JP2003183587A - Composition for lubricating film and metal plate excellent in lubricity using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a lubricating film having excellent corrosion resistance and blacking resistance without a chromate treatment and having excellent press-formability without a liquid lubricant. <P>SOLUTION: The composition for the lubricating film comprises, based on (A) 100 pts.wt. solids content of a water-soluble resin and/or a water-dispersible resin, (B) 2-50 pts.wt. solids content of an additive for imparting a lubricating function to the resulting film, (C) 5-50 pts.wt. silica particle and (D) 0.3-8.0 pts.wt. at least one vanadium compound selected from ammonium methavanadate, vanadium oxide, sodium methavanadate and potassium methavanadate wherein the dried film resulting from film formation using the composition has the value of a storage elastic modules E<SB>1</SB>at 60°C of not less than 1.0×10<SP>9</SP>dyn/cm<SP>2</SP>. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention eliminates the conventional chromate treatment, and further, by directly coating a degreased zinc-based plated steel sheet with a composition containing no chromate,
The present invention relates to a composition capable of forming a lubricious film excellent in workability, corrosion resistance, blackening resistance, suitability for top coating, and the like, and a metal plate excellent in lubricity coated with the composition.

[0002]

2. Description of the Related Art In recent years, various compositions and lubricative metal plates that can form a lubricating film have been studied for the purpose of further improving moldability and not using organic solvents that are unfavorable to health and the global environment. Has been done.

The prior art relating to a lubricious metal plate is as follows:
(1) A film-free lubricant composition used for forming a lubricious film on the surface of a chromate steel plate having a chromate film formed on the surface of a cold-rolled steel plate or a zinc-based plated steel plate The lubricating composition contains a resin and a lubricating additive as main components, and the resin is a urethane-based resin in an amount of 30 to 95% by weight in a solid content weight ratio with respect to the total amount of the resin, and further includes an acrylic resin and an epoxy resin. Of these, one or two are contained, and the lubricating additive is a wax having a saponification value of 30 or less (see Japanese Patent Publication No. 8-32907). ), (2) A resin coating made of a resin having a hydroxyl group and / or a carboxyl group, silica and a polyolefin wax on a zinc- or zinc-based or aluminum-based alloy-plated steel sheet having a chromate film. And a composition capable of forming a lubricative film comprising a water-dispersible polyurethane resin, colloidal silica and a lubrication function-imparting agent, and a composition for forming a lubrication resin-treated steel sheet (see Japanese Patent Publication No. 5-86916). Steel sheet formed by forming a film on a metal plate (Patent 3026
No. 385), (4) A composition capable of forming a lubricity film comprising a water-dispersible polyurethane resin, an acrylic resin, colloidal silica and a lubricant function-imparting agent, and a lubrication formed by forming the composition on a metal plate. Steel plate (JP-A-7-
No. 11089), etc. are disclosed.

However, the above (1), (2),
The lubricated steel sheets obtained by (3) and (4) are both effective when the metal plate is chromated, but without the chromate treatment, not only the corrosion resistance and blackening resistance are poor, but also, for example, 500 mm / sec. In the high-speed press working, there was a problem in that the adhesion of the film to the material was poor and peeling occurred.

Furthermore, the toxicity of chromium has become a social problem in recent years. The surface treatment method using chromate has problems such as dispersion of chromate fumes in the treatment step, great cost for wastewater treatment, and problem of elution of chromic acid from the chemical conversion coating. On the other hand, the hexavalent chromium compound is
IARC (International Agency for Research on Can)
cer Review) has been designated as a carcinogen to the human body by many public institutions, including cer Review, and is a very harmful substance.

An object of the present invention is to provide a composition having sufficient corrosion resistance and blackening resistance even without a chromate treatment step and capable of forming a film having sufficient press formability without application of a liquid lubricant. It is to be.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a composition obtained by adding a lubricating function-imparting agent, silica particles and a specific vanadium compound to an aqueous resin is used. Then, it was found that a composition in which a dry film obtained from the composition exhibits a specific viscoelasticity can achieve the above object, and the present invention has been completed.

