JP2001192850A - Surface treating solution for sliding parts, surface treating method for sliding parts and sliding parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-cost surface treating solution by which films provided with properties suitable for its application can be deposited in sliding parts of various stocks, treating equipment is simple and the management of chemicals is easily executable. SOLUTION: This surface treating solution for sliding parts contains a reducing agent, a complex forming agent, a stabilizing agent, a buffering agent and an activating agent and contains nickel ions, at least either metallic ions selected from phosphorous ions and boron ions and at least one ore more metallic ions selected from tungsten ions, cobalt ions, palladium ions, rhenium ions, yttrium ions, molybdenum ions, titanium ions, manganese ions, vanadium ions, zircon ions, chromium ions, copper ions, gold ions, silver ions, zinc ions, iron ions, lead ions, tin ions, and platinum ions, and whose pH is controlled to 9 to 14.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment liquid for a sliding part which enhances slidability, a method for treating a surface of a sliding part, and a sliding part treated by the surface treatment method.

[0002]

2. Description of the Related Art For example, sliding parts such as a valve shim of an automobile engine, a valve lifter, a retainer, and a spinning roll of an AT (automatic transmission) part are based on the environment and function in which they are used. Corrosion resistance, low friction (friction), lubrication, seizure resistance, abrasion resistance, scuffing resistance, etc.
Various characteristics (hereinafter collectively referred to as slidability) are required, and copper alloys, zinc alloys, stainless steels, and special steels (JISG-44) that make use of the characteristics of each metal are required.
01, G-4409, G-4403 to G4409, G4
High carbon steel such as 311 to 4312, or SCR steel containing a large amount of chromium or molybdenum, or JIS G410.
SCM steels such as 4, G4105, and G4202 are used. Further, aluminum alloys, magnesium alloys, engineering plastics other than metals have been used for weight reduction, and ceramics and the like have been used for heat resistance. Some sliding parts formed from such a material have been subjected to a surface treatment to improve the slidability on the surface. For this surface treatment, for example, manganese phosphate type, zinc phosphate type,
In some cases, a surface treatment is performed by forming a crystalline chemical conversion film of a fluoride salt or basic copper system. The crystalline chemical conversion film on the surface of this sliding component was effective in terms of corrosion resistance and initial adaptability because a relatively thick film could be formed and the hardness of the film was high. In some cases, an amorphous iron-based composite metal oxide film containing molybdenum, tungsten, copper ions, or the like is formed with an iron phosphate-based chemical conversion film-forming agent to perform surface treatment. With this composite metal oxide film, a film having a higher density and a lower coefficient of friction could be obtained.

[0003]

However, manganese phosphate-based, zinc phosphate-based, fluoride-based, basic copper-based crystalline chemical conversion films and iron phosphate-based film-forming agents include molybdenum, tungsten, and the like. All amorphous composite oxide films containing copper metal ions, etc. have a large friction coefficient between metal parts due to the rough surface of the sliding surface, and have abrasion resistance, seizure resistance, lubricity, In addition, there is a problem that the formed film lacks uniformity.

More specifically, the surface roughness of a chemical conversion film formed on the surface of a metal sliding component before and after peeling is Rz value (JIS) 2.0-2.5 μm for manganese phosphate, The oxide film was rough with an Rz value of 0.4 to 0.8 μm. The surface roughness was measured using Surftest SV402 manufactured by Mitutoyo Corporation (the same applies hereinafter).

[0005] Further, a film made of an iron phosphate chemical conversion film forming agent containing metal ions such as molybdenum, tungsten and copper becomes an amorphous composite metal oxide film, which is dense and has a low coefficient of friction. However, the film thickness is small, and the surface roughness of the material surface of the sliding parts is reduced by etching, the wear resistance is reduced, and the slidability is deteriorated. Also in the test, peeling was caused by running at 2,000 km to 3,000 km. In addition, when trying to increase the film thickness, a crystalline metal grows, so it was difficult to increase the film thickness while maintaining the amorphous property.

[0006] In addition to these chemical conversion coatings, a hard alumite treatment by an electrolytic treatment (alumite is a registered trademark) has been partially adopted in a coating for sliding parts made of aluminum alloy. Alternatively, films such as electroplating have been employed, but these have the problems of high cost and lack of uniformity, which may cause pinholes. In addition, sliding parts such as ceramics and resins have the problems that they are nonconductive, cannot be electroplated, and cannot be hard anodized.

The present invention has been made to solve the above-mentioned problems, and has various kinds of sliding parts made of alloys such as iron, stainless steel, aluminum, and copper, or ceramics and resins. A coating with low friction, lubricity, abrasion resistance, seizure resistance, etc., can be formed, the processing equipment is simple, chemical management is easy, and low cost surface treatment liquid for sliding parts and sliding. An object of the present invention is to provide a surface treatment method for a component and a sliding component.

[0008]

Means for Solving the Problems As a means for solving the above-mentioned problems, the present inventor has proposed a method for measuring the surface roughness of a material of a sliding part by using R
A special sliding part which has an a value (JIS) of 0.03 μm or less, desirably an Ra value of about 0.01 μm to 0.02 μm and does not roughen the surface roughness of the smoothed material surface. We developed a surface treatment method that can produce sliding parts with high slidability by treating the surface with a treatment liquid, and succeeded in solving the above-mentioned problems in sliding parts surface-treated by this surface treatment method.

First, it is necessary to form a film having high smoothness on the surface in order to exhibit excellent sliding characteristics of the sliding component. For this purpose, it is necessary to maintain a high smoothness of the substrate. The present inventor, who paid attention to the premise of forming a film having high slidability, first studied a method for adjusting the surface of the substrate. Here, cutting with a machine or polishing with a diamond whetstone has the drawback of lacking mass productivity and uneven surface roughness, and the sliding surface having an uneven surface roughness is not smooth. Film cannot be formed. Therefore,
The present inventor has succeeded in smoothing the surface by making the surface roughness uniform at a high level by employing a chemical polishing method in addition to the mechanical and physical polishing methods. Here, in order to polish only the required flat surface without polishing the edge portion within a single time by the chemical polishing method, a special compound that simultaneously provides a compound with excellent polishing properties and gloss and smoothness A large amount of compounding agent is required. Specifically, a compound having a composition in which sodium alkylbenzene sulfonate, tetrasodium ethylenediaminetetraacetate, and polyoxyethyleneoxypropylene glycol are used as main bases and a builder of an alkali inorganic salt is used is used. As the alkali inorganic salt, sodium tripolyphosphate, sodium pyrophosphate and the like are used. As a result, this chemical polishing method enables mass production of sliding parts having a uniform surface roughness, and the surface roughness of the sliding parts is 0.02 μm or less in Ra value (JIS), Rz 0.1 in value
It is adjusted to 2 μm or less, preferably Ra value 0.015 μm and Rz value 0.10 to 0.12 μm.

