JPS59182993A - Composite plating method - Google Patents

Abstract

PURPOSE:To increase the extent of deposition without using a nonionic surfactant in the composite plating of a water insoluble org. polymer contg. fluorine by adding sulfamate ions and a cationic or amphoteric surfactant contg. fluorine to a plating soln. CONSTITUTION:A water insoluble org. polymer contg. fluorine is dispersed in a plating soln. contg. >=0.5mol sulfamate ions and a cationic surfactant contg. fluorine or an amphoteric surfactant contg. fluorine and showing cationic properties in the plating soln. Electroplating is carried out using the plating soln. Said polymer is polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-ethylene, copolymer, a chlorotrifluoroethylene-alkylene copolymer or the like. One or more kinds of such polymers may be dispersed.

Description

Detailed Description of the Invention The present invention provides polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoroglobylene copolymer, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene copolymer, selected from fluoroethylene-alkylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-interfluoronorobylene copolymer One or more water-insoluble fluorinated organic molecular substances preferably selected from polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoropropylene copolymer. The present invention relates to a composite plating method, and more specifically, to a composite plating method that can increase the amount of eutectoid deposition of a water-insoluble organic polymer substance.

Conventionally, it has been known to eutectoid a water-insoluble fluorine-based organic polymer substance as described above into a metal electroplated film, but increasing the amount of eutectoid deposition has become an important issue. That is, the eutectoid coating of the water-insoluble fluorine-containing organic polymer substance can be applied for various purposes such as lubricity and wear resistance, but the amount of the fluorine-containing organic polymer substance eutectoid is small. Therefore, it has been required to increase the amount of eutectoid.

To this end, it has been proposed to add a combination of a cationic surfactant and a nonionic surfactant to the plating solution to co-deposit the fluorine-based organic polymer substance.
In this method, the maximum amount of the fluorine-based organic polymer substance eutectoided on the metal plating film is about 13 capacitances. In this case, it is possible to achieve a higher eutectoid amount by appropriately selecting the type, amount, and combination ratio of cationic and nonionic surfactants, but strict control is required and reproducibility is difficult. There is a problem that it is not practical in terms of on-site production. In addition, when using a cationic surfactant and a nonionic surfactant in combination, it is difficult to control the amount of each and the ratio of the two, and furthermore, it is difficult to control the amount of each and the ratio of the two. In the conventional composite plating method, it is troublesome to manage the stirring of the plating solution, how to rack the objects to be plated, etc. In other words, when performing composite plating, it is necessary to uniformly disperse the organic polymer substance to be eutectoid in the plating solution, but if the amount of the activator and the ratio of its combination are not controlled, good composite plating cannot be performed. In addition, especially for conventional composite plating of fluorine-based polymer materials, the strength and uniformity of stirring have a significant effect on the quality of composite plating.If the stirring is weak, the amount of eutectoid decreases,
Even when strong stirring is applied, if the stirring is uneven, the amount of eutectoid will be reduced in the weakly stirred area. Therefore, in one object to be plated, the eutectoid amount will be different between the strongly agitated area and the weakly stirred area. There may be a considerable difference in the amount of eutectoid, or there may be unevenness in the amount of eutectoid depending on the amount of objects to be plated on the upper and lower sides attached to one rack, or the position of the rack relative to the plating tank. There was a problem.

The present inventor conducted various studies on increasing the amount of eutectoid when performing composite plating with the water-insoluble fluorine-based organic polymer substance described above, and found that 0.5 mol or more of sulfamic acid ion was added to the plating solution. Preferably, the content is 0.8 mol or more, and a fluorine-containing cationic surfactant or a fluorine-containing amphoteric surfactant that exhibits cationic properties in the plating solution is added to the plating solution, and from this solution the water-insoluble When composite plating is performed with a fluorine-based organic polymer material, (
5) As the amount of eutectoid increases, it is possible to perform good composite plating with an increased amount of eutectoid even when only a fluorine-based cationic surfactant is used alone without adding a nonionic activator. The inventors have discovered that the amount of eutectoid deposited by stirring is less affected than in conventional methods, and that plating management is therefore extremely simple, leading to the present invention.

Therefore, the present invention provides a plating solution containing 0.5 mole or more of sulfamate ions and a fluorine-based cationic surfactant or a fluorine-based amphoteric surfactant that exhibits cationic properties in the plating solution. The present invention provides a composite plating method characterized by dispersing an organic polymer substance and performing electroplating using this plating solution.

The present invention will be explained in more detail below.

In the composite plating method for a water-insoluble fluorinated organic polymer material according to the present invention, the water-insoluble fluorinated organic polymer material includes polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexane, (6) Fluoroglobylene copolymer, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-alkylene copolymer, vinylidene fluoride-hexafluoronoropyrene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer It uses 18i or 2 or more selected from polymers, vinylidene fluoride-bentafluorozolobylene copolymers, and these fluorine-based organic polymer substances are used in the form of powders, short fibers, etc. By the method of the present invention, these fluorine-containing organic polymer substances are composite plated in a high amount of eutectoid. In this case, among the above-mentioned fluorine-based organic polymer substances, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride,
Tetrafluoroethylene-hexafluoronoropyrene copolymer is effective, and according to the present invention, composite plating can be performed using these substances with a high amount of eutectoid deposition and good uniformity. In addition,
The amount of the fluorine-based organic polymer substance used is 1 plating solution! It is preferably 1 to 500 p, particularly 10 to 200 g.