Thus, in the present invention, the solid content of (B) the lubricating function-imparting agent is 2 to 50 parts by weight based on 100 parts by weight of the solid content of the water-soluble resin and / or the water-dispersible resin.
(C) 5 to 50 parts by weight of silica particles, and (D) 0.3 to 8. at least one vanadium compound selected from ammonium metavanadate, vanadium oxide, sodium metavanadate and potassium metavanadate.
A composition containing 0 parts by weight, wherein the dry film obtained from the composition has a storage elastic modulus E ₁ at 60 ° C. of 1.0 ×.
It is intended to provide a composition capable of forming a lubricating film, which is characterized by having 10 ⁹ dyn / cm ² or more.

Further, the present invention provides a zinc-based plated steel sheet,
The present invention provides a metal plate having excellent lubricity, which is formed by applying the composition in a dry film weight of 0.3 to 5.0 g / m ² to form a film.

The present invention will be described in more detail below.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention contains an aqueous resin (A), a lubricating function-imparting agent (B), silica particles (C) and a specific vanadium compound (D) as essential components. .

Aqueous Resin (A) The aqueous resin as the component (A) in the present invention is a water-soluble or water-dispersible resin, and may be a mixture of a water-soluble resin and a water-dispersible resin. . Examples include water-dispersible or water-soluble polyurethane resins, acrylic resins, copolymers of ethylene and a polymerizable unsaturated carboxylic acid, and emulsion-polymerized resins, epoxy resins, epoxy ester resins, etc. using this polymer. You can

As the polyurethane resin, a polyurethane composed of a polyol such as polyester polyol and polyether polyol and diisocyanate may be used, if necessary.
Chain extension in the presence of a chain extender, which is a low molecular weight compound having two or more active hydrogens such as diols and diamines,
It is one which is stably dispersed or dissolved in water, and known ones can be widely used.

As a method for stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used. (1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, an amino group or a carboxyl group into a side chain or a terminal of a polyurethane polymer and dispersing or dissolving in water by self-emulsification; (2) reaction A method in which a completed polymer or a polymer obtained by blocking a terminal isocyanate group with a blocking agent such as oxime, alcohol, phenol, mercaptan, amine and sodium bisulfite is forcibly dispersed in water by using an emulsifier and mechanical shearing force; (3) A method in which a urethane prepolymer having a terminal isocyanate group is mixed with water, an emulsifier and an elongation agent, and mechanical dispersion is used to disperse and polymerize at the same time; (4) As a polyol for a polyurethane main raw material Use a water-soluble polyol, such as polyethylene glycol, to make water-soluble polyurethane water-soluble. A method of dispersing or dissolving the.

Commercially available products of the above polyurethane resin include:
For example, Hydran HW-330, HW-340, H
W-350 (all manufactured by Dainippon Ink and Chemicals, Inc.), Superflex 100, 110, 150, F-
8438D, 420 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.),
ADEKA BONTIDER HUX-232, 260, 32
0, 350 (all manufactured by Asahi Denka Co., Ltd.) and the like.

The acrylic resin is a resin obtained by emulsion-polymerizing, suspension-polymerizing, or solution-polymerizing a vinyl-based monomer mixture containing at least one of acrylic acid ester and methacrylic acid ester, and neutralizing and water-solubilizing as required. There are the following as typical examples. (1) In the presence of an emulsifier or a high molecular weight resin dispersion stabilizer,
An emulsion obtained by emulsion-polymerizing a vinyl-based monomer mixture in water. (2) A solution obtained by solution-polymerizing a vinyl-based monomer mixture containing a carboxyl group-containing monomer or an amino group-containing monomer in an organic solvent, neutralizing it with a neutralizing agent that is a base or an acid, and making it aqueous.

Of these, the acrylic resin is preferably an emulsion type resin. Further, the acrylic resin may have crosslinkability at room temperature, and for example, a method in which a carbonyl group is added to an acrylic resin emulsion and polyhydrazide is added to crosslink (USP 3,345,336).
Japanese Patent Laid-Open Publication No. 63-179910) and the like can be used.

Commercially available products of the acrylic resin are, for example, acrylic latex E-350, 360, and X-.
HK73 (all manufactured by Asahi Kasei Corp.), Aquabrid UM
-7760, 4635, 4790 (all manufactured by Daicel Chemical Industries, Ltd.) and the like can be mentioned.