Here, one of the desirable conditions for the sliding parts is that the relative sliding movement between the sliding parts is locally brought into a solid contact state due to various factors and is welded or fixed by the generation of frictional heat. Scuffing, which is a phenomenon to be removed, does not occur, and the friction coefficient is low. In order to obtain such high scuffing resistance and low friction property, the surface roughness of the sliding component formed extremely smoothly as described above is adjusted so that the surface roughness is not roughened by the coating. To form a uniformly smoothed film having an Ra value of 0.03 μm or less and an Rz value of 0.15 μm or less,
The present inventor considered that the film needs to be formed of a hard and dense metal rich in amorphous property.

Therefore, the inventor of the present invention has found that in the case of electroplating, which requires large-scale equipment, or in the case of a hard alumite-treated film by electrolysis, the cost is high, and a film having characteristics suitable for the application cannot be formed. In addition, there was a problem that the film lacked uniformity and a pinhole was sometimes generated. Therefore, a film having performance equal to or higher than that of the other films was sought. In order to develop such a film, we believe that it is effective to provide excellent slidability on the surface of sliding parts by making trial and error through repeated trial production experiments and making an amorphous composite metal film. It has been considered that a hard and highly wear-resistant smooth film which does not roughen the surface roughness can be formed on the surface of the smooth sliding component by ordinary electroless plating. Therefore, the present inventor
First, an experiment was carried out in consideration of processing using a commercially available processing solution for electroless plating.

(Experiment 1) Here, Experiment 1 will be described in which the inventor formed a sliding film of a sliding component treated with a commercially available treatment solution for electroless plating. Commercially available processing solutions for electroless plating include, for example, Epack RE-MU-II (Ni-P system), Unipack BN-S, M, R (Ni-B system), Evashield manufactured by Ebara Uzilite Co., Ltd. E
C (Cu-based), Top Nicolon L manufactured by Okuno Pharmaceutical Co., Ltd.
PH-S (Ni-P type), Top Chemialloy 66-M,
1, 2 (Ni-B system), capparaside (Cu system), Niiko ME-AR (Ni-P system), Niikoboron (Ni-B system), SEL-kappa (Cu system) manufactured by Kizai Co., Ltd.
Ni-P-based, Ni-B-based, and Cu-based treatment liquids are used. Among them, the treatment with each of the Ni-P and Ni-B treatment liquids will be described below.

[0013] Regarding the Ni-B-based processing liquids, Unipack BN-S, M, R, Nicoboron, Top Chemialloy 66-M, 1, 2, the temperature of the processing liquid is 63 ° C.
Adjust to 65 ° C., adjust the pH from 6.0 to 6.5,
The concentration of soluble nickel (Ni ²⁺ ) is from 6 g / l to 6.5
g / l and processed.

[0014] Regarding the Ni-P-based processing liquids, ENPACK RE-MU-II, Top Nicolon LPH-S, and Nikko ME-AR, the temperature of the processing liquid is 89 to 91.
° C, and the pH was adjusted to 5.0 for Enpack RE-MU-II and 6.5 for other treatment solutions, and the soluble nickel concentration was 7 g / kg for Empack RE-MU-II. 1 and the other processing solutions were processed while maintaining the nickel concentration at 6.5 g / l.

Here, as a representative, the Nikko ME-AR
Experiments using (Ni-P system) and Nicorboron (Ni-B system) will be described in more detail. As a test method, the test piece used had an Ra value of 0.01 to 0.5.
Using a SCM415 having a diameter of about 28 to 31 mm and a thickness of about 2.3 to 2.9 mm adjusted and polished to 02 μm, a film is formed in the following steps according to the work standard specified by each manufacturer. went. The process of the work standard specified by the manufacturer is Niiko ME-AR (Ni-P system).
And Nicoboron (Ni-B type), both immersion degreasing, water washing, electrolytic degreasing, water washing, acid activity, water washing,
Niiko ME-AR (Ni-P system) and Niikoboron (Ni-B system) are processed in this order. In addition, a Ni electrodeposition strike plating step is performed between the processing steps depending on the material.

FIG. 1 is a diagram showing the steps of the processing in Experiment 1. As shown in FIG. 1, in all cases, the film forming process is performed in accordance with the work standard process specified by the manufacturer, followed by first degreasing 1, followed by first water washing 2, Ni
-P, Ni-B film formation 3, second water washing 4, hot water washing 5, drying 6 in this order. Details of each step are as follows.

Degreasing 1 was immersed in a weakly alkaline degreasing agent at 70 ° C. for 10 minutes while rocking. The swing of the test piece was based on handling (the same processing was performed for the following swing). Next, the first washing 2
This was performed by constantly overflowing tap water. The temperature at that time was room temperature, and it was immersed while rocking for 2 minutes. Next, the process of Ni-P, Ni-B film formation 3 was performed. In the process of forming the Ni-P and Ni-B coatings 3, the processing liquid was Nikko ME-AR (Ni-P type) (180).
g / l) and Nicorboron (Ni-B type) (180 g
/ L) using ammonium hydroxide (NH ₄ O).
H) or sulfuric acid (H ₂ SO ₄ ) as appropriate to adjust the pH to 6.5 as specified by the manufacturer, and to adjust the soluble nickel concentration to 6.0.
g / l. The temperature condition is Niiko ME-AR (Ni-
89-91 ° C in the case of P-type, Nicoboron (Ni-
In the case of (B type), the temperature was 63 to 65 ° C., and each was immersed while rocking for 20 minutes. Thereafter, the second washing 4 was performed while the tap water was constantly shaken by overflowing. The hot water washing 5 was performed by immersing tap water heated to 75 to 85 ° C. while oscillating for 2 minutes while always overflowing, and finally drying 6 by natural drying using self-heating.

As a result of the experiment 1, the film formed under the above-mentioned steps and the above-mentioned conditions was examined.
In both cases (Ni-P system) and Nicorboron (Ni-B system), the film formed on the test piece made of SCM415 has a thickness of about 5 to 10 μm and a hardness of Hv500.
A thick and hard film before and after was formed. However, the adhesion of the film was poor, and the film was easily peeled off by a scratch test that was lightly rubbed at the edge of an untreated test piece. The same result was obtained with other commercially available processing solutions.

[0019] This problem is caused by the fact that aluminum, nickel, cobalt, etc. are used in special steel stainless steel, high carbon steel, etc. containing a large amount of chromium / molybdenum used for sliding parts.
It was considered that chromium and the like were caused by forming a passivation film on the metal surface of the sliding component. If so, in the case of this type of alloy, activation of the metal surface with a treatment solution comprising a mixed acid (for example, a mixture of phosphoric acid, sulfuric acid, nitric acid and at least one of acid ammonium fluoride) is added. After processing or as in the process specified by the manufacturer, after applying a large current by electrolysis and forming a thin nickel or zinc plating layer by electrodeposition strike plating with a special bath composition It has been found that in the method of forming a film that performs a nickel-phosphorus-based and nickel-boron-based reducing action, the film is not completely adhered and is easily peeled. Then, a nickel-phosphorous or nickel-boron-based film treatment is performed after the activation treatment or the electrodeposition strike plating treatment, so that the formation of a film having a slightly high friction coefficient but high adhesion is achieved. We were able to.

However, the inventor of the present invention considered that a sliding film is formed without roughening the surface roughness as described above. Therefore, even if the treatment to increase the degree of adhesion, the etching activation treatment using such acids cannot be adopted, and performing the strike plating plating specified by the manufacturer requires a large amount of treatment. It could not be adopted because the manufacturing cost also increased. In addition, even with a metal that does not form a passivation film, it has been considered that etching with acids or the like is not desirable because the surface roughness is roughened.

