ltd., which is referred to in Table 1 as titanium coupling agent (TiCP)-A containing amino group, effective. Component 79%) 3.0 parts by mass, and ion-exchanged water 87.0 parts by mass are stirred and mixed to obtain a uniform state, which is then dispersed using a paint shaker (0.3 mm diameter zirconia beads) for a dispersion time of 2 Dispersion treatment was carried out for a period of time to prepare an aqueous dispersion of Example 1.

<Examples 2 to 12 and Comparative Examples 1 to 7>
The water dispersions of Examples 2 to 12 and Comparative Examples 1 to 7 were produced with the configuration shown in Table 1 in the same manner as in Example 1.

Details of the other dispersants mentioned in Table 1 are as follows:
Amino group-containing TiCP-B: Titanium diethanolaminate (Organics TC-500, Matsumoto Fine Chemical Co., Ltd., active ingredient 70%)
Amino group-containing TiCP-C: Titanium aminoethylamino amino etherate (Organix TC-510, Matsumoto Fine Chemical Co., Ltd., active ingredient 70%)
Amino group-containing TiCP-D: di-n-butoxy bis(triethanolaminato) titanium (TAT, Nippon Soda Co., Ltd., active ingredient 77%)
Cationic surfactant: Comb type amine weak cation (Hypermer KD2, Croda, 100% active ingredient)
Silane coupling agent: 3-aminopropyltriethoxysilane (KBE-903, Shin-Etsu Chemical Co., Ltd., 100% active ingredient)
Amino group-free TiCP: Titanium lactate ammonium salt (Organix TC-300, Matsumoto Fine Chemical Co., Ltd., active ingredient 41%)

<<Measurement of average particle size of silicon carbide particles in water dispersion>>
The average particle size of the silicon carbide particles in each of the obtained aqueous dispersions was measured by the dynamic light scattering method. Here, in the "average particle diameter" of Table 1 below, "-" indicates that the aggregation of the silicon carbide particles can be visually confirmed, and therefore the silicon carbide particles need not be measured for the average particle diameter. Shows that it was judged that it was not dispersed well.

<<Preparation of plating solution and plating layer>>
1 part by mass of each prepared dispersion liquid was mixed with 99 parts by mass of each diluted plating solution (SC-93-0, Nippon Kanigen Co., Ltd.: 19.8 parts by mass with 79.2 parts by mass of distilled water). To prepare a eutectoid plating solution.

Using each of the prepared eutectoid plating solutions, an iron base material having a thickness of 500 μm was coated with a plating layer by electroless plating.

<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 carbide particles are evenly present.
B: A sufficient amount of silicon carbide particles exist, but they are unevenly distributed.
C: Silicon carbide particles are not observed, or they are present but unevenly distributed or the amount thereof is not sufficient.

<Evaluation of wear resistance>
The wear resistance was evaluated for the plating layer whose evaluation of the eutectoid state was A.

The surface of the plated layer was rubbed 60 times with a load of 200 g using a high carbon chrome bearing steel (SUJ2) sphere having a diameter of 10 mm. The depth of scratches formed by rubbing was measured with a surface profilometer (Talisurf 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. In Table 1, the ratio of the mass of the titanium coupling agent in the eutectoid plating solution to the mass of silicon carbide is referred to as "D/P".

From Table 1, in each of the aqueous dispersions of Examples 1 to 12 using the titanium coupling agent containing an amino group, when any of the silicon carbide particles having an average particle diameter of 100 nm, 200 nm and 350 nm was used. , That the silicon carbide particles are well dispersed in the aqueous dispersion, and that when this aqueous dispersion is mixed with a commercially available plating solution to form a eutectoid plating solution, it exhibits good eutectoid properties. Can be understood.

On the other hand, in the water dispersions of Comparative Examples 1 to 6 using the cationic surfactant, the silane coupling agent, and the titanium coupling agent containing no amino group, carbonization with an average particle diameter of 100 nm and 350 nm was performed. When any of the silicon particles are used, the silicon carbide particles are not well dispersed in the aqueous dispersion, and when this aqueous dispersion is mixed with a commercially available plating solution to give a eutectoid plating solution. The eutectoid properties were not good.

Regarding the wear resistance, when the water dispersions of Examples 1 to 12 containing silicon carbide particles were used, the water dispersion of Comparative Example 7 containing no silicon carbide particles was used. It can be understood that good wear resistance is obtained as compared with the case.

Further, comparing Examples 1 to 12, it can be understood that the wear resistance is improved when the average particle size is smaller and when D/P is larger.

Claims (5)

A eutectoid plating solution containing at least water, a titanium coupling agent having an amino group, silicon carbide particles, and a metal source. The eutectoid plating solution according to claim 1, wherein the titanium coupling agent has an alkoxy group and an aminoalkoxy group. An aqueous dispersion containing at least water, a titanium coupling agent having an amino group, and silicon carbide particles. A kit for producing a eutectoid plating solution, which comprises an aqueous dispersion containing at least water, a titanium coupling agent having an amino group, and silicon carbide particles, and a metal plating solution containing at least a metal source. A plated product coated with a plating layer containing at least a titanium coupling agent having an amino group, silicon carbide, and a metal.