JP2001247891A - Carrier composition for drawing metallic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metallic material drawing composition which is environmentally advantageous because it contains no boron or produces no sludge. SOLUTION: This metallic material drawing composition contains an ingredient (A) which is an alkali metal sulfate, an ingredient (B) which is an alkali metal silicate, and an ingredient (C) which is a water-soluble or water-dispersible polymer, with their weight ratios being (B)/(A)=0.01 to 1 and (C)/[(A)+(B)]=0.01 to 0.5. The water-soluble or water-dispersible polymer may be one or more selected from the group consisting of polyurethane resins, polycarbonates, water-soluble polyolefins, and polyethers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a carrier for drawing metal materials such as steel, galvanized steel, stainless steel, copper, aluminum and titanium. More specifically, the present invention does not involve a chemical reaction, can form a film having excellent carrier properties on the surface of a metal material to be processed by a physical method such as spraying or immersion, and generates waste and waste liquid accompanying the reaction. The present invention relates to a carrier material composition for drawing a metal material which is excellent also in environmental measures such that no cracks occur.

[0002]

2. Description of the Related Art Conventionally, in the drawing process of a metal material, a carrier film is formed on the surface of the metal material for the purpose of preventing seizure and galling between a workpiece and a tool, and also for retaining and improving lubricant. Processing has been performed. This carrier treatment is divided into two methods: a method of forming a film by a chemical reaction, and a method of physically directly attaching the film. Usually, after the carrier treatment, the material is subjected to a drawing process by applying a lubricant, an oil or a wax mainly composed of metallic soap or slaked lime before processing.

The method of using a chemical reaction in the formation of a carrier film is called a chemical conversion treatment method, and is a phosphate treatment for forming a zinc phosphate or calcium phosphate film or an oxalic acid for forming an iron oxalate film. A film having a role as a carrier is formed on the metal surface by salt treatment or the like. This method has good adhesion to materials and very good seizure resistance, and is used in a wide range of plastic working fields such as forging, drawing and drawing.

However, in these chemical conversion treatment methods, it is inevitable that a large amount of sludge generated by a chemical reaction becomes an industrial waste, and it is necessary to wash with water after the chemical conversion treatment, so that various types of heavy metal ions, phosphate ions, Wastewater containing nitrate ions, fluorine ions and the like is generated, and the treatment thereof requires much labor and cost.

On the other hand, as a method of physically attaching a carrier film without a chemical reaction, a method mainly comprising borax is generally used. Borax is widely used because it has good adhesion to the material and its liquid management is simple. However, it has problems such as a decrease in lubricating performance due to moisture absorption of the film and a lower corrosion resistance than the chemical conversion film. In addition, the use of wastewater near lakes and marshes may be restricted due to the movement of boron. In addition, treatment with lime soap is widely performed, but has problems such as lubricity, corrosion resistance, and dust generation.

As a technique for solving these problems, Japanese Patent Application Laid-Open No. H10-36876 discloses an alkali metal sulfate and an alkali metal borate as essential components, and as an optional component, a fatty acid alkali metal salt and a fatty acid alkaline earth. A lubricant containing a metal salt, a solid lubricant, and a water-soluble thermoplastic resin is disclosed. This composition, while maintaining lubricity,
The liquid can be controlled only by adjusting the nonvolatile content and the pH, and no waste liquid is generated. However, there is a problem that boron is contained and lubricity is insufficient. Therefore, at present, a carrier composition for drawing a metal material which does not contain boron, has no environmental problems, and has excellent adhesion, lubricity and corrosion resistance has not been obtained.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and forms a carrier film having excellent adhesion, lubricity and corrosion resistance on the surface of a metal material, and An object of the present invention is to provide a carrier material composition for drawing a metal material, which does not contain boron, is easy to treat waste, and is also useful in environmental measures.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on means for solving the above problems, and as a result,
By dipping and drying the metal material in an aqueous solution containing alkali metal sulfate, alkali metal silicate and water-soluble or water-dispersible polymer in a specific ratio, it is boron-free and has a strong lubrication performance. The inventors newly found that a film was formed, and completed the present invention.

