JP2003268570A - Metallic surface control agent and lubrication treatment method for metallic surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic surface control agent which is used for improving the service life and reactivity to a lubrication treatment before a metallic surface is subjected to nonreactive or reactive lubrication treatment, and to provide the lubrication treatment method for the metallic surface. <P>SOLUTION: In a first method, a metallic surface cleaned by pickling is brought into contact with a surface control agent of pH 8 to 12 containing a carbonate, a bicarbonate and a nitrite in specified ratios at an ordinary temperature to 80°C for 1 to 10 min. The metallic surface is next brought into contact with a nonreaction series lubricant or an oil based lubricant. In a second method, the metallic surface with a chemical conversion coating formed by phosphate treatment or oxalate treatment is similarly contacted with the same control agent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to improve the life of a lubricating treatment liquid or the reactivity thereof before conducting a non-reactive or reactive lubrication treatment on the surface of a metal material such as steel, stainless steel, titanium, and aluminum. The present invention relates to a metal surface conditioner used for this purpose and a method for lubricating a metal surface. More specifically, in the present invention, when performing plastic working such as forging, wire drawing, and tube drawing of a metal material, the pH of the metal surface is subjected to a non-reactive or reactive lubrication treatment on the surface of the metal material. The present invention relates to a metal surface conditioner used for improving the life of a lubricating treatment liquid or improving reactivity by adjusting the above, and a method of lubricating a metal surface for pretreatment with the metal surface conditioner.

[0002]

2. Description of the Related Art Generally, when plastic working a metal material such as steel or stainless steel, a lubricating film is formed on the metal surface in order to prevent seizure or galling caused by metal contact between the work material and the tool. There is. As a film formed on the metal surface, there are a type in which a lubricant is physically attached to the metal surface and a type in which a lubricant is used after a chemical conversion film is chemically formed on the metal surface. Lubricants that physically adhere to the metal surface are generally used for light processing because they have poor adhesion compared to those used by forming a chemical conversion coating on the metal surface. For the chemical conversion film-lubricant type, after forming a phosphate film or an oxalate film having a role as a carrier on the surface, a lubricant having a slip property is used. This type has a two-layer structure consisting of a chemical conversion film as a carrier film and a lubricant, and exhibits extremely high seizure resistance. Therefore, the chemical conversion coating-lubricant type is used in a very wide range in the field of plastic working such as forging, wire drawing and pipe drawing. Particularly in fields where plastic working is difficult, a method in which a phosphate film or an oxalate film is used as a base film and a lubricant is formed on it is often used.

Prior to the lubrication treatment for forming a lubricating film on the metal surface, pickling with hydrochloric acid, sulfuric acid, nitric acid or a mixed acid thereof is performed for the purpose of removing oxides (scale) on the metal surface. When the lubricant is physically attached to the metal surface, the acid component remaining on the metal surface is mixed in the lubricant. Similarly, when a lubricating film is formed on the chemical conversion film, the acid-based chemical conversion treatment liquid is mixed with the lubricant. The deterioration of the lubricant is promoted by the mixing of the acid component or the chemical conversion treatment liquid, and it becomes necessary to frequently dispose of the lubricant and renew it. This is a major issue for industrial waste from the viewpoint of global environmental protection in recent years, and a treatment process for reducing waste is desired.

When forming a lubricating film on a chemical conversion film, a treatment with a reactive soap such as sodium stearate is often performed as a lubricant. Sodium stearate reacts with the chemical conversion treatment film to form a reactive soap having high lubricity. Since the amount of reactive soap produced by reacting sodium phosphate with the phosphate coating greatly contributes to lubricity, stable reaction formation is indispensable when a highly lubricious coating is required. It is known that the chemical conversion film and sodium stearate react most when the pH is about 10 to 12, but the pH of the treated material interface changes from acidic to weakly alkaline due to the chemical conversion treatment liquid remaining on the metal surface, and the amount of reaction soap produced. Is reduced. From this point of view, a surface conditioner capable of stably producing a reaction soap on the chemical conversion film is used.

The surface conditioner used to solve such problems is a borate or phosphate system. By using these surface modifiers, the carry-in of the acid component or the chemical conversion treatment liquid to the lubricant was reduced. However, boron and phosphorus contained in borate or phosphate are themselves regulated wastewater, and the treatment of wastewater containing these is a problem.

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention is to solve the problems of the above-mentioned prior art, and in consideration of global environmental protection, in the reaction system or non-reactive system lubrication process of various metallic materials. The purpose is to provide a surface conditioner that can be used for.

