JP2002309385A - Surface lubricated metallic product environment- friendly having excellent formability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface lubricated metallic product the environment- friendly having excellent formability. SOLUTION: The surface lubricated metallic product is obtained by coating both sides or one side thereof with a lubrication film essentially consisting of (A) wheat flour and (B) a lubricating function impartion agent of 1 to 30 mass% to the wheat flour and controlled to 0.5 to 50 g/m<2> . Preferably, silica particles (C) are incorporated therein by to 30 mass% to the wheat flour.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a good environmentally friendly lubricated surface-treated metal product having excellent formability and having a lubricating film composed of flour and a lubricating function-imparting agent on the surface.

[0002]

2. Description of the Related Art Conventionally, when a metal plate is processed by press molding or the like, lubricating oil or the like is applied for the purpose of preventing the metal surface and the die surface from being damaged due to poor lubrication. In addition, the application of the lubricating oil complicates the manufacturing process, and the scatter causes deterioration of the working environment. Further, in the degreasing step after press molding, the removal of lubricating oil was performed using an organic halogen-based solvent such as freon, trichloroethane, and dichloromethane, but these not only adversely affected the health of workers, but many of them were remarkable. It is an environmentally hazardous substance. From the viewpoint of protection of the ozone layer, many of the products were scheduled to be completely abolished according to the Montreal Protocol, so an alternative method was needed to avoid the use of these solvents. Eliminating the need for degreasing using volatile lubricating oils and degreasing with organic solvents have been attempted. However, volatile lubricating oils do not provide sufficient moldability during severe press molding. It is not a good solution because of the problem described above.

[0003] A non-delaminated lubricating steel sheet using a resin film which provides excellent formability far exceeding lubricating oil without using a lubricating oil or a removing solvent has been developed. In some cases, a drying step is required, or a resin-based lubricating film remains on the metal surface even after molding and after product disposal, which may cause a problem from the viewpoint of recycling and reuse. On the other hand, a delaminated lubricating steel sheet that has the same formability as a non-delubricated lubricating steel sheet and in which the film is dissolved and removed by alkali degreasing has been developed. Processing and disposal of resin components may be required.

[0004] Japanese Patent Application Laid-Open No. 10-180391,
JP-A-11-140481, JP-A-11-2707
No. 86 proposes a lubrication method that is environmentally friendly in which a suspension mainly composed of cereal powder such as flour is used as a lubricant during processing. However, there is a problem that it has not yet been achieved.

[0005]

SUMMARY OF THE INVENTION The present invention solves these problems and provides a good environmentally friendly lubricated surface-treated metal product excellent in formability and having a lubricating film composed of flour and a lubricating function-imparting agent on the surface. The purpose is to provide.

[0006]

Means for Solving the Problems The inventors of the present invention have solved the above-mentioned problems and have conducted intensive studies to obtain a good environmentally friendly lubricated surface-treated metal product excellent in formability. It has been found that the above-mentioned object can be achieved by coating a lubricating film mainly composed of on both surfaces or one surface of a metal, and the present invention has been completed. The gist of the present invention is as follows. (1) Flour (A), and 1-3 to the flour
A good environment excellent in formability, in which a lubricating film mainly containing 0% by mass of a lubricating function-imparting agent (B) is coated on both sides or one side so that the amount of adhesion is 0.5 to 50 g / m ^2. Corresponding lubrication surface treated metal products. (2) The lubricating film is 1 to 30% by mass with respect to the flour.
The environmentally friendly lubricated surface-treated metal product excellent in moldability according to the above (1), further comprising the silica particles (C) of (1). (3) The lubricating function-imparting agent (B) is characterized by comprising one or more of a polyolefin-based wax, a paraffin-based wax, a stearic acid-based solid lubricant, and a wax containing a fluorine-containing resin. The environmentally friendly lubricated surface-treated metal product excellent in formability according to (1) or (2). (4) The lubricating function-imparting agent (B) is a biodegradable aliphatic polyester-based, polyvinyl alcohol-based, polyamino acid-based, starch-based, chitosan-based, or cellulose-based solid lubricant, or two or more thereof. The environmentally friendly lubricated surface-treated metal product excellent in formability according to the above (1) or (2), comprising:

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
The flour used in the present invention exhibits good environmental compatibility,
It has been found that it has excellent coating properties and has an effect of retaining a lubricating function-imparting agent and improving moldability. Either strong flour or light flour may be used. Wheat flour can be dissolved in water or a solvent and used as a suspension. Water is preferred. It was confirmed that the flour had coating properties that were more than expected. It is desirable that the suspension is a suspension using water from the viewpoint of the environmental load of the coating process on the metal product.