The copolymer of ethylene and a polymerizable unsaturated carboxylic acid is a copolymer of ethylene and a polymerizable unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid or itaconic acid.
It is a copolymer of two or more species. In this copolymer, the content of unsaturated carboxylic acid is suitably in the range of 10 to 60% by weight, preferably 20 to 40%. When the content of unsaturated carboxylic acid is low, it becomes difficult to disperse in water, while when it is high, the corrosion resistance is
Insufficient solvent resistance. This copolymer can be dispersed in water by neutralizing the acid group in the copolymer with a basic substance. As the basic substance used for neutralization,
Examples thereof include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, ammonia, morpholine, triethylamine, dimethylethanolamine, and the like, among which ammonia and lower amines are preferable. The method for producing an aqueous dispersion of this copolymer is, for example, generally 60 to
It can be obtained by mixing ethylene, a polymerizable unsaturated carboxylic acid, a polymerization initiator and a neutralizing agent in 100 ° C. hot water and reacting for about 1 to 8 hours.

Commercially available products of the above-mentioned copolymers of ethylene and a polymerizable unsaturated carboxylic acid, and emulsion-polymerized resins using this polymer are, for example, Chemipearl S-100 and S-6.
50, SE-65X, S-750N (all manufactured by Mitsui Chemicals, Inc.), Hitec S-3121, S-872.
1, S-8791 (both manufactured by Toho Chemical Co., Ltd.) and the like.

The water-dispersible epoxy resin is classified into an epoxy resin emulsion in which a suitable emulsifier is added to a hydrophobic epoxy resin to disperse and emulsify it in water, and an epoxy resin which itself dissolves in water. The water-soluble epoxy resin is
Aliphatic polyhydric alcohols such as 1,6 hexanediol, glycerol, and trimethylpropane are reacted with epichlorohydrin using a Lewis acid catalyst to form an adduct, and then NaOH is added for ring closure to generate NaCl and glycidyl ether. Obtained by separating.

Commercially available products of the above epoxy resins include, for example, ADEKA RESIN EM-0460, EM-107, EM-0470, EM-0477 (all manufactured by Asahi Denka Co., Ltd.), Epomic WR-94 (Mitsui Chemicals, Inc.). Manufactured) and the like.

Commercial products of epoxy ester resins include Waterzol CD-550LA and S-3.
70, the same EFD-5501 (all manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

Lubricating function imparting agent (B) The lubricating function imparting agent which is the component (B) in the composition of the present invention may be any agent that imparts lubricity to the obtained film. Specifically, for example, fluororesin fine powder (for example, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene- Fine powder of ethylene copolymer resin, ethylene trifluoride chloride resin, vinylidene fluoride resin, etc.), polyolefin wax (for example, polyethylene wax, polypropylene wax, etc.), one particle containing both polyolefin and fluororesin mixed Lubricants, graphite, boron nitride, carbon fluoride and the like.

The average particle size of the lubricating function-imparting agent (B) is preferably 0.3 to 5.0 μm, more preferably 0.5 to 3.0 μm. When the average particle size of the wax becomes smaller, the effect of improving the lubricity tends to decrease, and when the average particle size becomes too large, the number of protruding parts of the wax from the film increases and the wax peels off during continuous processing, There is a problem in that it easily adheres to the mold.

Further, in continuous high-speed machining accompanied by heat generation, the surface temperature rises due to frictional heat, so that the lubricating function imparting agent having a low melting point becomes liquid and is not fixed to the lubricating film but adheres to and accumulates on the die. It is not preferable because it damages the metal surface. For high-speed processing involving heat generation, it is suitable to use a polyolefin wax having a softening point of 100 ° C or higher, preferably 130 to 150 ° C, and the wax is evenly fixed to the film even at high temperatures and is effective without damaging the surface of the galvanized steel sheet. Can exert its lubricating function. Further, as the lubricating function-imparting agent, a combination of the above-mentioned polyolefin wax and fluororesin powder, or a fluororesin powder alone also exhibits excellent performance.

The amount of the lubricating function-imparting agent (B) added is suitably in the range of 2 to 50 parts by weight, preferably 8 to 30 parts by weight, based on 100 parts by weight of the solid content of the aqueous resin (A). . If the added amount is small, the effect of improving the lubricity is small, and if it is too large, the gloss value of the film decreases, the surface smoothness is lost as well as the transparency, and the film elongation and adhesive force sharply decrease. The film is easily peeled off, the lubricity function cannot be sufficiently exhibited, and the press workability is deteriorated. Further, when the topcoat paint is applied on this, the adhesion of the topcoat film is deteriorated.

