JPH06272049A - Formation of colored nickel composite plated film - Google Patents

Abstract

PURPOSE:To provide an economical method capable of forming a high hardness colored nickel composite plated film by compositing a metallic component mainly containing Ni with a fluorescent pigment treated with a specific surfactant. CONSTITUTION:In the method for forming the colored nickel composite plated film on the surface of a base material, the film is formed on the surface of the base material by electroless-plating of the base material in an electroless plating bath composed of (i) an Ni-B based or Ni-P based electroless plating solution and (ii) the fluorescent pigment to be a dispersed phase in the electroless plating solution treated with an anionic surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a plating film having excellent hardness and fluorescent characteristics on the surface of various products. More specifically, the present invention provides a novel method for forming a high-hardness color nickel composite plating film by combining a metal component mainly containing Ni and fluorescent particles on the surface of various products. Is.

[0002]

2. Description of the Related Art A desired metal is deposited on a predetermined product by an electrolytic plating method or an electroless plating method, and at the same time,
A technique of forming a composite coating by dispersing and co-depositing fine particles or fibers as the second phase in the deposited metal (also referred to as the first phase or matrix phase) is well known. The above-mentioned technique for forming a composite coating is called composite coating and is widely applied to improve the characteristics of various products, for example, the wear resistance of the surface.

The technique for forming a wear-resistant coating by the composite plating described above is, for example, "Surface technique" (Vol.41,
No. 11, 1990, pp. 22-28). In the above literature, it is emphasized that the pretreatment method is different for each material in order to obtain excellent coating adhesion when forming a wear resistant coating by an electrolytic method. For example, when forming a composite plating film on an Al-based material, the pretreatment process may be different for materials with different compositions, -Some Fe-based materials may require strike plating, -Ti material or Mg It has been shown that suitable pretreatment methods have not been developed for wood and the like.

Further, it is said that the formation of a coating film having a small internal stress by an electrolytic operation is an important factor for ensuring excellent adhesion of the coating film. Therefore, the importance of setting electrolysis conditions such as the type of plating solution, current density, and pH of the bath is shown.

It is also known that the above-mentioned composite plating technique is applied to the formation of a composite coating film comprising a deposited metal (first phase) and fluorescent particles as the second phase. That is,
"Metal surface technology" (Vol.31, No.10, 1980, pp. 66-67) mainly focuses on decoration by electrolytic plating method using Ni plating bath and melamine resin-based fluorescent pigment as dispersed particles. Color plating plate (metal fluorescent plate)
A technique for manufacturing is disclosed.

In the manufacturing technique of the color plating plate of the above-mentioned document, the fluorescent particles are simply stirred in the Ni plating bath,
Only the method of removing the water-repellent particle component is adopted, and it is possible to provide structural parts and structural members having excellent surface characteristics, especially hardness characteristics and abrasion resistance, and having a colored composite plating film. Not meant to be.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies to solve the above-mentioned problems and limitations of the conventional composite plating technique. As a result, by using an electroless plating method as the composite plating method, particularly by using a Ni-based electroless plating solution and a fluorescent pigment treated with a specific surfactant as a dispersed phase in the plating solution, The surface hardness is high, evenly and firmly bonded.
It was also found that a colored composite plating film was obtained. INDUSTRIAL APPLICABILITY The present invention provides a functional member or a structural member having a color nickel composite plating film having excellent surface characteristics, particularly, hardness characteristics and decorativeness, and makes it possible to add value to various products manufactured from these members.

[0008]

SUMMARY OF THE INVENTION The present invention will be described in brief. The present invention relates to a method of forming a color nickel composite plating film on the surface of a plating base material, wherein the plating base material is (i) Ni.
-B system or Ni-P system electroless plating solution, and (ii)
A plating base material characterized by performing electroless plating using an electroless plating bath composed of a fluorescent pigment treated with an anionic surfactant as a dispersed phase in the electroless solution of (i) above. The present invention relates to a method of forming a color nickel composite plating film on the surface of the.

The technical constitution of the present invention will be described in detail below. An electroless plating method is used as the composite plating method of the present invention. As is well known, the electroless plating method is a method of reducing and depositing metal ions in a plating bath on the surface of an object to be plated (plating base material) by using a chemical reducing agent without passing an electric current from the outside. The basic bath applied to the electroless plating method of the present invention is (a) surface characteristics,
Particularly excellent hardness characteristics (Vickers hardness, Hv 600 or more, preferably 700 or more) are given, and (b) the metal itself deposited by the chemical reduction reaction has a catalytic action for the reaction (plating film thickness From the viewpoint of (growth property), (c) stability of plating solution, and the like, Ni-based, more specifically, Ni-B-based or Ni-P-based electroless plating bath is adopted.