In the present invention, electroplating is performed using a plating solution in which the fluorine-based organic polymer substance is dispersed. In this case, metal ions added to the plating solution include niracle, cobalt, copper, etc. Accordingly, Niracle composite plating, cobalt composite plating, nickel-cobalt alloy composite plating, copper composite plating, etc. are performed. The amount of these metal ions added to the plating solution is as follows:
! Right! ? It is preferably 0.5 to 3 mol, particularly 1 to 2.5 mol.

In the present invention, it is essential that the plating solution contains sulfamic acid ions, and in this case, the sulfamic acid ions are contained in the plating solution in an amount of 0.5 mol or more, preferably 0.8 mol or more. It is necessary that the content of sulfamic acid ions is 1 in the plating solution! If the amount is less than 0.5 mole, the effect of increasing the eutectoid amount of the fluorine-based organic polymer substance will not be sufficiently exerted, and the object of the present invention will not be achieved. Further, the upper limit of the sulfamic acid ion is not particularly limited, but it is preferably about 3 moles. Note that the sulfamic acid ion may be added to the plating solution as a sulfamino acid (in this case, the metal ion can be added as a sulfate, chloride, etc.), or as a sulfamino acid such as nickel sulfamino acid. It may be added as a metal salt, or a portion may be added as a sulfamic acid and the remainder as a sulfamic acid metal salt.

It is necessary to further add to the plating solution a fluorine-based anionic surfactant or a fluorine-based amphoteric surfactant that exhibits cationic properties in the plating solution. By using a fluorine-based anionic or amphoteric surfactant in combination, the amount of the fluorine-based organic polymer substance eutectoid can be easily increased and good composite plating can be performed.

In this case, the fluorine-based cationic or amphoteric surfactant is a water-soluble one having a C-F bond in the molecule, such as JP-A-52-56026 and JP-A-54-159343.
One type (9) or two or more types of those exemplified in the above publication may be used. Specifically, 3M's FC
-134, FC-172, etc. are preferably used. In addition,
The amount of these activators added is 0.1 to 1 in 1 plating solution.
097G, particularly preferably 0.3 to 5p value.

If the amount of activator added is too small than the above range, the amount of eutectoid cannot be sufficiently increased, and if it is too large, a good composite plating film may not be obtained.

In the present invention, as mentioned above, a fluorine-based cationic or amphoteric surfactant is used, but these surfactants can be used alone or in combination with other active agents, especially nonionic surfactants, surfactants, etc. It is not necessary to use it together with other drugs. That is, it has been known that composite plating of water-insoluble fluorine-based organic polymer substances can be performed using one of cationic, amphoteric ionic, and nonionic surfactants; Since the amount of eutectoid is small when only one type of activator is used alone, composite plating is actually performed using a cationic activator and a nonionic activator in combination, but the present invention ( 10) When performing composite plating with the fluorine-based organic madder molecular substance, the combination of sulfamic acid ions and fluorine-based cations or amphoteric activators results in better eutectoid deposition than conventional methods even without the combined use of nonionic activators. It was possible to increase the amount.

In addition, to the above-mentioned plating solution, it is possible to further add rhodanides such as nickel chloride and nickel bromide, buffering agents such as boric acid, etc., as well as commercially available brighteners and other additives. be able to.

In addition, - of the plating solution is acidic, especially for nickel composite plating,
In the case of cobalt composite plating, it is preferable to adjust it to a range of 3 to 5.

As mentioned above, the composite plating method according to the present invention comprises dispersing the above-mentioned water-insoluble fluorinated organic polymer substance containing metal ions and sulfamic acid ions, and adding a fluorinated cation or an amphoteric surfactant. Electroplating is performed using a plating solution, and the plating conditions are a temperature of 20 to 80°C, and a polar current density of 0.1 to 80°C.
The conditions may be 100 A/dm2, particularly 1 to 30 A/dm2. Further, as the stirring method, a liquid flow method using a pump to circulate the liquid, stirring using a stirrer, a cathode rocker, etc. can be adopted. In this case, since the present invention has less influence on the eutectoid amount due to stirring than the conventional method, strong stirring is not necessarily required, and the stirring can be applied evenly to the object to be plated. The degree of consideration given to this can also be simplified compared to conventional methods.

In the present invention, the material of the plated object to be composite plated is not particularly limited, and may be any material that can be electroplated, such as metal, conductive glass, fiber, etc. The thickness of the composite plating film is
Although it is appropriately selected depending on the purpose of use of the plated product, it is usually 1 to 50 μm.