Silica Particles (C) The silica particles, which are the component (C) in the composition of the present invention, contribute to maintaining the dry coating film's weak alkalinity and improve the corrosion resistance of the lubricating steel sheet. Effective to remove. As the silica particles (C), both colloidal silica (water dispersion type) and fumed silica (gas phase silica) can be used. Examples of commercially available products of colloidal silica include Snowtex C, Snowtex N (both manufactured by Nissan Chemical Co., Ltd.) and Adelite AT-20.
A, AT-20N (all manufactured by Asahi Denka Kogyo Co., Ltd.), and the like. Examples of commercially available fumed silica include hydrophobic silica AEROSIL R-811,
Hydrophilic silica AEROSIL 200V (all manufactured by Nippon Aerosil Co., Ltd.) and the like can be mentioned. The average particle diameter (primary particle diameter) of the silica particles is 5 to 100 nm, preferably 10 to 5 from the viewpoint of the stability of the resin dispersion.
A range of 0 nm is suitable.

The amount of silica particles (C) added is 5 to 5 parts by weight of SiO _{2 based} on 100 parts by weight of the solid content of the aqueous resin (A).
Amounts of 50 parts by weight, preferably 10 to 30 parts by weight are suitable. When the amount of silica particles added is small, not only the film exhibits tackiness but also the corrosion resistance is insufficient. On the other hand, if the addition amount is too large, the hardness of the coating becomes high, the elongation of the coating rapidly decreases, and the press formability deteriorates.

Vanadium Compound (D) The vanadium compound which is the component (D) in the composition of the present invention is ammonium metavanadate, vanadium oxide,
It is at least one compound selected from sodium metavanadate and potassium metavanadate, and is a component that prevents white rust on the surface of a galvanized steel sheet and black discoloration of an aluminum-containing galvanized steel sheet.

The addition amount of the vanadium compound (D) is 0.3 to 8.0 with respect to 100 parts by weight of the solid content of the aqueous resin (A).
Suitably, parts by weight, preferably in the range 0.5 to 5.0 parts by weight. When the addition amount of the vanadium compound (D) is small, the corrosion resistance of the lubricating steel sheet is reduced, while when the addition amount is too large, not only the dry film is colored brown but also the coloring in the heat resistance test (30 minutes at 200 ° C). Is also remarkable.

If necessary, a basic alkali silicate can be added to the composition of the present invention. When a composition containing a basic alkali silicate is applied to a zinc-aluminum alloy plated steel sheet, the effect of preventing blackening of the coated steel sheet becomes more remarkable. Examples of the basic alkali silicate include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, and the like. As sodium silicate (Na ₂ O.XSiO ₂ ), the value of X is 2 (No. 1), 2.5 (No. 2), 3 (No. 3), lithium silicate (Li ₂ O.XSiO ₂ ) having an X value of 3.5 (lithium silicate 35), 4.5 (lithium silicate 4
5) and 7.5 (75 lithium silicate) are commercially available.

The amount of basic alkali silicate added is
0.3 to 1 with respect to 100 parts by weight of the solid content of the aqueous resin (A)
It is preferable to add 5 parts by weight, particularly 1 to 8 parts by weight.

The composition of the present invention comprises, in addition to the above components and water,
A curing agent, a neutralizing agent, a reaction accelerator, a thickener, a defoaming agent, an organic solvent and the like may be appropriately contained. As the curing agent, for example, an aziridinyl group-containing compound, a polyvalent carbodiimide compound, an oxazoline group-containing compound and the like can be preferably used, and solvent resistance, alkali resistance and the like can be improved.

In the composition of the present invention, the dry film obtained from the composition has a viscoelastic modulus E ₁ at 60 ° C. of 1.0 ×.
It is necessary to show 10 ⁹ dyn / cm ² or more. Here, the viscoelastic coefficient E ₁ is a vertical type dynamic viscoelasticity measuring apparatus DVE-V4 type FT-Rheospectler (manufactured by Rheology Co.) with forced vibration non-resonance and a frequency of 110.
It is a value measured under the conditions of Hz, temperature rising rate of 4.0 ° C./min and constant static load of 10 g.

When the value of the viscoelastic modulus E ₁ at 60 ° C. of the dry film is less than 1.0 × 10 ⁹ dyn / cm ² , the film softens due to the temperature rise on the surface of the work material during high speed press working,
Since the film strength decreases, the film itself easily peels off, and at the same time, the lubricating function-imparting agent cannot be fixed uniformly in the film, resulting in a marked decrease in continuous formability, which is not preferable.