Therefore, the inventor of the present invention has proposed the first washing 2 in FIG. 1 and the treatment liquids Nikko ME-AR (Ni-P type) and Niikoboron (N
Step of forming a film using an amorphous film of a composite multi-dimensional metal, for example, a nickel-tungsten-phosphorus-based composite three-dimensional metal, during the process of forming the Ni-P, Ni-B film 3 by the i-B system). And, it is expected that a film with good adhesion will be formed by performing the treatment by adding the water washing process,
As will be described later in detail, when an amorphous film of a composite three-dimensional metal such as a nickel-tungsten-phosphorous system is formed, a composite three-dimensional metal such as a nickel-tungsten-phosphorus system formed with good adhesion on the surface of a sliding component is formed. It has been found that a film performing a nickel-phosphorous or nickel-boron-based reducing action is formed on the amorphous film with extremely good adhesion.

The nickel-phosphorus-based or nickel-boron-based film thus formed with good adhesion was a thick, hard and glossy film. By forming such a hard and thick film with good adhesion,
A film having good corrosion resistance and initial familiarity could be obtained.

However, it was found that, when used as a sliding part between metals, when the film thickness was 15 μm or more, the surface roughness of the film surface was rough and the friction coefficient was excessive. When used as a sliding part, no matter how hard it is, it is not necessarily effective in terms of abrasion resistance against attack by sliding between metals if the coefficient of friction is large. Further, conventionally, for example, a coating of a sliding part in which metals are in contact with each other, such as a valve shim that contacts and slides on a cam, is formed of a nickel-phosphorous or nickel-boron-based hard coating having a thickness of about 15 to 50 μm. However, in such a structure of the film, the amorphous structure is lost, the metal particle layer changed from Ni ₂ P to Ni ₃ P is crystallized, and a high hardness is obtained. Has been maintained. Although the same properties can be obtained by applying heat treatment, the coefficient of friction seems to be sufficiently low in a very thin film layer on the surface of the film.
However, by using for a long time, the hardness and the thickness of the low coefficient of friction portion formed in the very thin film layer on the surface of this film are easily peeled off by attack between sliding parts, There is a problem that a crystalline layer having a high coefficient of friction is exposed.

From these results, the present inventor considered that it is desirable that the surface film of the sliding component should be composed of an amorphous film having a low friction coefficient. And
In the above development process, through the embodiments described below,
Developing multi-dimensional composite metals while maintaining nanometer-class ultra-fine metal coatings with high amorphous properties,
In order to laminate the film while maintaining the smoothness without roughening the sliding component surface by etching, a plurality of metal ion supply sources, an appropriate reducing agent, an appropriate metal complexing agent, etc. are used. By controlling the bath composition and the treatment liquid so that the pH of the treatment liquid is in the range of 9 to 14, a specific method for forming an extremely dense and uniform film without roughening the surface of the sliding component is found. Was.

It has also been found that it is effective to co-deposit a plurality of types of metal particles in a coating film. More preferably, the present inventors have also found out that the film has a matrix having a continuous phase so that a metal corresponding to the characteristics of the sliding component can be retained in the film according to the purpose of use. Then, it has been found that a nickel-phosphorous or nickel-boron composite film is suitable for such a matrix, and a film containing tungsten in particular can realize high hardness.

In a scratch test with a coin-shaped metal edge, and in a test in which a high-speed rotation is performed together with a highly aggressive deformed media having an acute angle in a fluid centrifugal barrel, a film having high adhesion of the film and having difficulty in peeling is obtained. Has been confirmed.

[0027] Such a film in which a nanometer-class ultrafine metal film having a high amorphous property is laminated is not only improved in abrasion resistance of the film itself, but also has a very smooth surface and a high friction. Since the coefficient is extremely low, a low friction coefficient is maintained even when used as a sliding component for a long period of time, so that high durability can be exhibited.

Since a passivation film is not formed on a nanometer class ultrafine particle metal film having a high amorphous property, another film can be carried on the film with good adhesion. For example, a hard film is formed, such as a nickel-phosphorous or nickel-boron-based film as described above, but there was a problem in adhesion due to a passivation film depending on the material of the sliding part. Even if it is a film, such a film having poor adhesion can be carried to the outside to form a two-layer structure having high adhesion through the film according to the present invention. For this reason, the sliding parts that are in contact with each other are slid by the outer layer until they become more familiar, and after the outer layer is worn, the hard amorphous material with a low coefficient of friction and excellent wear resistance is used. It has also been found that an inner layer of a material having a high surface tension is exposed and that sliding on this inner layer achieves a very low coefficient of friction and very high wear resistance. For example, when applied to a cam of an automobile engine and a shim sliding with the cam, the cam first slides with a hard upper layer film, the surface of the cam itself is smoothed, and the upper layer film is worn. The lower layer having a low coefficient of friction is exposed. As a result, the cam and shim that have been familiar in shape slide on the surface with a very low coefficient of friction and a high degree of smoothness, resulting in extremely high durability and a low coefficient of friction. It becomes possible to slide. In other words, depending on the purpose of use of the sliding part, a film with different properties was formed with good adhesion to the outside, with a film developed and laminated while maintaining a nanometer-class ultrafine metal film with high amorphousness One having a two-layer structure composed of a film can be used depending on the purpose.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a surface treatment liquid for a sliding component, a method for treating a surface of a sliding component, and a sliding component treated by the surface treatment method according to the present invention will be described by way of a preferred embodiment. explain.

(Embodiment 1) The following is a processing example 1 of the embodiment 1.
Table 1 showing the bath composition is shown.

[0031]

[Table 1]

The processing steps of the first embodiment are as follows.
FIG. 2 is a diagram illustrating the steps of the processing according to the first embodiment.
The treatment is degreasing 101, first rinse 102, Ni-WP
Film formation 103, second water washing 104, hot water washing 105, and drying 106 are performed. The basic process is Ni-W-
It is the same as Experiment 1 except for the P film formation 103. Details of each step are as follows.

(A) Regarding the degreasing step 101, a surfactant (Daiichi Kogyo Co., Ltd.) which is based on a non-silicate weak alkaline builder and which gives the most importance to the wettability of the sliding component surface polished to a glossy mirror surface is used. Pharmaceutical Plysurf A-215
A degreasing treatment liquid characterized by using C) and using metal salt fine particles (CT-1 manufactured by Surfacetex Co., Ltd.) as a film constituent element in a subsequent step as a binder.
It was immersed in this treatment solution at 70 ° C. for 10 minutes while rocking.
The swing was based on handling (the same applies to the swing in each of the following embodiments).

(B) Next, the treatment of the first water washing 102 is performed by overflowing the tap water and immersing it for 2 minutes while oscillating, and confirming that there is no water cissing or the like.

(C) Next, a process for forming a Ni-WP film 103 was performed. In the immersion, the processing temperature is 89-95.
° C, here, 89-91 ° C, and the immersion time is 15
２０20 minutes. In addition, it rocked during immersion. Ni-W-
The treatment liquid used in the treatment of forming the P film 103 was as shown in Table 1.