According to the plating method of the present invention, in addition to containing 0.5 mole or more of sulfamic acid ions, a fluorine-based cation or an amphoteric surfactant is added, and the water-insoluble fluorine-based organic polymer substance is dispersed. By using a plating solution, it is possible to increase the amount of the eutectoid organic polymer substance, and stable composite plating can be performed at an eutectoid amount of usually 10 to 40 volumes. In particular, the content of sulfamic acid ions is 0.5 to 3 mol, preferably 0.8 to 3 mol, and the amount of fluorine-based cation or amphoteric surfactant added is 0.1 to 10 gμ,
and the amount of the fluorine-based organic polymer substance added is 10 to 20
By using a tightening solution of 0 g/'e, it is possible to reliably achieve a eutectoid amount of 15 to 35 volumes, and such a high eutectoid amount cannot be achieved with conventional methods. This was something that could not be achieved consistently. Moreover, according to the present invention, the plating film is good despite such a high amount of eutectoid. Furthermore, according to the method of the present invention, good composite plating can be performed at a high eutectoid amount even if one type of 7-aryl cation or amphoteric surfactant is used alone as an activator. The plating work is easily managed and is not easily affected by stirring, and the amount of eutectoid is less likely to be uneven due to uneven stirring, so the plating work is easy to manage.

(13) Products with a plating film formed by the method of the present invention can be used for various purposes depending on the type of eutectoid water-insoluble fluorinated organic polymer material, such as automobiles intended for wear resistance and low friction. All sliding parts related to width and precision machinery, metal and non-metal molds or kitchen equipment for non-adhesive and releasable properties, various architectural and daily use parts for corrosion resistance and discoloration prevention, etc. However, since the plating film produced by the method of the present invention has a high amount of eutectoid as described above, it effectively exhibits its effect.

EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1, Comparative Examples 1 and 2] Using a plating solution with the following composition, under the following conditions, 10 c
After composite plating was performed on a polished steel plate of m x 5 crn, the amount of eutectoid was measured, and the results shown below were obtained.

(14) ρp” liquid composition Example 1 Comparative example 1 Comparative example 2 Receiving liquid composition 450 El/A
--Nickel sulfate K 26
0 g/A 260 Vlt chloride chloride 0
45 45 Boric acid 35
40 40 cationic activator
1 1 1 nonionic activator
-10.5 PTFE 30 50
50PH4,24,24,2 Plating condition temperature 50℃ 501C50C
Cathode current density 4A/dm2 4A/dm2
4 people/dm2 anode Contains 6-'・ke'' Same left Same left Anode stirring Mechanical stirring Same left Same left Plating film is non-uniform Non-uniform appearance Uniform grayish white Pear-like pear shape, eutectoid Volume 35 volumes = 5 volumes 9 Capacity Note:
(1) Per70-roalkyltrimethylammonium salt was used as the cationic activator.

(2) A /-P-70 loalkyl ethylene oxide adduct was used as the nonionic activator.

(3) PTFE represents polytetrafluoroethylene.

From the above results, it has been found that the amount of eutectoid increases by adopting the plating method according to the present invention.

[Example 2, Comparative Example 3] Composite plating was performed on a polished steel plate under the same conditions using a plating solution having the same composition as in Example 1 and Comparative Example 2, and then the amount of eutectoid was measured.

In addition, 150t of plating solution was used, 10mX5ctn
As shown in the drawing, six polished steel plates were attached to each side of the rack in three stages, top, middle, and bottom, and plated.
The amount of eutectoid deposited on three polished steel plates of , B, and C was measured (in the figure, 1 is the rack and 2 is the polished steel plate).

Eutectoid amount Example 2 Comparative example 3A
33 capacity Chi 6.8 capacity Chi 8
35 8.5
C389,8 Note that similar results were obtained for polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoropropylene copolymer.

From the above results, it was confirmed that the plating method according to the present invention is less affected by stirring and can perform composite plating with a high eutectoid amount and a uniform eutectoid amount.

[Brief explanation of the drawing]

The drawing is a schematic side view showing how the object to be plated (polished steel plate) used in the experiment of the composite plating method is mounted on a rack. Applicant Uemura Kogyo Co., Ltd. Agent Patent Attorney Takashi Kojima

Claims (1)

[Scope of Claims] 1. Adding a fluorine-based cationic surfactant or a fluorine-based amphoteric surfactant that exhibits cationic properties in the plating solution, which contains 0.5 mole or more of sulfamate ions, Ethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoro7'ropylene copolymer, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-alkylene copolymer, vinylidene fluoride One or more water-insoluble fluorinated organic polymer substances selected from hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-pentafluoropropylene copolymer 1. A composite plating method for water-insoluble organic polymeric substances, characterized by electroplating using a plating solution in which is dispersed. 2. Claim 1, wherein the water-insoluble fluorine-based organic polymer substance is selected from polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoronoropyrene copolymer. Composite plating method described in section. 3. The amount of fluorine-based cationic surfactant or fluorine-based amphoteric surfactant that shows cationic properties in the plating solution is 1! The composite plating method according to claim 1 or 2, wherein the average particle diameter is 0.1 to 1094.