Manufacture of Metal Plate with Excellent Lubricity Conventionally, a lubricated steel plate is generally subjected to a chromate treatment as a surface treatment. The composition of the present invention can omit the conventional chromate treatment step, and obtains a metal plate excellent in corrosion resistance and lubricity by directly applying it to an untreated zinc-based plated steel sheet, an aluminum-plated steel sheet or an aluminum plate and drying it. be able to. Even if the composition of the present invention is applied to a chromate-treated steel sheet, there is no problem in terms of performance, and the composition can be used according to the application.

Examples of the zinc-based plated steel sheet include electrogalvanized steel sheet, hot-dip galvanized steel sheet, nickel-zinc alloy plated steel sheet, and zinc-aluminum alloy plated steel sheet. As a zinc-aluminum plated steel sheet,
In the case of zinc base, 5% Al-Zn system, 8% Al-Zn
System, 15% Al-Zn system and the like, and as the aluminum base, 55% Al-Zn system, 75% Al-Zn system and the like are known, but the composition of the present invention is not limited to these. The plating layer can be applied to a composite plated steel sheet whose main components are aluminum and zinc. For example, in an Al-Zn alloy, Mg, Mn, Si, Ti, Ni, Co, Pb, S
n, Cr and rare metals (La, Ce, Y, Nb, etc.)
It is also applicable to those added with.

The composition of the present invention has a dry coating weight of 0.3 to 5.0 g / m ² , more preferably 0.5 to 3.0 on the steel sheet.
It is desirable that the coating be applied so as to be g / m ² and then dried to form a film. When the film is thin, the corrosion resistance, black discoloration resistance and lubricity are deteriorated, and when the film is thick, the corrosion resistance is improved but the press workability is deteriorated and the cost is increased.

Further, in order to impart welding suitability to the steel sheet coated with the composition of the present invention, the coating weight is preferably 1.5 g / m ² or less, more preferably 1.0 g / m ² or less. If the coating weight exceeds 1.5 g / m ² , dust tends to be generated during spot welding, and the welding strength becomes insufficient, so that the appropriate continuous welding point deteriorates.

Upon coating the steel sheet with the composition of the present invention to form a film, the viscosity of the composition is appropriately adjusted to about 5 to 30 centipoise depending on the coating amount with a diluent such as water, and then roll coater coating, After applying a predetermined coating weight by a generally known method such as spray coating or depping coating, the ambient temperature is 150 to 250 ° C.
Dry for 40 seconds. Maximum temperature of steel plate at this time (PM
T) is preferably in the range of 90 to 160 ° C. By coating and drying the coating composition in this manner,
A steel sheet excellent in black discoloration resistance and press workability is manufactured.

[0042]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. In the following, "part" and "%"
All are based on weight.

Examples 1 to 20 and Comparative Examples 1 to 11 Each composition was prepared according to the formulation shown in Table 1 below. In addition,
The formulations in Table 1 are shown in terms of solid content. Further, each composition was adjusted to a solid content of 20% with deionized water.

Each of the compositions obtained above was coated with a bar coater and kept at 240 ° C. for 10 seconds (PMT110
(° C) and dried to form a film. The combination of coating material and coating amount (dry film weight, g / m ² ) was performed according to Table 1. Various performance tests were performed on the obtained coated plates. The results obtained are shown in Table 1.

The material symbols in Table 1, the raw materials used in the notes and the coating film performance test method are shown below.

Material symbol and content A: hot-dip galvanized steel sheet; plate thickness 0.6 mm plating amount 100 g / m ² B: zinc-aluminum alloy plated steel sheet; zinc / aluminum = 95/5 (weight ratio) Trade name Super Zinc Plate thickness 0.5 mm Plating adhesion amount 140 g / m ² C: Zinc-aluminum alloy plated steel sheet; Zinc / aluminum = 45/55 (weight ratio) Trade name Galvalume plate thickness 0.5 mm Plating adhesion amount 90 g / m ² D: Electricity Zinc-plated steel plate; Trade name: Zincoat plate thickness 0.6 mm, coating weight 20 g / m ² E: Ni-Zn plating steel plate; Zinc / nickel = 88/12 (weight ratio) Plate thickness 0.6 mm, coating weight 20 g / m ² For each material, degreased ones are used as they are without chrome treatment and cosmetics are used as chrome treated ones. 50 (Kansai Paint Co., coating type chromate) was used after 5 mg / m ² coated with a metal chromium conversion.