The lubricating function-imparting agent used in the present invention has a function of further improving lubricity by reducing the coefficient of friction of the film surface, preventing mold seizure and the like, and improving press workability. Lubricating function imparting agent used in the present invention,
(A) a solid lubricant or wax composed of a long-chain aliphatic hydrocarbon and having no polar group; (b) a solid lubricant having a long-chain aliphatic hydrocarbon group (long-chain alkyl group) and a polar group in one molecule Alternatively, the particles are not particularly limited as long as they are particles composed mainly of wax or solid lubricant or wax composed of (c) fluorine-containing resin and can be stably and uniformly dispersed in the aqueous treatment liquid. a) is a polyolefin wax such as polyethylene or polypropylene having a hydrocarbon group of 125 to 700 carbon atoms or paraffin (microwax) having a hydrocarbon group of 32 to 72 carbon atoms, and (b) is a stearic acid-based wax. Solid lubricant,
Examples of (c) include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and the like, and one or more of these solid lubricants or waxes (a), (b), and (c). What mixed or modified is mentioned.

Examples of the solid lubricant or wax (b) include higher aliphatic alcohols having 12 to 22 carbon atoms (such as cetyl alcohol and stearyl alcohol) and hydrocarbon groups having 12 to 22 carbon atoms. Higher fatty acids having 13 to 17 carbon atoms (e.g., stearic acid and 12-hydroxystearic acid); metal soaps comprising higher fatty acids having 12 to 30 carbon atoms in the hydrocarbon group and divalent metals (lead stearate, stearic acid) Zinc acid, calcium stearate, etc.) and ester-based esters of higher fatty acids having 13 to 17 carbon atoms in the hydrocarbon group with other hydrocarbons, higher aliphatic alcohols having 13 to 17 carbon atoms in the hydrocarbon group. Esters of fatty acids with fatty dicarboxylic acids or fatty acids, esters of polyhydric alcohols with higher fatty acids (glycerin tristearate, trimethylolpropanate) And fatty acid amides such as monoamides or bisamides of higher fatty acids having 15 to 17 carbon atoms in the hydrocarbon group (palmitic acid amide, stearic acid amide, oleic acid amide, ethylene bisstearamide, methylene bisstear). Loamide, etc.), and waxes having a hydrocarbon group of 27 carbon atoms.
Higher fatty acid wax having a carbon number of 2
A wax comprising an ester of 7 to 34 higher fatty acids and an aliphatic diol, wherein the hydrocarbon group has 125 to 700 carbon atoms.
(Eg, a polyethylene chain having a carboxyl group at the end of a polyethylene chain and an acid group such as a hydroxyl group bonded at various positions in the chain) and the like.

The biodegradable lubricating function-imparting agents include polycaptolactones, polyglycolic acids,
Examples thereof include aliphatic polyesters based on polylactic acid, polybutylene sac-ethylene succinate, polyvinyl alcohol, polyamino acid, starch, chitosan, cellulose, nylon oligomer, and polyurethane. Also, starch and aliphatic polyester,
A composite such as starch and polyvinyl alcohol is exemplified.

The amount of the lubricating function-imparting agent to be added is 1 to 30% by mass, preferably 5 to 20% by mass, based on the solid content of the flour. If it is less than 1%, the required lubricating effect cannot be obtained. If it exceeds 30% by mass, the effect of improving the moldability will level off, and problems such as the detachment of the lubricating agent during the process will occur. It is known that the lubricating function imparting agent has a particle size slightly larger than the film thickness in the lubricating film. Therefore, in the present invention, the particle size should be adjusted in consideration of the film thickness of the film. Is preferred.

[0012] Silica is added to improve the film strength. The silica particles may be any of silica particles such as water-dispersible colloidal silica, crushed silica, and fumed silica. The addition amount of silica is preferably 1 to 30% by mass based on the solid content of flour. If it is less than 1%, a sufficient effect of improving the film strength cannot be obtained. If it exceeds 30%, the coating becomes brittle and, conversely, the galling property decreases.

[0013] In addition to the above-mentioned components (A), (B) and (C), the lubricating film coated on the lubricated surface-treated metal product of the present invention may be provided with a pigment for imparting a design property or imparting conductivity. Conductive additives, thickeners, defoamers, dispersants, desiccants, stabilizers, anti-skinning agents, fungicides, preservatives, antifreezing agents, etc., depending on the purpose, do not reduce the physical properties of the film It can be added within the range.

The amount of the lubricating film applied to the lubricated surface-treated metal product of the present invention is in the range of 0.5 to 50 g / m ² . If the amount of adhesion is less than 0.5 g / m ^2, damage to the base metal due to pressing during processing cannot be prevented, and the required workability due to the addition of sliding cannot be obtained. If it exceeds 50 g / m ² , the amount of film peeling powder increases at the time of molding, and it is necessary to frequently carry out maintenance of the mold, which lowers productivity. The lubricating resin film of the present invention is coated on both front and back surfaces or one surface of a metal according to the purpose.

As a method of forming a lubricating film for coating the lubricated surface-treated metal product of the present invention, generally, a flour is dissolved in a solvent such as water and a solvent dispersion such as an aqueous solution of a lubricating function-imparting agent is used. Can be applied by using a coating solution obtained by uniformly mixing the components by a conventionally known method such as a roll coater coating method or a spray method, followed by drying. After drying, the suspension medium of the flour and the lubricating function-imparting agent disappears,
A solid mixture film of flour, a lubricating function-imparting agent and silica particles is obtained.

In the present invention, the base may be subjected to a phosphate treatment or a chromate treatment in order to impart corrosion resistance and the like. In this case, the chromate treatment may be any of electrolytic chromate, reactive chromate and coating chromate. The chromate film is preferably formed by applying a chromate solution containing one or more of silica, phosphoric acid and a hydrophilic resin to partially reduced chromic acid, followed by drying. In the above-mentioned phosphate treatment, the amount of the attached phosphate is 0.5 to 3.5 as phosphate.
g / m ² is preferred. The amount of chromate adhered in the chromate treatment is 5 to 150 in terms of metal chromium.
mg / m ² is preferable, and 10 to 50 mg / m ² is more preferable. If the amount is less than 5 mg / m ² , an excellent corrosion resistance effect cannot be obtained. If the amount exceeds 150 mg / m ² , cohesive failure of the chromate film occurs during molding and workability is reduced. Further, depending on the purpose, the base may be pickled, treated with alkali, treated with electrolytic reduction,
A cobalt plating treatment, a nickel plating treatment, a silane coupling agent treatment, and an inorganic silicate treatment may be performed.

In the present invention, the metal used is not particularly limited, and for example, aluminum, titanium, zinc, copper, nickel, alloys containing these metals, and steel can be applied. When steel is used, the components are not particularly limited, and may be ordinary steel or chromium-containing steel such as stainless steel. The shape of the steel product is not limited, and it can be used for steel sheets such as cold-rolled steel sheets and hot-rolled steel sheets, as well as steel pipes and wires. Further, a coating plating layer may be provided on the surface of the steel, but the type thereof is not particularly limited. Examples of applicable plating layers include zinc plating, zinc-nickel plating, zinc-iron plating, and zinc-chromium. Plating, zinc-aluminum plating, zinc-titanium plating, zinc-magnesium plating, zinc-based plating such as zinc-manganese plating, and aluminum or aluminum alloy plating, lead or lead alloy plating, tin or tin alloy plating, and A small amount of different elements such as cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium,
Examples include those containing one or more of lead, antimony, tin, copper, cadmium, arsenic, and the like, and those in which inorganic substances such as silica, alumina, and titania are dispersed. The present invention is also applicable to multi-layer plating in combination with the above-mentioned plating and other types of plating, for example, iron plating, iron-phosphorus plating and the like. The plating method is not particularly limited, and electroplating, hot-dip plating, vapor deposition plating, and the like can be applied. In the case of a steel sheet, as a post-plating treatment, there are a zero spangle treatment which is a uniform appearance treatment after hot-dip plating, an annealing treatment which is a modification treatment of a plating layer, a temper rolling for surface condition and material adjustment, and the like. In the present invention, these are not particularly limited, and any of them can be applied.