That is, the carrier material composition for drawing a metal material of the present invention comprises an alkali metal sulfate as the component (A), an alkali metal silicate as the component (B), and (C)
It contains a water-soluble or water-dispersible polymer as a component, and the weight ratio of (B) / (A) is in the range of 0.01 to 1,
The weight ratio of (C) / (A + B) is in the range of 0.01 to 0.5.

The water-soluble or water-dispersible polymer includes a urethane resin, a polycarboxylate, a water-soluble polyolefin,
It is preferably at least one selected from the group consisting of polyethers and polysaccharides.

[0011]

Hereinafter, the contents of the present invention will be described in more detail. The alkali metal sulfate of the component (A) used in the carrier material for drawing a metal material of the present invention is not particularly limited in composition, and Na ₂ SO ₄ , K ₂ SO ₄ , NaKSO _{4 and the} like can be used. Also, a mixture of these can be used.

The alkali metal silicate of the component (B) used in the present invention is not particularly limited, and lithium silicate, potassium silicate, sodium silicate, sodium orthosilicate,
Sodium metasilicate, water glass and the like can be used. Also,
Mixtures of these can also be used.

Here, the weight ratio (B) / (A) of the alkali metal sulfate (A) and the alkali metal silicate (B) is preferably in the range of 0.01 to 1, more preferably. , 0.05 to 0.7. For the component (A),
When the weight ratio (B) / (A) of the component (B) is less than 0.01, the film hardness becomes low and the load resistance becomes poor, so that seizure between the metal material and the tool is liable to occur. Further, in this case, the corrosion resistance is significantly reduced. (B) / (A)
Is more than 1, the coating hardness becomes too high, and the coating itself tends to damage tools and materials, which is not preferable.

Next, the water-soluble or water-dispersible polymer compound (C) used in the present invention is not particularly limited, but may be selected from urethane resins, polycarboxylates, water-soluble polyolefins, polyethers and polysaccharides. At least one selected from the group consisting of:

The urethane resin used in the present invention is preferably an aqueous urethane, and any of those generally available may be used, and an aqueous urethane made from polyester polyol, polyol or polyisocyanate can be used.

The polycarboxylate used in the present invention is
Any commonly available one may be used, but polymers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid or copolymers containing these as monomers and their derivatives and potassium salts, sodium salts, ammonium It is preferable to use a salt or the like.

As the water-soluble polyolefin used in the present invention, any generally available water-soluble polyolefin may be used, but it is preferable to use polyvinyl alcohol, polyvinylpyrrolidone and derivatives thereof.

As the polyether used in the present invention, any generally available polyether may be used, but it is preferable to use polyethylene glycol, polypropylene glycol and derivatives thereof.

As the polysaccharide used in the present invention, any generally available polysaccharide may be used, but methylcellulose, methylstarch, methylguar gum, ethylcellulose, ethylstarch, ethylguar gum, carboxymethylcellulose, carboxymethylcellulose Starch, carboxymethyl guar gum, carboxymethyl hydroxyethyl cellulose, carboxymethyl hydroxyethyl starch, carboxymethyl hydroxyethyl guar gum, hydroxyethyl cellulose, hydroxyethyl starch, hydroxyethyl guar gum, hydroxyethyl methyl cellulose, hydroxyethyl methyl starch, hydroxyethyl methyl guar gum, hydroxypropyl Cellulose, hydroxypropyl starch, hydroxypropyl guar It is preferable to use at least one selected from the group of gum, hydroxypropylmethylcellulose, hydroxypropylmethylstarch, hydroxypropylmethylguar gum, tricarboxystarch, tricarboxyamylose, tricarboxypectin, xanthan gum, sulfoacetic acid-β1.3 glucan and the like. preferable.

The compounding ratio of the component (C) is (C) / (A + B)
Is preferably 0.01 to 0.5 as a weight ratio. More preferably, it is 0.05 to 0.2. If the weight ratio (C) / (A + B) is less than 0.01, crystals of the alkali metal sulfate grow too large in the course of film formation in the drying step after the treatment, and the retention and introduction of the lubricant are poor. Become. The weight ratio (C) / (A + B) is 0.5
If the ratio exceeds the above range, the adhesion of the film is reduced, and seizure tends to occur. Furthermore, in this case, the hygroscopicity also increases significantly.