Note Content of raw material (Note 1) ADEKA BONTIDER HUX320: Asahi Denka Kogyo Co., Ltd., aromatic polyester polyurethane emulsion, solid content 30% (Note 2) Aquabrid 4635: Daicel Chemical Industry Co., Ltd., anion acrylic Emulsion, Tg 60 ° C., solid content 35% (Note 3) Chemipearl S-100: manufactured by Mitsui Chemicals, Inc., ethylene acrylic copolymer resin dispersion, pH 12, solid content 27
% (Note 4) ADEKA RESIN EM0460: Asahi Denka Co., Ltd., anionic epoxy emulsion, PH 7.8, solid content 50
% (Note 5) Chemipearl W-700: Mitsui Chemicals, high-density polyethylene wax, molecular weight 4,000, softening point 132 ° C., average particle size 1.1 μm (Note 6) SLIP AID SL-92: San Nopco , Polyethylene wax, softening point 92 ° C., average particle diameter 2 μm (Note 7) PTFE: polytetrafluoroethylene resin powder, particle diameter 2 to 5 μm (Note 8) Snowtex C: Nissan Chemical Co., colloidal silica, particle diameter 10-20 nm, SiO ₂ content 20% Coating film performance test method Film appearance ⊚: The film is transparent. ○: The film is slightly white and cloudy. Δ: The film is cloudy or colored. X: A clean film is not formed.

Elastic Modulus E ₁ Each of the coating compositions of Examples and Comparative Examples was recoated so that the thickness of the coating after drying was 50 μm, and finally dried at 150 ° C. for 10 minutes to obtain a free coating having a thickness of 50 μm. A coating film was obtained.
About this free coating film, a dynamic viscoelasticity measuring device DVE-
Using a V4 FT Rheospectr (Rheology), the elastic modulus E ₁ was measured under the conditions of a frequency of 110 Hz, a temperature rising rate of 4.0 ° C./min and a static load of 10 g. The elastic modulus E ₁ was measured at 20 ° C. and 60 ° C.

The deep-drawing workability test plate is a metal thin plate deep-drawing tester 142 manufactured by Erichsen.
A test was conducted using a mold under the following conditions, and the test temperature was 20 ° C. and 80 ° C., the sheet holder pressure was 1500 Kg, the punch diameter was 50 mm, the blank diameter was 110 mm, the drawing ratio was 2.2, and the processing speed was 10 mm / sec. ⊚: There are no deposits on the die, and no scratches are found on the surface of the work piece. ◯: There is a slight amount of deposit on the die, and slight scratches are recognized on the surface of the work piece. Δ: The die has a slightly large amount of deposits, and many scratches are recognized on the surface of the workpiece. X: A large amount of deposits are present on the die, and scratches are observed on the entire surface of the workpiece.

The corrosion resistance salt spray test was carried out in accordance with JIS Z-2371.
The test time was 360 hours for the flat plate before processing and 240 hours for the sample after deep drawing, and the area of occurrence of white rust or black rust in the coated plate was evaluated according to the following criteria. ⊚: No rust is observed. ◯: Rust is observed in an area of less than 5%. Δ: Rust is observed in an area of 5% or more and less than 20%. X: Rust generation is recognized in an area of 20% or more.

After the high-temperature and high-humidity test piece was left for 48 hours in an environment of a temperature of 80 ° C. and a humidity of 95%, the color difference ΔE of the coated plate before and after the test was measured using a color difference meter to measure the extent to which the coated plate turned black. And evaluated according to the following criteria. ⊚: ΔE is less than 2. ◯: ΔE is 2 or more and less than 5. Δ: ΔE is 5 or more and less than 10. X: ΔE is 10 or more.

After the boiling water resistant test piece was immersed in boiling water for 1 hour, the degree to which the coated plate was discolored black was evaluated according to the following criteria by measuring the color difference ΔE between the coated plate before and after the test using a color difference meter. ⊚: ΔE is less than 2. ◯: ΔE is 2 or more and less than 5. Δ: ΔE is 5 or more and less than 10. X: ΔE is 10 or more.

The test plate was immersed in a 5% aqueous solution of sodium hydroxide for 2 minutes, washed with water and dried, and the color difference ΔE of the coated plate before and after the test was measured using a color difference meter to measure the extent to which the coated plate turned black. The following criteria evaluated. ⊚: ΔE is less than 2. ◯: ΔE is 2 or more and less than 5. Δ: ΔE is 5 or more and less than 10. X: ΔE is 10 or more.