The components of the electroless plating bath are basically composed of a metal salt (which constitutes a metal ion in the plating bath) and a chemical reducing agent, and auxiliary components are a pH adjusting agent, a buffering agent and a complexing agent. It comprises an agent (anti-settling agent), a reaction accelerator, a stabilizer (anti-aging agent for plating bath), an improving agent (property improving agent for plating film) and the like. The latter auxiliary component has the role of stabilizing the plating bath, prolonging its life, or improving the efficiency of the reduction reaction.

The basic bath components of the Ni-based electroless plating bath of the present invention will be described below. (1) Ni-B system electroless plating bath The use mode of the metal salt as the main component differs depending on whether it is an alkaline bath or an acidic (weakly acidic) bath, but nickel sulfate, nickel chloride, nickel acetate, etc. may be used. As the reducing agent, a borohydride compound such as sodium borohydride (NaBH ₄ ) or an amine borane compound such as diethylamine borane (C ₂ H ₅ ) ₂ · HN
・ BH ₃ , dimethylamine borane (CH ₃ ) ₂・ NH ・
BH ₃ or the like is used.

(2) Ni-P electroless plating bath The metal salt as the main component has bath characteristics (acidic, neutral, alkaline, high temperature or low temperature type, etc.).
Depending on the conditions, nickel sulfate, nickel chloride, etc. may be used. As a reducing agent, hypophosphite, such as N
aH ₂ PO ₂ , KH ₂ PO _{2 and the} like are used. In addition, a borohydride compound such as NaBH as a reducing agent
₄ , KBH ₄ , hydrazine, formalin and the like may be used in combination.

Next, the above-mentioned N which is the most characteristic feature of the present invention.
The fluorescent pigment that serves as the dispersed phase in the i-based electroless bath will be described. As demonstrated by the examples below,
In order to enhance the dispersibility of the fluorescent pigment and to co-deposit the fluorescent pigment uniformly in the composite plating film, a specific surfactant, particularly an anionic surfactant, particularly preferably alkylaryl sulfonate (R- _{C 6 H 4 -SO 3 M)} , alkyl sulfate (ROSO ₃ M), anionic surfactants such as alkyl sulfonate is of the best. In the above general formulas, R is an alkyl group of C ₈ -C _16, M represents an alkali metal atom.

The above-mentioned anionic surfactant is not only useful for uniformly co-depositing the fluorescent pigment in the composite plating film as described above, but also the properties of the film to be formed, that is, the hardness property and the like. Useful to improve,
In addition, it is important to firmly bond the coating to the base material. As a usage mode of the anionic surfactant, before adding the fluorescent pigment to the electroless plating bath solution, it may be mixed with the fluorescent pigment in advance, or may be sufficiently stirred and mixed in the plating bath solution. May be.

In the present invention, the fluorescent pigments used for imparting the fluorescent emission characteristics to the composite plating film include organic fluorescent pigments and inorganic fluorescent pigments depending on the use. As the above-mentioned fluorescent pigment, for example, a fine powder fluorescent pigment FZ, F manufactured by Shin Loihi Co., Ltd.
A, FR series, SW series, SP series, etc. are used. The FR series has red (FR-53), orange (FR-54), and lemon as fluorescent colors.
Yellow (FR-55N), Orange / Yellow (FR
-56), pink (FR-57), magenta (FR-6)
7), and these have an average particle size of 3.5-
The thickness is 4.5 μm.

The SW series includes SW-07 (cerise), SW-11 (red orange), and SW-12.
(Green), SW-13 (Red), SW-15 (Lemon yellow), SW-16 (Orange yellow), S
W-17 (pink), SW-27 (rose), SW-3
7 (rubin) and the like, which have an average particle size of 1.0 μm. The SP series includes SP-13 (red), SP-14 (orange), SP-15 (lemon yellow), SP-16 (orange yellow), SP-1.
7 (pink), SP-27 (rose), SP-37 (magenta), SP-47 (rubin) and the like, which have an average particle size of 1.0 μm. The inorganic fluorescent pigment is
Generally, it is a powder of a heavy metal salt. Since these may dissolve in the plating bath, those which are insoluble in the plating bath are used.

The object to be plated (plating base material) to be treated by the electroless plating system of the electroless plating solution of the present invention and the fluorescent pigment dispersed with a specific surfactant is especially used for the surface layer. Those that require high hardness and color are targeted. Needless to say, the subject to which the method for forming the color nickel composite plating film of the present invention is applied may be that the plating base material is made of metal, ceramic, or synthetic resin for electroless plating. . For example, the object to which the method for forming the color nickel composite plating film of the present invention is applied is golf clubs, sports goods such as metal bats and leisure goods, aluminum sashes, gates, building materials such as fences, doorknobs, balconies, automobiles, etc. Various products such as parts, furniture and metal parts for household electric appliances, exterior parts for watches, guidelines for measuring instruments, etc., with high hardness, wear resistance and decorativeness are important.