[0007]

[Means for Solving the Problems] As a result of intensive studies for solving the above problems, the present inventors have found that excellent surface conditioning can be achieved by adding a carbonate, a bicarbonate and a nitrite in a specific ratio. The present invention has been completed and the processing method thereof has been established to complete the present invention.

That is, the metal surface conditioner of the present invention is
(A) 50 to 80 parts by weight of carbonate, and (B) bicarbonate 10
-40 parts by weight and (C) 5 to 15 parts by weight of nitrite are contained, and the first method of lubricating a metal surface according to the present invention is to remove a metal surface cleaned by pickling. (A) Carbonate 0.05 to 7.0 g / L, (B) Bicarbonate 0.1 to 5.0 g / L, and (C) Nitrite 0.05 to
1.0 g / L and a pH of 8 to 12 at a room temperature to 80 ° C. for 1 to 10 minutes, and then a non-reactive lubricant or oil lubricant. The second characteristic is that the metal surface on which the chemical conversion film is formed by either the phosphate treatment or the oxalate treatment is (A) carbonate 0.5 to 7.0 g / L, and (B) bicarbonate. Salt 0.1-5.
0 g / L and (C) nitrite 0.05-1.0 g / L, pH 8-12 surface conditioning solution and room temperature-80 ° C
The method is characterized by contacting for 1 to 10 minutes, and then contacting a non-reactive lubricant, an oil lubricant or a reactive lubricant.

[0009]

When the metal subjected to pickling or chemical conversion treatment is treated with the surface conditioner of the present invention, pH adjustment in the treatment liquid, hydrogen ion transfer and oxidation inhibiting action are realized cooperatively, as will be described later in detail. Thus, it is possible to prevent the adverse effects of pickling and the like on the lubricant.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The contents of the present invention will be described in detail below. The (A) carbonate used in the metal surface conditioner of the present invention is for increasing the pH of the surface conditioner and imparting a sufficient neutralizing power. Therefore, it is necessary that the carbonate to be applied is uniformly dissolved in the treatment liquid and has the property of sufficiently neutralizing the mixture of acid components. Furthermore, when performing a treatment with a reactive lubricant containing sodium stearate as a main component on a metal surface having a film formed on it by one of the chemical conversion treatment methods of phosphate treatment and oxalate treatment. Must have the property of raising the pH of the interface between the metal and the lubricant and promoting its reaction. Specific examples of the carbonate having such a property include sodium carbonate and potassium carbonate.

Next, the (B) bicarbonate salt is for imparting a buffering action by giving and receiving hydrogen ions to the mixing of the acid. Therefore, it is necessary that the bicarbonate to be applied is uniformly dissolved in the treatment liquid and has a sufficient buffering action against the inclusion of acid components. Furthermore, a surface on which a chemical conversion coating is formed by a phosphate treatment or an oxalate treatment on the metal surface,
It is necessary that the bicarbonate has the property of adjusting the pH so that the chemical conversion film is not excessively dissolved when the surface conditioning liquid is contacted at room temperature to 80 ° C. for 1 to 10 minutes. Specific examples of such bicarbonate include sodium bicarbonate and potassium bicarbonate.

The nitrite (C) used in the present invention is for suppressing the oxidation of the metal surface by taking in oxygen in the adjusting solution. Therefore, it is necessary that the applied nitrite is uniformly dissolved in the treatment liquid and has a sufficient inhibitory effect on the oxidation of the metal surface. Specific examples of such nitrites include sodium nitrite and potassium nitrite.

The amount of carbonate (A) in the metal surface conditioner according to the present invention is preferably 50 to 80 parts by weight. More preferably, it is in the range of 55 to 70 parts by weight. If the amount is less than 50 parts by weight, a sufficient surface conditioning effect may not be obtained depending on the shape of the agent to be treated. Also,
If it exceeds 80 parts by weight, dissolution of the chemical conversion coating is promoted, which is not preferable.

The blending amount of the (B) bicarbonate in the metal surface treating agent according to the present invention is preferably 10 to 40 parts by weight. It is more preferably in the range of 20 to 35 parts by weight. If the blending amount is less than 10 parts by weight, the buffering effect of the treatment liquid is small, which may cause a problem in stability of the treatment liquid. Also, 4
If it exceeds 0 part by weight, a sufficient surface conditioning effect may not be obtained, which is not preferable.

The compounding amount of (C) nitrite in the metal surface treating agent according to the present invention is preferably 5 to 15 parts by weight.
It is more preferably in the range of 7 to 12 parts by weight. If the amount is less than 5 parts by weight, sufficient rust prevention may not be obtained, which is not preferable. Further, if it exceeds 15 parts by weight, a sufficient surface conditioning effect may not be obtained, which is not preferable.

In the surface conditioning liquid according to the present invention, the amount of the carbonate (A) is preferably 0.5 to 7.0 g / L. The range is more preferably 0.7 to 5.0 g / L. If this amount is less than 0.5 g / L, a sufficient surface adjusting effect may not be obtained depending on the shape of the material to be treated, which is not preferable. Further, if it exceeds 7.0 g / L, dissolution of the chemical conversion treatment film is promoted, which is not preferable.

In the surface conditioning liquid of the present invention, the amount of the (B) bicarbonate is preferably 0.1 to 5.0 g / L. The range is more preferably 0.3 to 3.0 g / L. If this amount is less than 0.1 g / L, the buffering effect of the treatment liquid is small, which may cause a problem in the stability of the treatment liquid. Also 5.0g /
If it exceeds L, a sufficient surface conditioning effect may not be obtained, which is not preferable.

In the surface conditioning liquid according to the present invention, the amount of (C) nitrite is preferably 0.05 to 1.0 g / L.
The range is more preferably 0.1 to 0.5 g / L. If this amount is less than 0.05 g / L, sufficient rust prevention may not be obtained, which is not preferable. If it exceeds 1.0 g / L, a sufficient surface conditioning effect may not be obtained, which is not preferable. The pH of the surface conditioning liquid needs to be in the range of 8-12. If the pH is less than 8, the surface conditioning effect will be insufficient, and if it exceeds 12, the metal surface will be eluted, which is not preferable.

The target metals of the metal surface conditioner and the lubricating surface treatment method according to the present invention are iron, steel, stainless steel,
It is a metal material such as copper or copper alloy, aluminum or aluminum alloy, titanium or titanium alloy.
The shape of the metal material is not limited to a material such as a rod material or a block material, but may be a shape material (gear, shaft, or the like) after plastic working such as drawing or forging, and is not particularly limited.

The surface conditioner of the present invention is for adjusting the metal surface such as degreasing metal material which has been washed with water and then pickled, and which has been subjected to a chemical conversion coating. The surface modifier used in the present invention is not particularly limited in terms of the material and surface condition of the metal material. The chemical conversion treatment is a known method such as a phosphate film (zinc phosphate, manganese phosphate, calcium phosphate, iron phosphate, tin phosphate, etc.), an oxalate film (iron oxalate, etc.), cryolite, calcium aluminate, hydroxy. It can be performed by coating with apatite. As a lubricant used as a post-treatment after pickling and surface preparation, there is a non-reactive lubricant or an oil lubricant. The non-reactive lubricant is one containing lime soap or an inorganic salt and wax or molybdenum disulfide. As the oil-based lubricant, mineral oil, fats and oils are used as the base oil, and there are those containing S-based, P-based, Cl-based extreme pressure agents and other additives. The type and concentration of these are not particularly limited.
Further, when the surface is adjusted after forming the chemical conversion film, the lubricant used in the post-treatment also includes a non-reactive lubricant, an oil lubricant or a reactive lubricant. The non-reactive lubricant contains lime soap or an inorganic salt and wax or molybdenum disulfide as a component. Some oil-based lubricants use mineral oil or fats and oils as the base oil, and contain S-based, P-based, Cl-based extreme pressure agents and other additives. The reactive lubricant contains metal stearate as a main component. The concentration of these lubricants and the reaction time are not particularly limited.

The method of treating the metal surface with the surface conditioner of the present invention is not particularly limited, but the dipping method,
A flow coat method, a spray method or the like can be used. Depending on the shape of the material, it is suitable to contact for 1 to 10 minutes, preferably 3 to 5 minutes in order to sufficiently replace the residual acid content on the metal surface. In addition, in the case of the spray method, carbon dioxide gas in the air may be absorbed and the pH may drop, so care must be taken. The liquid temperature varies depending on the material and the situation, but it is preferable to use it in the range of normal temperature to 80 ° C. More preferably, it is 40 to 70 ° C.

[0022]

EXAMPLES Examples of the present invention will be given together with comparative examples to more specifically describe the effects thereof.

[0023]

[Rust resistance] A test piece (SPCC-SD material 70m
m × 150 mm × thickness 0.8 mm) was treated in the following steps, and the degree of rusting during drying and indoor exposure in the factory was visually determined. The evaluation criteria are as follows.

<Treatment Step> Degreasing: Commercially available degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.), concentration 20 g / L, temperature 60 ° C., immersion for 10 minutes Rinse: tap water, room temperature, immersion for 10 seconds Pickling: hydrochloric acid, concentration 17.5%, room temperature, soaking for 10 minutes Water washing: tap water, room temperature, soaking for 10 seconds Surface preparation: treatment agent of the present invention, 60 ° C, soaking for 1 minute (1): natural drying, room temperature , 5 minutes drying (2): 80 ℃, 10 minutes

<Evaluation Criteria> A: No rust occurred during drying and exposure. B: Rust is generated on the edge portion during the exposure test, but no significant rusting occurs. C: Spot rust is generated on the entire surface during the exposure test, or significant rust is locally generated. D: The entire surface is rusted during the exposure test. E: Rust occurred during drying. Generally, a performance of C or higher is required.

[Solubility of chemical conversion film] The solubility of the chemical conversion film was measured by using a test piece (SPCC-SD material 70 mm x 150 mm x thickness 0.
8 mm) was treated in the following steps, and the evaluation was performed by a method of measuring the dissolved amount of the chemical conversion film.

<Process> Degreasing: Commercially available degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.), concentration 20 g / L, temperature 60 ° C., immersion for 10 minutes Rinse: tap water, room temperature, immersion for 10 seconds Acid Washing: Hydrochloric acid, concentration 17.5%, normal temperature, soaking for 10 minutes Water washing: Tap water, normal temperature, soaking for 10 seconds Chemical conversion treatment: Commercially available phosphate chemical conversion treatment agent (registered trademark)
Palbond 181X, Nippon Parkerizing Co., Ltd.
Manufactured), concentration 90 g / L, temperature 80 ° C., immersion 10 minutes, water washing: tap water, room temperature, immersion 10 seconds Surface adjustment: treatment agent of the present invention, 60 ° C., immersion 30 minutes water washing: tap water, room temperature, immersion 10 seconds Drying (2): 80 ° C, 10 minutes

<Evaluation Criteria> A: The amount of dissolution is 0.1 g / m ² or less. B: The amount of dissolution is 0.3 g / m ² or less. C: The dissolved amount is 0.8 g / m ² or less. D: Dissolved amount exceeds 0.8 g / m ² . Generally, a performance of B or higher is required.

[0029]

[Lubricating film reactivity] Lubricating film reactivity is determined by test pieces (SPCC
-SD material 70 mm × 150 mm × thickness 0.8 mm) was evaluated by a method of measuring the amount of lubricating film when it was processed in the following steps.

<Process> Degreasing: Commercially available degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nippon Parkerizing Co., Ltd.), concentration 20
g / L, temperature 60 ° C, immersion for 10 minutes Rinse: tap water, room temperature, soak for 10 seconds Pickling: hydrochloric acid, concentration 17.5%, room temperature, soak for 10 minutes Wash: tap water, room temperature, soak for 10 seconds Chemical conversion treatment: Commercially available phosphate chemical conversion treatment agent (registered trademark
Palbond 181X, Nippon Parkerizing Co., Ltd.
Made), concentration 90 g / L, temperature 80 ° C., immersion 10 minutes water washing: tap water, room temperature, immersion 10 seconds Surface preparation: treatment agent of the present invention, 60 ° C., immersion 1 minute lubrication treatment: commercially available lubricant treatment agent (registered) Trademark Palube 235), Concentration 70g / L, 70 ° C Immersion 3 minutes Drying: 80 ° C, 10 minutes

<Evaluation Criteria> A: The amount of the metallic soap film increases by 30% or more. B: The amount of the metallic soap film increases by 15% or more and less than 30%. C: The amount of the metallic soap film increases by 5% or more and less than 15%. D: The amount of increase in the reaction amount of metal soap is less than 5%. Generally, the performance of B or higher is required as a metal surface conditioner.

[0032]

[Lubricity] Lubricity was measured by a spike test. The spike test was conducted according to the invention of JP-A-5-7969. The spike test piece is an S45C spheroidized annealed material, and the size of the test piece is 25 mmφ and the height is 30 mm. Lubricity was evaluated by the spike height after the test. The higher the spike height, the better the lubricity. Generally, 13.0 mm or more is accepted.