In processing example 1, nickel sulfate hydrate (NiSO ₄ .6H ₂ O) as nickel ions was 20 g /
l. The hydrate of nickel sulfate is 14-84 g /
l, preferably 20 g / l. Sodium tungstate hydrate (Na ₂
WO ₄ · _4H 2 O) and containing 35 g / l. The hydrate of sodium tungstate contains 16 to 98 g / l, preferably 35 g / l. In addition, as a supply source of nickel ions, nickel chloride, nickel acetate, and the like are also preferable. Further, the soluble nickel contained in the treatment liquid is 6 to 7 g / l, preferably 6.5 g / l, and in the processing example 1, the soluble nickel is 6.0 to 7.0 g / l.
Adjusted to l.

The metal ions contained in the processing solution are as follows:
Not limited to nickel ion, tungsten ion, phosphorus ion, nickel ion, at least one metal ion of phosphorus ion or boron ion, tungsten ion, cobalt ion, palladium ion, rhenium ion, yttrium ion, molybdenum ion, titanium ion , Manganese ions, vanadium ions, zircon ions, chromium ions, copper ions, gold ions, silver ions, zinc ions, iron ions, lead ions, tin ions, at least one or more metal ions selected from platinum ions It can also be carried out by a material containing a metal ion.

(D) 15 g / l of sodium hypophosphite hydrate (NaH ₂ PO ₂ .H ₂ O) as a reducing agent
contains. The hydrate of sodium hypophosphite is 5 to 50
g / l, preferably 15 g / l. As a result, the phosphorus in the hypophosphite is added to the composite metal film component by 2 to 2.
15 (% by weight), preferably 8 to 12 (% by weight). By blending in this range, high corrosion resistance, high lubricity and low friction can be maintained without lowering the amorphousness of the film.

The reducing agent is not limited to sodium hypophosphite, but includes sodium phosphite, sodium or potassium borohydride, dimethylamine borane, diethylamine borane, hydrazines, formaldehydes, Rossier salts, glucose and the like. It can be selected from such as types.

(E) In the present treatment example 1, citric acid (C ₆ H ₇ O ₈ ) is contained as a complexing agent in an amount of 20 g / l. The concentration of citric acid is 10 to 25 g / l, preferably 20 g / l
It is. Also, hydrates of ethylenediaminetetraacetic acid salts
(Hereinafter abbreviated as EDTA · 4H ₂ O) at 10 g / l.
contains. EDTA · 4H ₂ O is at least 5 g / l
５０50 g / l, desirably 10 g / l.

Since the complexing agent contains rich metal ions of nickel, tungsten, and phosphorus, it is possible to complex a metal substance other than the minimum necessary metal ions at the time of film formation into an inactive ion. It is an indispensable factor for measuring the long-term stability of the processing solution and averaging the contents of nickel, tungsten and phosphorus in the formed film.
It is also a measure for improving the quality of the film that the impurity such as iron generated during the film formation reaction is not contained in the film structure. Furthermore, it suppresses precipitation of nickel hydroxide and nickel phosphite, stabilizes nickel ions and phosphorus ions, stabilizes film formation, prevents spontaneous decomposition of the bath, and contributes to preventing roughening of the film surface. I do.

The complexing agent is not limited to citric acid and EDTA, but oxycarboxylic acids such as tartaric acid, lactic acid and glycolic acid and their alkali salts, and dicarboxylic acids such as malonic acid, succinic acid and maleic acid. And alkali salts thereof, amines such as ammonia, triethanolamine and ethylenediamine, amino acids such as glycine and alanine, and pyridine.

(G) In the present processing example 1, ammonium chloride (NH ₄ C
l) at 5 g / l. Ammonium chloride is 5.3
Desirably, the content is 53.5 g / l. This treatment liquid has the effect of increasing the phosphorus content and the amorphousness at a relatively low temperature of 60 ° C. to 85 ° C. and the effect of accelerating the film formation temperature. Is finally controlled and adjusted to a predetermined value of pH 9 to 10.

The pH adjuster is not limited to ammonia alkali salts and caustic soda, but inorganic alkali salts such as sodium carbonate, organic alkali bases containing ammonia, inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as sulfamic acid. You can choose from.

In the present treatment example 1, sodium phosphate pyrophosphate (Na
₄ P ₂ O ₇ ) and boric acid (H ₃ BO ₃ ) as boron. Generally, all commercially available processing liquids are processing liquids containing propionic acid, acetate and the like in the pH range of 4 to 6.5 on the acidic side, and are characterized by a monocarboxylic acid that hardly forms a complex with nickel ions. Means that buffering and suppressing the pH fluctuation at the electrode interface that reacts with the material of the sliding part increases the plating rate, that is, increases the film thickness per unit time, but decreases the P content in the film structure. Loses amorphousity and crystallizes,
Although the coefficient of friction is low in the initial stage, the coefficient of friction increases in continuous sliding for a long time.

Therefore, the treatment liquid of this treatment example 1 contains sodium pyrophosphate 3-6 g / l, here 5 g / l, boric acid 5-15 g / l, here 10 g / l. By maintaining the pH at an alkaline level, the film speed can be increased without losing the amorphous property.

As a buffer for suppressing pH fluctuation,
Depending on the purpose, it can be selected from boric acid, carbonates, acetic acid, butyric acid, propionic acid, valeric acid, or alkali salts thereof. Here, it contains 3 g / l of sodium carbonate (Na ₂ CO ₃ ).

Urea (H ₂ NCSN) is used as a stabilizer for adsorbing fine particles in the processing solution in order to suppress spontaneous decomposition.
H ₂₎ is contained 0.1 g / l. As a stabilizer,
In addition to urea, it is desired to contain thiourea or at least one or more selected from organic adsorbents such as lead sulfide, lead chloride and antimony chloride.

Examples of the activator include an anionic water-soluble special polymer, a cationic water-soluble special polymer, an anionic ethoxylate α-naphtholsulfonic acid, a nonionic polychain high molecular weight nonionic activator, and an anionic sodium dialkyl sulfosuccinate. It is desirable to contain at least one or more selected from ethers, nonionic high molecular weight polyethylene glycols and the like. Here, 1 g / l of an anionic ethoxylate α-naphtholsulfonic acid is contained.

Further, in the treatment example 1, 10 g / l of copper sulfate hydrate CuSO ₄ .5H ₂ O is contained. Copper sulfate supplies copper ions, improves the corrosion resistance, spreadability, and contact resistance of the film, and can be used as a conductive film. Also,
If copper ion is contained, the film is antibacterial due to its oxidative decomposition effect
Obtains sterilization and rot prevention effects. Further, by containing copper ions, an antibacterial effect by oxidative decomposition of far-infrared rays is generated, and an effect of preventing spoilage of water and especially a water-soluble oil is generated.

After the film is formed, the second water washing 104 is performed.
It was performed while tap water was constantly shaken by overflowing. In the hot water washing 105, tap water heated to 75 to 85 ° C. was immersed while rocking for 2 minutes while constantly overflowing, and finally, drying 106 by natural drying using self-heating was performed.