The carrier agent composition for drawing a metal material of the present invention contains a rust preventive additive such as nitrite, molybdate, alkanolamine or heterocyclic amine which is generally used for improving rust preventive properties. May be added.

The carrier material composition for drawing a metal material of the present invention may contain a chelating agent such as tartrate, gluconate, EDTA and the like generally used for improving liquid stability. Absent.

The carrier agent composition for drawing a metal material of the present invention has a sulfur-based, phosphorus-based, and sulfur-based, phosphorus-based or phosphorus-based material, particularly for improving seizure resistance under processing conditions in which the enlargement ratio of the metal surface is high. An extreme pressure additive such as chlorine may be added.

In order to improve the wettability of the surface of the target metal, the carrier material composition for drawing a metal material of the present invention contains a commonly used nonionic surfactant, anionic surfactant and amphoteric surfactant. At least one selected from surfactants may be added.

Since the carrier composition for drawing a metal material of the present invention does not utilize a chemical reaction when forming a film, the target material is not particularly limited, but practically, iron, steel, stainless steel, copper, aluminum, It is preferably used when a metal such as titanium or an alloy thereof is drawn. In the carrier agent composition of the present invention, it is preferable that the surface of the metal material is subjected to a pretreatment such as degreasing (an ordinary alkaline degreasing agent can be used), washing with water, pickling, and washing with water, and after cleaning the surface, is adhered. The pickling may be omitted if no oxide scale is attached. These pretreatments may be performed by a conventional method.

The carrier material composition for drawing a metal material of the present invention does not utilize a chemical reaction when forming a film on the metal material, and therefore does not generate waste such as chemical sludge. Therefore, unless the acid or alkali is brought in a large amount, the renewal of the liquid and the removal of the waste are not required, and the component hardly fluctuates. Therefore, the bath may be managed by replenishing the taken out.

The carrier agent composition of the present invention is applied to a metal material by a conventional method such as dipping, spraying or pouring. The application may be performed as long as the metal surface is sufficiently covered with the carrier agent composition, and there is no particular limitation on the application temperature and time. After application, it is necessary to dry the carrier composition. The temperature of the bath and the drying temperature may be room temperature, but for more efficient drying, the temperature of the bath is 50 to 80 ° C and the drying temperature is 60 to 120 ° C.
Is preferred. The amount of the carrier film formed on the metal material is not particularly limited, but is preferably ³ to 20 g / m ² in consideration of lubricity, adhesion, and corrosion resistance. More preferably, it is 5 to 15 g / m ² .

[0028]

Example 1 Examples of the present invention will be described together with comparative examples, and effects thereof will be described more specifically. Examples 1 to 9, Comparative Example 1
~ 3 Carrier agent compositions were prepared at the ratios shown in Table 1. Preparations were made by dissolving or dispersing sulfates, silicates, and water-soluble or water-dispersible polymers in water.

Further, the carrier agent compositions shown in Examples 1 to 9 and Comparative Examples 1 to 3 were heated to 60 ° C., and a test material (material: S45C spherical annealed material, a wire having a diameter of 3 mmφ and a length of 20 m) was cooled to 30%. After immersion for 2 seconds, dried at 100 ℃ for 30 minutes,
Carrier processing was performed.

Comparative Examples 4 to 6 (lime soap, borax,
(Phosphate) The current carrier was treated under general conditions.

The wire drawing test material was subjected to the following pretreatment steps (1) to (4) prior to the application of the carrier composition. (1) Alkaline degreasing: Fine Cleaner 4360 (registered trademark) manufactured by Nippon Parkerizing, concentration: 20 g / L, temperature: 60 ° C, immersion for 10 minutes) (2) Rinse: normal temperature tap water immersion for 60 seconds (3) Pickling: hydrochloric acid , Concentration 17.5% by weight, temperature RT, immersion time 10 minutes (4) water washing: normal temperature tap water immersion 60 seconds

In the drawing test, a single-head drawing machine was used to perform continuous drawing in the following step. Element wire: 3.00mmφ → 1 extension: 2.76mm → 2 extension: 2.40mm → 3 extension:
2.17 mm → 4 elongation: 1.90 mm 5 elongation: 1.72 mmφ → 6 elongation: 1.51 mm For each pass of the drawing, a commercially available calcium-based dry powder was used.