[0018]

EXAMPLES The present invention will be described in more detail with reference to Examples / Comparative Examples. Needless to say, the present invention is not limited to the examples.

(Example 1) (i) Electroless plating bath An electroless plating bath was prepared with the following components. In addition,
The amount of each component used is the amount used per 1 dm ³ (1 liter) (hereinafter the same).・ Nickel sulfate …………………… 0.1 mol. ・ Sodium citrate ………… 0.1 mol. ・ Sodium acetate ……………… 0.1 mol. ・ Thallium sulfate …………………… 0.0001 mol. Dimethylamine borane: 0.05 mol.-Sodium dodecylbenzenesulfonate: 1 g. (Anionic surfactant) -Fluorescent pigment FA-46 (orange yellow):
0.5 g. (Manufactured by Shin Roihi Co., Ltd.) (ii) Composite plating method A test piece made of stainless steel (5 cm × 5 cm, thickness 3 mm) was immersed in an electroless plating bath, and electroless composite plating was performed at 80 ° C. for 60 minutes. (iii) Evaluation The obtained composite plating film has a reddish nickel bronze color and the hardness of the film is as high as Hv700.

Comparative Example 1 In the electroless plating bath of Example 1, sodium dodecylbenzene sulfonate (anionic surfactant) was changed to lauryl methyl ammonium chloride (cationic surfactant).
Composite plating was performed by the same method using the same plating bath. No fluorescent pigment was co-deposited on the obtained plated coating.

(Example 2) (i) Electroless plating bath An electroless plating bath was prepared with the following components.・ Nickel sulfate …………………… 0.1 mol. ・ Sodium citrate ………… 0.1 mol. ・ Sodium acetate ……………… 0.1 mol. ・ Thallium sulfate …………………… 0.0001 mol. Dimethylamine borane ………… 0.05 mol. ・ Sodium alkylnaphthalene sulfonate ………… 1
g. (Anionic surfactant) ・ Fluorescent pigment SW-18 (blue) ………… 0.5g. (manufactured by Shin Roihi) (ii) Composite plating method A copper test piece (5 cm × 5 cm, thickness 3 mm) It was immersed in an electroless plating bath and subjected to electroless composite plating at 80 ° C. for 60 minutes. (iii) Evaluation The obtained composite plating film has a bluish nickel bronze color, and the hardness of the film is as high as Hv700.

Comparative Example 2 In the electroless plating bath of Example 2, the sodium alkylnaphthalene sulfonate (anionic surfactant) was changed to polyoxyethylene stearyl ether (nonionic surfactant). Composite plating was performed by the same method using a plating bath. No fluorescent pigment was co-deposited on the obtained plated coating.

[0023]

The Ni-based electroless plating solution of the present invention and the electroless plating system of the fluorescent pigment dispersed in the plating solution with a specific surfactant allow the surface characteristics, particularly hardness characteristics and abrasion resistance. It is possible to efficiently form, on the surface of various products (plating base material), a color nickel composite plating film which is excellent and has fluorescent emission characteristics of various colors.

As a conventional method of forming a chromatic color coating, there is a method of plating gold or copper (electrolytic or electroless plating) to form a metal-colored plating film, but there is a limitation in color tone. Further, there are a CVD method, a PVD method and the like, but in addition to the limited color tone, the cost is extremely high.
Further, a composite plating method for forming a composite plating film of a deposited metal and fine particles is known, but a technique that sufficiently satisfies both surface characteristics and colorization has not been proposed. That is, a method for uniformly and firmly forming a color nickel composite plating film having excellent surface characteristics on the surface of the plating base material has not been proposed.

According to the present invention, for example, sports goods and leisure goods, building materials, automobile parts, exterior parts for watches, metal parts for furniture and household electric appliances, instrument guidelines, general structural parts and structural members, etc. Vickers hardness (H
v) is 600 or more, preferably 700 or more, and various products having excellent surface properties such as high hardness and abrasion resistance, which have not been found in the past, and excellent decorativeness (colorization) are economically provided. .

Claims (3)

[Claims] 1. A method for forming a color nickel composite plating film on the surface of a plating base material, wherein the plating base material is (i) Ni-B system or Ni-P system electroless plating solution, and (ii) (i) A plating base material characterized by performing electroless plating using an electroless plating bath composed of a fluorescent pigment treated with an anionic surfactant as a dispersed phase in the electroless solution. A method of forming a color nickel composite plating film on the surface. 2. The anionic surfactant is an alkylaryl sulfonate represented by the following general formula.
A method of forming the color nickel composite plating film according to. _{(Formula) R-C 6 H 4 -SO} 3 M ( where, R represents an alkyl group of C ₈ ~C _16, M represents an alkali metal atom.) 3. Anionic surfactant, alkyl sulfate (ROSO ₃ M) or alkyl sulfonate (RSO)
_The method for forming a color nickel composite plating film according to claim 1, wherein the color nickel composite plating film is ₃ M).