The sliding parts subjected to the above processing are SCM41
Scratching test with coin-shaped metal edge similar to the test piece of No. 5, and high-speed rotation with highly aggressive Alundum-formed deformed media in a fluid centrifugal barrel. No film was peeled off. Also, the film was not peeled off by the test using the fluidized centrifugal barrel. From the above experimental results, in the sliding parts subjected to the surface treatment as described in the processing example 1, the sliding property when used continuously for a long time from the beginning of use also shows
The effect of maintaining stable low friction was confirmed.

It should be noted that nickel-phosphorous or nickel-
In the formation of a film made of boron, a structure is formed in which a matrix made of nickel-phosphorus or nickel-boron is formed, and various metals can be stably contained in the film. The composition of the metal contained in the film can be changed to give various characteristics.

For example, when tungsten is contained as in the processing solution of the present processing example 1, there is an effect that hardness is increased. In addition, when copper ions are contained, corrosion resistance, spreadability, and contact resistance are improved, and they can be used as a conductive film. Also,
In addition to the copper ion described in the present processing example 1, by containing each ion of yttrium ion, titanium ion, vanadium ion, zirconium ion and silver ion, an antibacterial effect by oxidative decomposition of far-infrared ray is generated, and water and especially water-soluble This has the effect of preventing oil from spoiling. Further, by containing titanium ion, zirconium ion, silver ion, and platinum ion in addition to copper ion, antibacterial, sterilization, and rot preventive effects by oxidative decomposition effect are obtained. In addition to the ions contained in the treatment liquid of the present treatment example 1, if a titanium ion or a vanadium ion is contained, a superconducting effect, high toughness, and a high melting point can be obtained. Further, a platinum ion, a vanadium ion, yttrium ion, there is cracking effect catalytic effect by containing titanium ions is carried out for example NOx, SOx, degradation such as CO _2. Corrosion resistance and abrasion resistance are improved by containing tantalum ions and palladium ions, and the film can be used as a magnetic material by containing iron ions, cobalt ions, manganese ions, and boron ions. In addition, a heat-resistant material having a high melting point can be obtained by containing rhenium ions. The ion configuration is not limited to three types, but may be four or more types. In this way, the ion in the processing liquid is composed of a plurality of types of ions to provide high slidability and to change the type of metal ions to be contained in the processing liquid depending on the purpose of use to make the characteristics of the film appropriate. can do.

Further, in the film formation of the processing example 1, since the pH of the processing liquid is maintained at 9 to 10, the surface of the sliding component is not etched by the acid, and the mirror-finished sliding is performed by the chemical polishing method. The surface roughness of the moving part is not roughened, and the surface roughness of the coating surface can be maintained at a high level. Therefore, even at the beginning of use, not only the friction coefficient is small, but even if the film becomes thin due to some wear, the sliding component itself is hardly exposed, and the state where the friction coefficient is small can be maintained for a long time.

(Processing Example 2) Here, processing example 2 of Embodiment 1 will be described. Table 2 shows the composition of the processing liquid of Processing Example 2.

[0057]

[Table 2]

In processing example 2, the Ni-WP of FIG.
PH of the treatment liquid in the process of forming film 103 is 9 to 10,
The treatment was performed at 89 to 93 ° C for 20 minutes. As a result, the adhesion was improved and the coefficient of friction was reduced. The glossiness of the film surface was good, and both the corrosion resistance and the hardness were good.
The surface roughness was as good as the Ra value of 0.015 μm.

(Processing Example 3) Here, Processing Example 3 of Embodiment 1
Will be described. Table 3 shows the composition of the processing liquid of Processing Example 3.

[0060]

[Table 3]

In processing example 3, the Ni-WP of FIG.
The pH of the treatment liquid in the process of forming the coating 103 was adjusted to 7 to 8.5, and treatment was performed at 89 to 93 ° C. for 20 minutes. Nickel ions and tungsten ions were increased to increase the amount of complexing agent sodium citrate. As a result, the adhesion was good, but the coefficient of friction was large, the surface became a dull film with a white tint, and it was found that the surface roughness became rough even by visual inspection. Ra up
The value was about 0.06 μm, which was not suitable for a sliding film.

When the pH was adjusted to 9 or more, a good film could be obtained particularly at pH 11.5 or more.
Therefore, it has been clarified that the pH has an important influence on the smoothness of the film even when there is no difference in the ion content. That is, a pH of 9 or more is desirable because the surface of the material dough is not roughened by etching.
It was found that 1.5 or more is desirable for forming a film having high smoothness.

(Processing Example 4) Here, Processing Example 4 of Embodiment 1
Will be described. Table 4 shows the composition of the processing liquid of Processing Example 4.

[0064]

[Table 4]

In processing example 4, the Ni-WP of FIG.
The pH of the treatment liquid in the process of forming the coating film 103 was set to 6.5 and 8
The treatment was performed at 9 to 93 ° C for 20 minutes. The treatment was performed for comparison using an acidic treatment liquid. As a result, the adhesion was good, but the friction was poor, and the surface was matte and the Ra value was 0.06 μm due to the effect of etching with acid.
m, which is not suitable for a sliding film.

(Processing Example 5) Next, a processing example 5 of the first embodiment will be described. Table 5 shows the composition of the processing liquid of Processing Example 5.

[0067]

[Table 5]

In processing example 5, the Ni-WP of FIG.
The pH of the treatment liquid in the process of forming the coating film 103 was set to 6.5 and 8
The treatment was performed at 9 to 93 ° C for 20 minutes. This type is also acidic type, in particular NiSO ₄ · 6H ₂ O and _Na 2 WO
Is obtained by increasing the content of ₄ · 2H ₂ O. As a result, the adhesion was good, but even though nickel ions and tungsten ions increased, the surface of the film was white, rough, matte, and poor in friction due to etching by acid, and the surface roughness was Ra value. It was found to be 0.06 μm, which was not suitable for a sliding film.

(Processing Example 6) Next, a processing example 6 of the first embodiment will be described. Table 6 shows the composition of the processing liquid of Processing Example 6.

[0070]

[Table 6]

In processing example 6, the Ni-WP of FIG.
The pH of the treatment liquid in the process of the formation film 103 was set to 11 to 12, and treatment was performed at 89 to 93 ° C. for 20 minutes. This type is an alkali type and does not contain any other than the necessary auxiliaries. As a result, the adhesion was good and the coefficient of friction was small, almost the same result as in processing example 2. The glossiness of the film surface was good, and both the corrosion resistance and the hardness were good. The surface roughness was as good as the Ra value of 0.015 μm. However, the thickness of the film was slightly thinner than that in the processing example 2.
Therefore, it was found that by controlling the pH, it was possible to prevent the etching of the base material by acid. And it turned out that the auxiliary | assistant etc. which are not included in the processing example 6 but are included in the processing example 2 increase the film thickness of a film | membrane.

(Processing Example 7) Here, processing example 7 will be described. Table 7 shows the composition of the processing liquid of Processing Example 7.