The carrier film adhesion amount and the remaining adhesion amount (g /
m ² ) was calculated from the weight difference before and after heating 5% chromic acid to 75 ° C. and immersing for 15 minutes to peel off the carrier film. The lubricating property was evaluated based on the pull-out load after 6 consecutive elongations and the remaining amount of the film. Corrosion resistance is performed by treating the wire with a carrier and leaving it for 4 weeks in an environment with a constant temperature and high humidity bath temperature of 30 ° C and a relative humidity of 80%.
The rust generation area% on the material surface was evaluated.

From Table 1, it can be seen that Examples 1 to 9 using the carrier composition for drawing a metal material of the present invention are drawn after 6 consecutive elongations as compared with Comparative Examples 1 to 3 which do not satisfy the constitutional requirements of the present invention. The load is low, the residual adhesion amount is large, and it is apparent that the lubrication is excellent. Example 1
9 show that they have performance comparable to that of Comparative Examples 4 to 6, which are the current processing. On the other hand, the corrosion resistance is also clearly improved as compared with Comparative Examples 4 and 5, and it is considered that the corrosion resistance may be sufficient as an alternative to the current treatment.

[0035]

[Table 1]

[0036]

Example 2 In the mass production drawing test, continuous drawing was performed using a continuous drawing machine. Material: Si / Cr steel wire (9254) Original wire: rod (φ8.00mm) → shaving (φ7.40mm) → heat treatment → inline coating Wire drawing schedule: (φ7.40mm) → 6.40mm → 5.60m
m → 5.00mm → 4.50mm → Deformed wire φ4.07mm (round wire conversion) →
Deformed wire φ3.67mm (round wire conversion)

In the examples of Table 2, those of Example 6 of Table 1 were used as carrier agents. In Comparative Examples of Table 2, 5 and 6 of Comparative Examples in Table 1 were used. The lubricant for wire drawing for each pass is a calcium-based dry powder.

[0038]

[Table 2]

From the above results, it can be determined that the present coating has significantly improved drawability compared to Borax and has drawability comparable to that of zinc phosphate. The corrosion resistance is higher than that of Borax, and it can be used without problems in mass production. In addition, wastewater such as borax does not contain boron and does not generate waste such as sludge like zinc phosphate, so it is very useful for environmental problems such as wastewater and waste treatment, and for reducing the burden on workers. It is.

[0040]

As is clear from the above description, the carrier material composition for drawing a metal material of the present invention can form a film having high lubricity and corrosion resistance comparable to a chemical conversion treatment by a simple treatment. Can be done. In addition, since no waste such as chemical sludge is generated and boron and the like are not contained, wastewater treatment is good, so that it is useful for users in terms of workability and environmental measures.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10M 107/32 C10M 107/32 107/36 107/36 107/42 107/42 107/44 107/44 125 / 22 125/22 125/26 125/26 145/04 145/04 145/14 145/14 145/16 145/16 145/24 145/24 145/40 145/40 149/10 149/10 149/18 149/18 // C10N 10:02 C10N 10:02 20:00 20:00 Z 30:12 30:12 40:24 40:24 Z 50:02 50:02 (72) Inventor Shuji Nagata Central Tokyo 1-17-1 Nihonbashi-ku, Japan Nippon Park Coloring Co., Ltd. (72) Inventor Tetsuo Jimbo 10-1 Hamacho, Amagasaki-shi, Hyogo Shinko Wire Industry Co., Ltd. F-term (reference) 4H104 AA18A AA18C AA21A AA21C CB02A CB02C CB08A CB08C CB09A CB09C CB14A CB14C CB19A CB19C CE05A CE05C CE13A CE13C EA17A EA17C FA01 LA06 PA23 QA01 QA08

Claims (2)

[Claims] An alkali metal sulfate as the component (A),
It contains an alkali metal silicate as the component (B), a water-soluble or water-dispersible polymer as the component (C), and (B) /
(A) weight ratio within the range of 0.01 to 1, (C) / (A
+ B) The weight ratio of (B) is in the range of 0.01 to 0.5. 2. The method according to claim 1, wherein the water-soluble or water-dispersible polymer is at least one selected from the group consisting of urethane resins, polycarboxylates, water-soluble polyolefins, polyethers, and polysaccharides. A carrier material composition for drawing a metal material according to the above.