A lubricating oil or a lubricating rust preventive oil can be further applied to the metal product having the lubricating film of the present invention formed thereon. However, it is preferable that the lubricating oil or the lubricating rust preventive oil to be applied does not swell or dissolve the lubricating film of the present invention.

[0019]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. 1. Test metal plate The following metal plates were used to cover the lubricating film.

· Electrogalvanized steel sheet (sheet thickness 0.8 mm,
Coating weight 20g / m ²⁾ · electrolytic zinc - nickel alloy plated steel sheet (sheet thickness 0.8m
m, plating adhesion amount 20 g / m ² ) ・ Electric zinc-iron alloy plated steel sheet (sheet thickness 0.8 mm, plating adhesion amount 20 g / m ² ) ・ Hot-galvanized steel sheet (sheet thickness 0.8 mm, plating adhesion amount 150 g / m ² ) ・ Hot-dip zinc-iron alloy plated steel sheet (sheet thickness 0.8 mm, coating weight 45 g / m ² ) ・ Hot-dip zinc-aluminum alloy plated steel sheet (sheet thickness 0.8
mm, coating weight 150g / m ² ) ・ Molten aluminum-silicon alloy plated steel sheet (sheet thickness 0.
8mm, coating weight 50g / m ² ) ・ Molten aluminum-silicon-magnesium alloy coated steel sheet (sheet thickness 0.8mm, coating weight 50g / m ² ) ・ Stainless steel sheet (sheet thickness 0.8mm, SUS436) ・ Cold rolling Steel plate (plate thickness 0.8 mm) Note that all the above metal plates were not subjected to chromate treatment. 2. Lubricating film composition A lubricating film was prepared using the following flour, a lubricating function-imparting agent, and silica particles. 1) Flour The following was used as flour.

A 10% by weight aqueous suspension of light wheat flour A 10% by weight aqueous suspension of strong wheat flour 2) Lubricating function-imparting agent The following was used as a lubricating function-imparting agent.・ PE wax A (low density polyethylene wax, softening temperature 110 ° C., average particle size 4.0 μm, dispersed as an aqueous emulsion, solid content 40% by mass) ・ PE wax B (low density polyethylene wax, softening temperature 110 ° C., average particle) 2.5 μm diameter, dispersed as an aqueous emulsion, solid content 40% by mass) PTFE wax (polytetrafluoroethylene wax, average particle diameter 0.8 μm, dispersed as an aqueous emulsion, solid content 60% by mass) Paraffin wax (synthetic paraffin) Wax, melting point: 105 ° C., average particle size: 5.0 μm, dispersed as an aqueous emulsion, solid content: 33% by mass. Calcium stearate (average particle size: 2.0 μm, dispersed as an aqueous emulsion, solid content: 40% by mass). Wax A (cellulose acetate wax, Vicat soft Point 110 ° C., powder dispersing an average particle diameter of 30 [mu] m) · biodegradable wax B (polycaprolactone wax,
Vicat softening point 103 ° C, powder dispersion, average particle size 40μ
m) ・ Biodegradable wax C (starch and polyvinyl alcohol mixed wax, powder dispersion, average particle size 30 μm) ・ Biodegradable wax D (butanediol succinic acid + adipic acid mixed wax, powder dispersion, average particle size 40 μm) 3) Silica particles As silica particles, a particle size of 10 to 20 nm, pH 8.6,
Colloidal silica having a heating residue of about 20% by mass was added so that the content in the film became 10% by mass. 3. Production of lubricated surface-treated metal products (Example 1)-Flour (water suspension) ... 500.0 parts by mass (90% by mass in terms of solid content in film)-PE wax A (aqueous emulsion) ... 12.5% Part (10% by mass in terms of solid content in the film) The coating liquid having the above composition is coated on a metal plate with a bar coater,
, And a lubricating film having the composition shown in Table 1 was formed on the metal plate. (Examples 2 to 23 and Comparative Examples 1 to 5) Similarly to Example 1, Table 1 (Examples 2 to 23 and Comparative Examples 1 to 5) was applied to each metal plate.
A lubricating film having the composition shown in 5) was applied and dried to produce a lubricated surface-treated metal plate. Adhesion amount is 1.5 as comparison material
g / m ² , a metal plate coated with lubricating oil (lubricating oil Z3 made by Idemitsu), a metal plate coated only with flour, and a metal plate coated with a non-delaminated urethane-based lubricating film were produced (Comparative Example 1).
~ 5). 4. Test and evaluation method The following press formability evaluation was performed on the lubricated surface-treated metal plate. A molding test was carried out under the following conditions using a cylindrical punch hydraulic molding tester, the maximum molding height of each sample was measured, and a lubricating oil was applied as a comparative material so that the amount of adhesion was 1.5 g / m ^2. The ratio to the maximum molding height when using the original plate (this is defined as the molding height ratio) was determined. The definition formula of the molding height ratio is shown below. The shape test was performed at room temperature. <Molding height ratio> = Maximum forming height of lubricated metal plate A 最大 Maximum forming height of lubricated metal plate A <Molding conditions> Punch diameter: 70 mmφ, Blank diameter: 150 mmφ, Pressing load: 2 ton, Molding speed: 20 mm / min Tool condition: FCD-500 The appearance of the sample after working was observed, and the mold galling was evaluated according to the following index.

○: No defects on the metal plate surface △: Slight scratches on the metal plate surface ×: Many galls on the metal plate surface As shown in Table 1, the lubricated surface-treated metal product according to the present invention is excellent. It is clear that it has good moldability.

[0023]

The metal product according to the present invention is a lubricated surface-treated metal product which has excellent formability, has a low environmental load and is environmentally friendly, and has an extremely high industrial value.

[0024]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10M 105/22 C10M 105/22 107/02 107/02 107/32 107/32 107/36 107/36 107 / 38 107/38 107/44 107/44 125/26 125/26 159/02 159/02 169/04 169/04 173/02 173/02 // C10N 20:06 C10N 20:06 Z 30:06 30 : 06 40:24 40:24 Z 50:02 50:02 50:08 50:08 (72) Inventor Hiroshi Kanai 20-1 Shintomi, Futtsu-shi, Chiba F-term in the Technology Development Division, Nippon Steel Corporation (reference 4D075 CA04 CA07 DA06 DA23 DB02 DB03 DB05 DB06 DB07 EA06 EA10 EB07 EB13 EB16 EB19 EB35 EB38 EB40 EB56 EB57 EC03 EC07 EC54 4H104 AA22C BA02A BB17A CA01A CB02A CB13A CB19A01 Q02A01A02 BC01 CA53

Claims (4)

[Claims] Claims 1. A flour (A) and, for the flour,
1 to 30% by mass of a lubricating function-imparting agent (B) as a main component
Lubricating film with an adhesion amount of 0.5 to 50 g / m ^TwoWill be
Good ring with excellent moldability coated on both sides or one side
Environmentally friendly lubricated surface treated metal products. 2. The method according to claim 1, wherein the lubricating film is 1 to 3 with respect to flour.
The environmentally friendly lubricated surface-treated metal product excellent in formability according to claim 1, further comprising 0% by mass of silica particles (C). 3. The lubricating function-imparting agent (B) comprises one or more of a polyolefin wax, a paraffin wax, a stearic acid solid lubricant, and a wax containing a fluorine-containing resin. The good environmentally friendly lubricated surface-treated metal product excellent in formability according to claim 1 or 2. 4. The lubricating function-imparting agent (B) comprises a biodegradable aliphatic polyester, a polyvinyl alcohol,
3. The good environmentally friendly lubrication excellent in formability according to claim 1 or 2, wherein the lubrication is composed of one or more of polyamino acid-based, starch-based, chitosan-based, and cellulose-based solid lubricants. Surface treated metal products.