[0073]

[Table 7]

The treatment liquid of the treatment example 7 is a Ni—B-based film, and is treated in the same process as in the experiment 1 to obtain the N-B film shown in FIG.
The pH of the treatment liquid in the process of the i-B forming film 3 was set to 11.7, and the treatment was performed at 90 to 92 ° C. for 20 minutes. As a result, a good film was obtained with good adhesion in terms of gloss, surface roughness and coefficient of friction. Therefore, even in the Ni-B type coating, p
It was found that when H was maintained at 11.7, a film having good surface roughness could be obtained.

(Processing Example 8) Here, processing example 8 will be described. Table 8 shows the composition of the processing liquid of Processing Example 8.

[0076]

[Table 8]

In the treatment example 8, the treatment was carried out in the same process as in the experiment 1, the pH of the treatment solution in the process of the Ni—B forming film 3 in FIG. Was performed. As a result, it was found that, as compared with the treatment example 7, a film having better adhesion in terms of gloss, surface roughness, and coefficient of friction could be obtained with a higher pH value.

(Processing Example 9) Here, processing example 9 will be described. Table 9 shows the composition of the processing liquid of Processing Example 9.

[0079]

[Table 9]

In the treatment example 9, the treatment was carried out in the same manner as in the experiment 1, and the pH was adjusted to 14 to 15 while measuring with the pH meter of the treatment solution in the step of the Ni—B forming film 3 in FIG. A treatment was performed at -92 ° C for 20 minutes. as a result,
As compared with the treatment example 8, a better film was obtained with better adhesion in terms of gloss, surface roughness, and coefficient of friction. However, pH 14
It was also found that the pH was preferably up to 14, since the decomposition of the processing solution was promoted when the pH exceeded 1.

(Embodiment 2) Next, Embodiment 2 will be described. Here, FIG. 3 is a diagram illustrating the steps of the processing of the second embodiment. The processing steps of Example 2 include degreasing 201, first rinsing 202, Ni-WP film formation 203, and second rinsing 20.
4. Ni-WP-BN film formation 205, third water washing 2
06, hot water washing 207, and drying 208. The step of the second water washing 204 can be omitted.
Example 2 is a suspension in which particles of boron nitride (BN) are further dispersed in the bath composition of Example 1 after the treatment of forming the Ni-WP film 103 of Example 1 shown in FIG. 1. BN
This is a process for forming a film using a processing solution obtained by adding a slurry (Nissin Refurtec) to the processing solution of Example 1. In a suspension such as a BN slurry, fine particles such as boron nitride are sufficiently dispersed in a water-based liquid by a polymer-based polymer, an emulsifier, an activator, and the like. Fine particles such as boron can be easily dispersed in the processing solution. As described above, 0.5 g / l of the BN slurry is added to the treatment liquid, and the treatment liquid is further subjected to immersion treatment after washing with water. The processing steps are the same as those in Example 1 and the formation of the Ni-WP-BN film 20
Since it is the same process except for the fifth and third washing 206,
These explanations are omitted, and Ni-WP-BN film formation 2
Only the process step 05 will be described.

In the process of forming the Ni—WP—BN film 205, the immersion in the treatment liquid is performed at 90 ° C. for 5 minutes while rocking, as in the immersion with the treatment liquid of the first embodiment.

The particles added to the treatment liquid are not limited to boron nitride, but may be any of dispersed particles of alumina, silicon dioxide, tungsten trioxide, zirconia, titanium dioxide, etc., or graphite, molybdenum disulfide, fluororesin, etc. You can choose from Further, the particles to be added are not limited to those processed into a suspension, and may be powdery particles. However, a suspension has the effect of facilitating dispersion in a treatment liquid.

In the second embodiment, by performing the above-described surface treatment, the film thickness is increased and the surface roughness is slightly increased as compared with the film formed by the surface treatment method described in the first embodiment. It can be said, however, that it has an equivalent hardness. Then, the coefficient of friction is lowered by the action of the fine particles of boron nitride taken into the film. Therefore, although the surface roughness is somewhat roughened, the sliding property is improved by lowering the friction coefficient, the hardness is the same, and the film thickness is large, which is a desirable characteristic in terms of wear resistance. Further, when boron nitride is contained, there is an effect that the heat resistance is improved and it can be applied to a mold or the like.

Third Embodiment Next, a third embodiment will be described. Here, FIG. 4 is a diagram showing the steps of the processing of the third embodiment. The treatment in the third embodiment includes the steps of degreasing 301, first washing 302, formation of a Ni-WP-BN film 303, second washing 304, hot washing 305, and drying 306. In Example 2, the BN slurry was added to the bath composition by 0.5 after the treatment of forming the Ni-WP film 203 of Example 1 shown in FIG.
g / l Ni-WP-
Although the BN film formation 205 was treated, in Example 3, Ni-WP- which was immersed and formed a film at a time with a bath composition in which the BN slurry was added to the treatment liquid of Example 1 was used.
The BN film formation 303 is performed. Therefore,
Except for the process of forming the Ni-WP-BN film 303, the same process as that of the second embodiment is performed, so that the description thereof is omitted, and only the process of the process of forming the Ni-WP-BN film 303 is described. I do.

The bath composition in the process of forming the Ni-WP-BN film 303 will be described. In the processing liquid used in the process of forming the Ni—WP film 103 (see FIG. 2) in Example 1 and the process of forming the Ni—WP film 203 in Example 2, Ni ^{+ 2}
Is treated using a treatment solution adjusted to 6.0 to 7.0 g / l. However, if the treatment is continued, the soluble nickel is consumed. Therefore, the treatment is continued to dilute the soluble nickel. Therefore, a high concentration of nickel sulfate is appropriately replenished to raise the soluble nickel concentration to a predetermined range. At this time, it is necessary to collect and dispose of the processing solution in which the soluble nickel has dropped to 3.6 g / l. is there. BN was added to the treatment solution in which the recovered soluble nickel was reduced to 3.6 g / l.
By adding 0.5 g / l of the slurry, the N
A processing solution used for the process of forming the i-WP-BN film 303 can be prepared. The pH is adjusted to pH 9.0. The immersion is performed at 90 ° C. for 5 minutes while rocking. After the film is formed, a second water washing 304, a hot water washing 305, and a drying 306 are similarly performed.
I do.

In this case as well, the particles dispersed in the treatment liquid are not limited to boron nitride, but are dispersed particles of alumina, silicon dioxide, tungsten trioxide, zirconia, titanium dioxide, etc., or graphite, molybdenum disulfide, fluorine resin. And so on. The particles to be added are not limited to those processed into a suspension, but may be powdery particles.

By performing the processing according to the process of the third embodiment,
Compared to the film formed by the surface treatment method described in Example 1, it can be said that the film thickness is large and the surface roughness is slightly rough.
Hardness is equivalent. Then, the coefficient of friction is lowered by the action of the fine particles of boron nitride taken into the film. Therefore, although the surface roughness is somewhat roughened, the sliding property is improved by lowering the friction coefficient, the hardness is the same, and the film thickness is large, which is a desirable characteristic in terms of wear resistance. Further, when boron nitride is contained, there is an effect that the heat resistance is improved and it can be applied to a mold or the like.