On top of the coating film adhesion test piece, a film of amylak # 1000 which is a thermosetting alkyd paint and Magicron # 1000 which is a thermosetting acrylic paint (both manufactured by Kansai Paint Co., Ltd., color is white) are formed. Each of them is coated to a thickness of 25 μm.
Baking for 15 minutes, or 15 for Magiclon # 1000
After baking at 0 ° C for 20 minutes to create two types of coated plates, each coated plate is cut into squares (10 x 10 squares at 1 mm intervals), and adhered / peeled with an adhesive tape. The peeled area ratio of the coating film was evaluated. The evaluation criteria are as follows. ⊚: No peeling area. ◯: Peeling area is less than 1%. Δ: Peeling area is 1% or more and less than 5%. X: Peeling area is 5% or more.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

The film obtained from the composition of the present invention is a composition containing a water-soluble resin or a water-dispersible resin as a main component and containing no chromate, and is excellent in environmental hygiene. When the composition of the present invention is applied to a degreased galvanized steel sheet, a test method of immersing the composition in boiling water for 60 minutes and a temperature of 80 ° C.
It shows excellent corrosion resistance and black discoloration resistance even in the test method of being installed in an environment with humidity of 95% or more for 48 hours, and since it has a good lubricating function, it can be pressed directly without applying liquid lubricant etc. Therefore, the liquid lubricant applying step and the degreasing step at the time of processing can be omitted, and not only the working environment can be improved but also the cost can be reduced. Further, it is difficult for stains such as fingerprints to adhere during handling, and exhibits excellent adhesion even when a general thermosetting acrylic paint, thermosetting aminoalkyd paint or the like is applied on this film.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10M 107/02 C10M 107/02 107/38 107/38 125/10 125/10 125/26 125/26 173 / 00 173/00 C23C 22/40 C23C 22/40 28/00 28/00 A // C10N 30:06 C10N 30:06 30:08 30:08 30:12 30:12 40:20 40:20 Z 50 : 02 50:02 F-term (reference) 4D075 CA09 DB05 4H104 AA11C AA13C AA21C AA22C CA01A CB06C CB08C CB12C CB13C CD01A CE13C EA08A EA08C EA17C FA01 FA05 LA03 LA04 LA06 PA21 QA08 4J038 CB002 CB061 CD092 CG141 DB031 DB471 DG001 DG131 EA011 HA036 HA086 HA216 HA246 HA326 HA446 HA456 HA476 KA07 KA20 MA09 MA10 NA03 NA11 NA12 PC02 4K026 AA02 AA07 AA11 BA01 BA12 BB04 CA27 CA30 CA39 DA02 DA11 4K044 AA02 AA06 BA10 BA12 BA14 BA21 BB03 BC02 BC04 BC05 CA11 CA18 CA53

Claims (5)

[Claims] 1. A solid content of (A) a water-soluble resin and / or a water-dispersible resin (B) is 2 to 50 parts by weight of a lubricating function-imparting agent, and (C) silica particles. 5-5
0 parts by weight and 0.3 to 8.0 parts by weight of (D) at least one vanadium compound selected from ammonium metavanadate, vanadium oxide, sodium metavanadate and potassium metavanadate, A composition capable of forming a lubricating film, wherein a dry film obtained from the composition has a storage elastic modulus E ₁ at 60 ° C. of 1.0 × 10 ⁹ dyn / cm ² or more. 2. The composition capable of forming a lubricating film according to claim 1, wherein the lubricating function-imparting agent (B) is composed of a polyolefin wax and / or a fluorine resin powder having a softening point of 100 ° C. or higher. 3. The lubricating coating according to claim 1 or 2, further comprising 0.3 to 15 parts by weight of a basic alkali silicate added to 100 parts by weight of the solid content of the aqueous resin (A). Possible compositions. 4. The composition capable of forming a lubricating coating according to claim 3, wherein the basic alkali silicate is at least one compound selected from sodium silicate, potassium silicate, lithium silicate and ammonium silicate. 5. A zinc-based plated steel sheet is coated with the composition according to any one of claims 1 to 4 in a dry film weight of 0.3 to
A metal plate with excellent lubricity formed by applying 5.0 g / m ² and forming a film.