<Process> Degreasing: Commercially available degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.), concentration 2
0g / L, temperature 60 ° C, immersion for 10 minutes Rinse: tap water, room temperature, soak for 10 seconds Pickling: hydrochloric acid, concentration 17.5%, room temperature, soak for 10 minutes Wash: tap water, room temperature, soak for 10 seconds Chemical conversion treatment: Commercially available phosphate chemical conversion treatment agent (registered trademark
Palbond 181X, Nippon Parkerizing Co., Ltd.
Manufactured), concentration 90 g / L, temperature 80 ° C, immersion 10 minutes water washing: tap water, room temperature, immersion 10 seconds Surface preparation: treatment agent of the present invention, 60 ° C, immersion 1 minute lubrication treatment: commercial non-reactive lubrication treatment Drug (registered trademark
Palube 235), Concentration 70g / L, 70 ℃ Immersion 3 minutes (10) Drying: 80 ℃, 10 minutes

[0034]

Comparative Example 1 The agent of the present invention in the processing step of each performance evaluation was carried out with a commercially available agent (registered trademark PREPAREN 21 manufactured by Nippon Parkerizing Co., Ltd.).

[0035]

Comparative Example 2 The agent of the present invention in the processing step of each performance evaluation was performed with caustic soda.

[0036]

[Comparative Example 2] It was carried out without using the agent of the present invention in the processing step of each performance evaluation.

The results of the above tests are shown in Table 1. As is clear from Table 1, Examples 1 to 7 using the metal surface conditioner of the present invention show a surface conditionability equal to or higher than that of the commercially available surface conditioner of Comparative Example 1. On the other hand, Comparative Example 1
As it contains a large amount of boron, the environmental impact of wastewater is large. Comparative Example 2 using caustic soda is not preferable as a surface conditioner because it significantly dissolves the chemical conversion film. Further, it is understood that Examples 1 to 7 exhibit superior rust preventive property, chemical conversion film solubility and metallic soap reactivity as compared with Comparative Example 3 in which no surface adjustment is performed, and exhibit excellent surface conditioning properties.

[0038]

As is apparent from the above description, the use of the metal surface conditioner and surface treatment method thereof according to the present invention
In the treatment of non-reactive or reactive lubricants, the life of the lubricating treatment liquid or the reactivity can be improved. In addition, since it does not contain regulated wastewater, it has a low impact on the global environment and has an extremely high industrial utility value.

[Brief description of drawings]

FIG. 1 is a chart (Table 1) showing performance evaluation levels of Examples 1 to 7 and Comparative Examples 1 to 3.

FIG. 2 is a chart (Table 1) showing performance evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10M 125/20 C10M 125/20 // C10N 10:02 C10N 10:02 10:04 10:04 10:12 10:12 40:20 40:20 Z 80:00 80:00 F term (reference) 4H104 AA13C AA17C AA19C BB17C DA05C FA01 FA02 FA06 PA21 RA02 4K044 AA02 AA03 AA06 BA11 BA17 BA21 BB03 BC01 CA04 CA16 CA53

Claims (7)

[Claims] (1) 50 to 80 parts by weight of (A) carbonate, and (B)
Bicarbonate 10-40 parts by weight, and (C) nitrite 5-15
And a metal surface conditioner. 2. A metal surface cleaned by pickling,
(A) Carbonate 0.5 to 7.0 g / L, (B) Bicarbonate 0.1 to 5.0 g / L, and (C) Nitrite 0.05 to
1.0 g / L is contained, and it is brought into contact with a surface conditioning solution having a pH of 8 to 12 at room temperature to 80 ° C. for 1 to 10 minutes, and then brought into contact with a non-reactive lubricant or an oil lubricant. Lubrication method for metal surface. 3. The method for lubricating a metal surface according to claim 2, wherein a chemical conversion treatment is performed between the surface conditioning with the surface conditioning liquid and the lubrication processing. 4. The method for lubricating a metal surface according to claim 2, wherein the non-reactive lubricant contains lime soap, an inorganic salt, wax or molybdenum disulfide as a main component. 5. A metal surface on which a chemical conversion coating is formed by either phosphate treatment or oxalate treatment is (A) carbonate 0.5 to 7.0 g / L, and (B) bicarbonate. 0.1-5.
0 g / L and (C) nitrite 0.05-1.0 g / L, pH 8-12 surface conditioning solution and room temperature-80 ° C
For 1 to 10 minutes, and then contacting with a non-reactive lubricant, oil lubricant or reactive lubricant. 6. The method for lubricating a metal surface according to claim 5, wherein the non-reactive lubricant contains lime soap, an inorganic salt, wax or molybdenum disulfide as a main component. 7. A method of lubricating a metal surface, wherein the reactive lubricant contains metal stearate as a main component.