The coatings of Example 2 and Example 3 were:
There is no difference in characteristics on the surface. However, in Example 3, in the processing of Ni-W-P film formation, in order to replenish the reduced solubility of nickel by continued treatment, nickel sulfate _(NiSO 4 · _6H 2 O)
The it is necessary to replenish, that time discard part a treatment liquid soluble nickel concentration is reduced, supplemented with new nickel sulfate in the same amount as the amount of waste and treatment liquid (NiSO 4 · 6H _{2 O)} Replace it. At this time, even the processing solution discarded in which the concentration of soluble nickel is reduced to about 3.6 g / l can be used for the surface treatment method of Example 3. for that reason,
The processing liquid discarded by the processing in the first embodiment or the second embodiment can be reused. Therefore, since the amount of wastewater to be discarded can be reduced, the treatment of wastewater becomes easy. And there is an effect that the cost by wastewater treatment can be reduced.

(Embodiment 4) Next, Embodiment 4 will be described. Here, FIG. 5 is a diagram illustrating the steps of the processing of the fourth embodiment. The processing steps in Example 4 are degreasing 401,
First water wash 402, Ni-WP film formation 403, second water wash 404, Ni-P, Ni-B film formation 405,3
It comprises a second water washing 406, a hot water washing 407, and a drying 408. The processing steps in the fourth embodiment are the same as those in the first embodiment shown in FIG.
After the film is formed by the process of forming the i-W-P film 103, a process of forming a nickel-phosphorous or nickel-boron-based film is added after the second water washing 104.

The same Ni-W as described in the first embodiment
At the time when the step of forming the -P film 403 is completed, a second water washing 404 is performed, and the Ni-P, Ni
-The process of forming the B film 405 is performed. The condition at this time is
Nikko ME-AR (Ni-P type), (180 g / l)
Alternatively, Nikon boron (Ni-B type) (180 g /
The pH was adjusted to 6.5 as specified by the manufacturer, and the soluble nickel was adjusted to 6.5 g / l. The temperature conditions were 90-92 ° C for Niiko ME-AR (Ni-P type) and 63-65 ° C for Niikoboron (Ni-B type). Then, similarly to Experimental Example 1, the third water washing 406 was performed while the tap water was constantly shaken by overflowing. 40
For No. 7, tap water heated to 75 to 85 ° C. was immersed while rocking for 2 minutes while constantly overflowing, and finally dried 408 by natural drying using self-heat.

The processing solution in this case is not limited to the above-mentioned processing solution, but is a commercially available processing solution for electroless plating, for example, ENPACK RE-MU- manufactured by Ebara Uzilite Co., Ltd.
II (Ni-P type), Unipack BN-S, M, R (N
i-B system), Evashield EC (Cu system), Top Nicolon LPH-S (Ni-P system) manufactured by Okuno Pharmaceutical Co., Ltd.,
Top Chemialloy 66-M, 1, 2 (Ni-B system), Capallaside (Cu system), Niiko ME manufactured by Kisai Co., Ltd.
-AR (Ni-P type), Niikoboron (Ni-B
System), SEL-kappa (Cu system) Ni-P system, Ni
Various processing liquids of -B type and Cu type are used. Of these, it goes without saying that various processing solutions for electroless plating can be used, including Ni-P-based and Ni-B-based processing solutions.

According to the treatment according to the fourth embodiment, a hard nickel-phosphorous, nickel-boron, or copper-based film having a constant film thickness is adhered on the fine amorphous metal film. Can be formed. For this reason, the sliding parts that are in contact with each other are slid by the outer layer until they become more familiar, and after the outer layer is worn out, the hard amorphous material with low friction and excellent wear resistance The inner layer made of a material having a high abrasion resistance was exposed, and extremely low friction and extremely high wear resistance could be achieved by sliding with the inner layer.

(Embodiment 5) Next, Embodiment 5 will be described. Here, FIGS. 6A and 6B are diagrams illustrating the steps of the processing of the fifth embodiment. One of the processes of the fifth embodiment is shown in FIG.
As shown in (a), degreasing 501, first washing 502,
Ni-WP-BN film formation 503, second water washing 50
4. Ni-P, Ni-B film formation 505, third water washing 5
06, hot water washing 507, and drying 508. The other is, as shown in FIG. 6B, degreasing 509, first rinsing 510, Ni-WP film formation 511, second rinsing 512, Ni-WPB film formation 513, third time The process comprises the steps of washing 514, forming Ni-P and Ni-B films 515, fourth washing 516, hot water 517, and drying 518. That is, according to the second and third embodiments, Ni-WPB
After the N film is formed, the Ni-P and Ni-B films are formed. Therefore, the process 50 shown in FIG.
1 to 504 are processes 301 to 30 of the second embodiment shown in FIG.
4 and the processing 509 to 514 shown in FIG.
Are the same as the processes 201 to 206 of the third embodiment shown in FIG.

As described in Examples 2-3, Ni-W-
At the stage when the process of forming the composite multidimensional metal film by P-BN is completed and the washing is completed, Ni-P, Ni-B film formation 505 (FIG. 6 (a)) and 515 (FIG. 6 (b)) Is performed. Ni-P, Ni-B film formation 505 (FIG. 6)
(A)) The processing of 515 (FIG. 6 (b)) is performed with the processing liquid shown in Experimental Example 1. The conditions at this time were as follows: Niiko ME-AR (Ni-P system) (180 g / l) processing solution,
Similarly, Nikon boron (Ni-B type) (180 g / l)
The pH was adjusted to 6.5 as specified by the manufacturer, and the soluble nickel was adjusted to 6.5 g / l. The temperature conditions are 90-92 ° C. for Niiko ME-AR and 63 for Niikoboron.
６５65 ° C., and immersed while rocking each for 20 minutes. Then, similarly to Experimental Example 1, the third washing 506 (FIG. 6)
(A)) or the fourth rinsing 516 (FIG. 6 (b)) was performed while tap water constantly overflowing and rocking. Hot water washing 507 (FIG. 6A), 517 (FIG.
(B)) is immersed in tap water heated to 75 to 85 ° C. while oscillating for 2 minutes while constantly overflowing, and finally drying 508 by natural drying using self-heating (FIG. 6).
(A)) and 518 (FIG. 6 (b)).

By performing the treatment in accordance with the steps as in Example 5, a hard nickel-based metal film having a certain film thickness is formed on a nanometer-class ultrafine metal film having a higher amorphous property.
A phosphorus-based or nickel-boron-based film could be formed in close contact. For this reason, the sliding parts that are in contact with each other are slid by the outer layer until they become familiar, and after the outer layer is worn, a hard amorphous material with extremely low friction and excellent wear resistance is obtained. The inner layer composed of highly nanometer class ultra-fine metal material is exposed,
By sliding with this inner layer, extremely low friction and extremely high wear resistance could be achieved.

Although the present invention has been described with reference to the embodiment, it is needless to say that the present invention is not limited to the above-described embodiment, and can be modified and implemented without departing from the scope of the claims. For example, by using copper powder, powder rubber, silica sand, or the like for the particles to be dispersed in Example 2 or Example 3, it is possible to increase the friction coefficient and prevent slip.

[0098]

According to the surface treatment liquid for sliding parts according to the first aspect of the present invention, the surface roughness of the sliding parts is not roughened by etching or the like, but is extremely uniform, high in hardness and dense and amorphous. There is an effect that a surface treatment for forming a highly-reactive film can be performed. In addition, since the processing solution itself can be made to have a stable quality by the complex forming agent, chemical management is also facilitated. Therefore, a sliding part having a film formed by such a surface treatment liquid for a sliding part is a film in which a nanometer-class ultrafine metal film having a high amorphous property is laminated, and the abrasion resistance of the film itself is reduced. In addition to being high, the friction coefficient is extremely low, in addition to the fact that the surface is formed extremely smooth, so that even if used as a sliding component for a long time, it shows high durability while maintaining low friction. It works. Furthermore, since various metals can be stably arranged in the structure in which the matrix of nickel-phosphorus or nickel-boron is formed, there is an effect that the configuration of the coating can be changed according to the purpose of the sliding component. .

According to the surface treatment liquid for sliding parts of the second aspect of the present invention, in addition to the effects of the surface treatment liquid for the sliding parts of the first aspect, phosphorus ions or boron ions are blended in a well-balanced manner. There is an effect that can be.

According to the surface treatment liquid for a sliding component of the third aspect of the present invention, in addition to the effect of the surface treatment solution for a sliding component of the first or second aspect of the invention, tungsten ions are contained. In this way, it is possible to extremely enhance the adhesion to the surface of the sliding component, and not only to form a film having high slidability on its own, but also to carry another film having poor adhesion with good adhesion. Therefore, there is an effect that a heterogeneous film having poor adhesion can be formed with good adhesion.

According to the surface treatment liquid for sliding parts of the invention according to claim 4, in addition to the effect of the surface treatment liquid for sliding parts according to any one of claims 1 to 3, especially the amorphous property There is an effect that a good film having high sliding characteristics can be formed.

According to the surface treatment liquid for sliding parts of the invention according to claim 5, in addition to the effect of the surface treatment liquid for sliding parts according to any one of claims 1 to 4, in addition to the effects of the particles contained therein, There is an effect that the slidability can be further enhanced by the characteristics.

According to the surface treatment method for a sliding part of the invention according to the sixth aspect, by using the surface treatment liquid for a sliding part according to any one of the first to fifth aspects, the surface is smoothly polished. In combination with the surface of the sliding component, the surface treatment of the sliding component having extremely high slidability can be performed.

According to the surface treatment method for a sliding component of the invention according to claim 7, in addition to the effect of the surface treatment method for a sliding component according to claim 6, the Ra value is polished to 0.03 or less. This makes it possible to form a smooth coating on the surface of the extremely smooth sliding component without roughening the surface roughness, and to perform a surface treatment with extremely good slidability on the surface of the sliding component. There is an effect that can be.

According to the surface treatment method for a sliding component of the invention according to the eighth aspect, in addition to the effect of the surface treatment method for a sliding component according to the sixth or seventh aspect, excellent mass productivity and stability are obtained. There is an effect that surface treatment of smooth sliding parts can be performed.

According to the surface treatment method for a sliding component according to the ninth aspect of the present invention, in addition to the effect of the surface treatment method for a sliding component according to any one of the sixth to eighth aspects, a film having different properties is provided. Can be formed on the surface with good adhesion, and there is an effect that surface treatment of a sliding component having high slidability utilizing the properties of the respective films can be performed.

According to a tenth aspect of the present invention, there is provided a sliding component having a high slidability, the surface of which is treated by the method of any of the sixth to ninth aspects. There is an effect that can be.

[Brief description of the drawings]

FIG. 1 is a diagram showing the steps of processing in Experiment 1.

FIG. 2 is a diagram showing the steps of the processing of Example 1.

FIG. 3 is a diagram showing a process of processing in a second embodiment.

FIG. 4 is a diagram showing a process of a process according to a third embodiment.

FIG. 5 is a diagram illustrating a process of processing according to a fourth embodiment.

FIG. 6A is a diagram illustrating an example of a process of a process according to a fifth embodiment. (B) It is a figure which shows another example of the process of the process of Example 5.

[Explanation of symbols]

101: degreasing, 102: first washing with water, 103: Ni-W
-P film formation, 104: second water washing, 105: hot water washing, 1
06 ... Dry

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 201/00 C09D 201/00 F term (reference) 4J038 AA011 CD092 HA036 HA216 HA356 HA446 HA476 KA02 NA01 NA11 PB06 PB07 PC02 PC03 4K022 AA02 AA48 BA01 BA02 BA03 BA04 BA05 BA06 BA07 BA08 BA09 BA11 BA12 BA13 BA14 BA15 BA16 BA17 BA18 BA19 BA20 BA21 BA22 BA24 BA25 BA26 BA28 BA32 BA33 BA34 BA36 CA11 CA28 DA01 DB01 DB02 DB03 DB04 DB05 DB06 DB07

Claims (10)

[Claims] 1. A reducing agent, a complexing agent for metal ions, a stabilizer for adsorbing fine particles in a processing solution for suppressing spontaneous decomposition, a buffering agent for suppressing pH fluctuation, and an activator. And nickel ions, at least one metal ion of phosphorus ions or boron ions, tungsten ion, cobalt ion, palladium ion, rhenium ion, yttrium ion, molybdenum ion, titanium ion, manganese ion, At least one metal ion selected from the group consisting of vanadium ion, zircon ion, chromium ion, copper ion, gold ion, silver ion, zinc ion, iron ion, lead ion, tin ion and platinum ion A surface for sliding parts, characterized in that the pH is adjusted to be 9 or more and 14 or less. Management solution. 2. The surface treatment liquid for a sliding part according to claim 1, wherein the metal ion of either the phosphorus ion or the boron ion is contained as a reducing agent. 3. The surface treatment liquid for a sliding part includes nickel ions, tungsten ions, and phosphorus ions.
The surface treatment liquid for a sliding component according to claim 1, wherein the surface treatment liquid contains a species ion or three types of ions, a nickel ion, a tungsten ion, and a boron ion. 4. The surface treatment liquid for a sliding part, wherein the content of phosphorus is 3 to 15% by weight of the formed film component.
The surface treatment liquid for a sliding component according to any one of claims 1 to 3, wherein the surface treatment liquid is contained so as to be: 5. The surface treatment liquid for a sliding component is selected from the group consisting of oxides such as alumina, silicon dioxide, tungsten trioxide, zirconia, and titanium dioxide, graphite, molybdenum disulfide, boron nitride, and fluororesin. The surface treatment liquid for a sliding component according to claim 1, wherein one or more selected particles are dispersed. 6. A film is formed by electroless plating on a smooth polished surface of a sliding component using the surface treating solution for a sliding component according to claim 1. A surface treatment method for a sliding component. 7. The method according to claim 6, wherein the surface of the sliding component to be subjected to the surface treatment is polished so that the Ra value becomes 0.03 μm or less. . 8. The surface of the sliding part to be subjected to the surface treatment is polished by a chemical polishing method after being polished by a mechanical polishing method.
The surface treatment method for a sliding component according to item 1. 9. A film formed by electroless nickel plating containing nickel and phosphorus or nickel and boron on the film formed by the surface treatment method according to claim 6. A surface treatment method for a sliding component. 10. A sliding component which has been treated by the surface treatment method for a sliding component according to claim 6. Description: