JPH032257A - Composition capable of forming lubricant coating film - Google Patents

Abstract

PURPOSE:To provide a composition capable of forming lubricant coating films having excellent processability and corrosion resistance by compounding a specific organic resin component with an organic silica sol and a lubricity-giving agent in specific amounts, respectively. CONSTITUTION:(A) 100 pts.wt. of an epoxy resin or an organic resin component mainly comprising the epoxy resin and having a glass transition point of >=80 deg.C is compounded with (B) an organosilica sol in a solid content of 10-60 pts.wt. and (C) 0.3-20 pts.wt. of a lubricity-giving agent comprising a polyolefinic wax having a melting point of >=90 deg.C, preferably >=110 deg.C, or comprising 100 pts.wt. of the wax and <100 pts.wt. of a fluororesin powder to provide the objective composition. The composition is coated on a metal plate in a dry weight amount of 0.2-5g/m<2>.

Description

[Detailed Description of the Invention] <Industrial Application Fields> The present invention is directed to a composition capable of forming a lubricating film with excellent processability and corrosion resistance, and to applications in particular in fields such as home appliances, building materials, and automobile products to which this composition is coated. This invention relates to a lubricating metal plate used for.

<Conventional technology and its problems> When performing processing such as press molding on a metal plate, it is necessary to apply a liquid lubricant to the metal plate for the purpose of preventing damage to the metal plate due to insufficient slippage. It is being done.

Liquid lubricants include oil-based lubricants and aqueous lubricants.Oil-based lubricants have a wide range of applications (can be used for most drawing processes, and have the advantage of providing rust prevention properties.
Lubricating performance changes due to changes in viscosity due to temperature, and in the case of high-speed production, heat generation makes work unstable and has the disadvantage of significantly polluting the work environment. In addition, aqueous lubricants can be applied to a wide range of applications, from light machining to difficult machining, by changing the dilution ratio with water, and while they have the advantage of high cooling performance and high-speed production, they are also difficult to prevent rust. It has the disadvantages of poor performance and difficulty in waste liquid treatment.

In addition, when manufacturing products through various processes using metal plates, the surface of the metal plate may be contaminated with fingerprints or other stains due to handling by workers, which can significantly reduce the product value. It is required that the metal plate be such that fingerprints and other stains are difficult to see during handling.

Therefore, from the viewpoint of contaminating the working environment and omitting the degreasing process,
Various lubricated steel plates and lubrication treatment methods have been proposed that can be formed without any problem without using the above-mentioned liquid lubricant during press working, and have excellent rust prevention properties and stain resistance during handling. For example, (1) After applying an organic substance to the steel plate surface and drying it, a rust preventive oil based on mineral oil is applied, thereby creating a solid layer mainly composed of organic substances and a layer of rust preventive oil on the steel plate surface. A lubrication treatment method that imparts a high degree of corrosion resistance and is characterized by forming both layers (Japanese Patent Publication No. 57-31471). (3) Chromate coating on galvanized steel plate 0.3 to 5% of a solvent-based coating composition containing urethanized epoxy ester resin, silica powder, hydrophilic polyamide resin, and polyethylene wax as a lubricant is applied thereon.
An organic composite steel sheet (Japanese Unexamined Patent Application Publication No. 35798/1983) has been disclosed which is coated with an organic composite material and has excellent cationic electrodeposition coating properties.

However, the lubricating steel sheets obtained by methods (1) to (3) above are all effective for low-speed processing such as Erichsen deep drawing at room temperature;
For high-speed press processing of about n+m/sec,
The resin coating layer is easy to peel off (there is a problem that the peeled resin powder adheres to the workpiece or processing tool, which scrapes the workpiece and impairs the surface appearance of the workpiece. (3) In this case, it was necessary to sufficiently disperse the silica powder.

Means for Solving the Problems> The present inventors have solved the above-mentioned drawbacks of the conventional technology, and have achieved continuous moldability and corrosion resistance without applying liquid lubricant even during high-speed press processing, and also have excellent corrosion resistance during handling. To obtain a composition that can form a lubricating film that is resistant to stains such as fingerprints (as a result of intensive research, we found that a combination of an organic solvent type, high molecular weight epoxy resin with a glass transition point of 80°C or higher and organosilica sol) was obtained. Furthermore, the present inventors have discovered that a composition containing a specific amount of a lubricity imparting agent containing a polyolefin wax can achieve the above object, and have thus arrived at the present invention.

That is, the present invention provides (A) a glass transition point 8 which is made of an epoxy resin or whose main component is an epoxy resin;
A composition capable of forming a lubricating film, characterized by containing 0.3 to 20 parts by weight of a lubricity imparting agent consisting of or mainly consisting of a polyolefin wax having a temperature of 0°C or higher and an organic resin component of 100 parts by weight or more. It is something that provides something.

Another object of the present invention is to provide a lubricating metal plate formed by coating a metal plate with the above-mentioned composition capable of forming a lubricating film at a dry coating weight of 0.2 to 5.0 g/rd.

The organic resin component which is component (A) in the composition of the present invention is an organic solvent soluble type or an organic solvent dispersion type, and consists of an epoxy resin or has an epoxy resin as a main component,
In addition, it is necessary that the glass transition point is 80° C. or higher.

If the glass transition point is less than 80° C., the coating becomes soft due to the temperature increase on the surface of the workpiece during high-speed press processing, and the coating strength decreases, making it easy for coating components to peel off and reducing continuous moldability, which is not preferable.

The above epoxy resin is a resin obtained by reacting a polyphenol compound with epichlorohydrin, or a resin obtained by partially reacting this resin with a polyol, polyether polyol, polyester polyol, polyamidoamine, polycarboxylic acid, polyisocyanate compound, etc. It may also be ε-caprolactone,
It may be a product obtained by graft polymerization of acrylic monomer, etc., but the resin content obtained by the reaction of a polyphenol compound and epichlorohydrin should be 50% by weight or more,
It is necessary that the content is preferably 70% by weight or more.

As the polyphenol compound for obtaining the above-mentioned epoxy resin, for example, bis(4-hydroxyphenyl)-2
, 2-propane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydronkydiphenyl)-1,1-ebutane, bis(4-hydroxy-tert- Butyl-phenyl)-2゜2-propane, bis(2-hydroxynaphthyl)methane, 1.5
-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4'-dihydroxydiphenylsulfone, phenol novolak, cresol novolak, etc. It will be done. Among them, bis(4-hydroxyphenyl)-2,2-propane is preferred from the viewpoint of corrosion resistance.

When a polyphenol compound and epichlorohydrin are reacted, more than an equivalent amount of epichlorohydrin may be reacted with the hydroxyl group in the polyphenol compound to form an epoxy resin having an epoxy group, or an epoxy resin may be obtained by reacting less than an equivalent amount of epichlorohydrin with the hydroxyl group in the polyphenol compound. The epoxy resin of the present invention may have a number average molecular weight of 3,000 to 16,000, more preferably 4,000 to 3,000.

When the organic resin component (A) is mainly composed of the above-mentioned epoxy resin, in addition to the epoxy resin, curing agents such as amino resins and polyisocyanate compounds, acrylic resins, polyester resins, vinyl resins, and polyacetal resins are used. However, it is necessary that the epoxy resin accounts for 50% by weight or more in component (A).

The organosilica sol, which is the component (B) in the composition of the present invention, is blended for the purpose of improving adhesion and corrosion resistance, and is dissolved in an organic solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, or isopropyl alcohol. Stably dispersed particle size 1-1
00 mμ, preferably 10 to 50 mμ, such as Applied MS-BE3 manufactured by Asahi Denka Kogyo ■.
0, Applied MS-BH30, Applied ES-30
, Oscar-1734 manufactured by Catalyst Kasei ■
, Oscar-1432, and the like.

The lubricity imparting agent, which is component (C) in the composition of the present invention, is mainly composed of polyolefin wax, carbonized olefin, such as polyethylene or polypropylene, having a melting point of 98°C or higher, preferably 110°C to 150°C. Examples include those made of hydrogen polymers, and one type of these can be used alone or two or more types can be used in combination.

The lubricity imparting agent of component (C) may consist only of polyolefin wax, but it may also contain fluororesin fine powder in combination with polyolefin wax (by using the combination, lubricity is further improved). do.

As the fluororesin fine powder, polytetrafluoroethylene,
Examples include fine powders of polyvinyl fluoride resin, polyvinylidene fluoride resin, polyfluoroethylene resin, etc. Among them, fine powder of tetrafluoroethylene resin having a maximum particle size of 15P or less is preferred.

When used in combination, the blending ratio is preferably less than 100 parts by weight, more preferably from 2 to 80 parts by weight, of the fluororesin fine powder per 100 parts by weight of the polyolefin wax. If the amount of the fluororesin fine powder exceeds 100 parts by weight per 100 parts by weight of the polyolefin wax, the dispersion stability will decrease and it will not be possible to uniformly disperse the powder in the composition.

When performing processing such as press working on a metal plate that has a lubricating film, during continuous high-speed processing that generates heat, the surface temperature rises due to frictional heat, so the lubricating agent with a low melting point becomes liquid, and the lubricating film is It is undesirable because it is not fixed to the mold and adheres and accumulates on the mold, damaging the surface of the workpiece.

In high-speed machining that generates heat, the melting point is 90"C or higher,
Preferably, a polyolefin wax having a temperature of 110° C. or higher is used. Even at a considerably high temperature, the wax is uniformly fixed to the lubricating film and can effectively exert its lubricating function without damaging the surface of the workpiece.

Furthermore, a combination of the polyolefin wax and fluororesin fine powder as a lubricity imparting agent exhibits even better performance. The reason for this is that the surface energy of the fluororesin fine powder is extremely low, giving it a low coefficient of friction, and the polyolefin wax improves the dispersibility and storage stability of the tetrafluororesin fine powder in the coating composition. It is thought that this is to further improve the lubricating function of the fluororesin fine powder.

The blending ratio of components (B) and (C) in the composition of the present invention is 15 to 40 parts by weight per 100 parts by weight of component (A), and 0.3 to 20 parts by weight of component (C), preferably 1 part by weight. ~15
Weight part.

The organosilica sol, which is the component (B), contributes to improving adhesion and corrosion resistance, but if the amount of fine-grained silica is less than 10 parts by weight, sufficient adhesion cannot be obtained and the obtained lubricity The effect of dispersing corrosion current by the coating is small, and the effect of improving corrosion resistance is small. In addition, if it exceeds 1 part by weight, the gloss value of the coating will decrease, the surface smoothness will be lost, and the elongation rate of the coating will drop sharply, the coating will easily peel off during processing, and press workability will decrease. This is not preferable because it tends to cause mold galling.

The lubricity imparting agent, which is component (C), imparts lubricity to the workpiece and allows processing such as press working to be performed without problems, but the amount of the lubricity imparting agent is 0.3 parts by weight. If it is less than that, the effect of improving lubricity is small. On the other hand, if the amount of the lubricity imparting agent exceeds 20 parts by weight, the gloss value of the coating will decrease and the surface smoothness will be lost, the elongation rate and adhesion of the coating will sharply decrease, and the coating will easily peel off. , the effect of imparting lubricating function cannot be fully utilized, and press workability deteriorates.
Makes mold galling more likely.

In addition, when using polyolefin wax and fluororesin fine powder together as component (C), the amount of fluororesin fine powder added is 10 parts by weight per 100 parts by weight of component (A).
It is preferable that it is not more than parts by weight. If the amount added exceeds 10 parts by weight, the dispersion stability will decrease, it will not be able to be uniformly dispersed in the coating liquid, and precipitation will easily occur in a short period of time.
In addition, the surface smoothness of the resulting lubricating film is lost, the elongation rate and adhesion of the film are rapidly reduced, and the film is likely to peel off (and the lubricity imparting effect cannot be fully utilized.
Decreases press workability and makes mold galling more likely.

The composition of the present invention may appropriately contain additives such as organic solvents; reaction accelerators, dispersants, and leveling agents in addition to components (A), (B), and (C).

The composition of the present invention fully functions when applied to a metal plate to form a lubricating film.

The metal plates mentioned above include cold-rolled steel plates, galvanized steel plates, iron-plated steel plates, etc.
Zinc alloy plated steel sheet, nickel-zinc alloy plated steel plate,
Examples include zinc-aluminum alloy plated steel sheets, aluminum plated steel sheets, tinplate plates, and copper plates. These metal plates are subjected to known chemical conversion treatments such as chromate treatment, zinc phosphate treatment, iron phosphate treatment, and phosphate-chromium treatment. From the viewpoint of corrosion resistance, it is preferable to use a chemical conversion treatment.

The amount of chromate film in the above chromate treatment is an amount of chromium element of 10 to 100 mg/m'', and the amount of treated film in iron phosphate treatment or zinc phosphate treatment is 0.3 to 1.5 g/m'' It is preferable from the viewpoint of corrosion resistance and processability.

The composition of the present invention is coated on the metal plate with a dry coating weight of 0.2 to 5.
．． 0g/m2, more preferably 0.8-4.0g/r
It is desirable to apply and dry to form a film so that the coating amount is less than 0.2g/rn', the effect of improving corrosion resistance is small, and sufficient lubricating function cannot be obtained. rr? If it exceeds this value, the corrosion resistance will improve, but the press workability will decrease, and the cost will be high, making it uneconomical.

Further, in order to impart weldability to the steel plate coated with this coating film, it is desirable that the coating weight be 2.0 g/rn' or less, more preferably 1.5 g/rrr or less. If the coating weight exceeds 2.0 g/rr1'', dust tends to occur during spot welding, and the welding strength also becomes insufficient, resulting in a sharp drop in continuous dot suitability.

When applying the composition of the present invention on a metal plate to form a film, the composition of the present invention may be mixed with a ketone solvent such as methyl ethyl ketone or cyclohexanone, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate,
After adjusting the viscosity as appropriate depending on the coating amount etc. in a Ford cup Nα4 for 11 to 60 seconds using a single or mixed solvent such as an ester solvent such as ethylene glycol monobutyl ether or an alcohol solvent, it is coated with a roll coater.
After coating to a predetermined coating weight by a generally known method such as painting, spray painting, dipping painting, brush painting, etc., the atmospheric temperature is usually 80 to 80°C, although it is not particularly limited. Dry at 300°C for 10-120 seconds. The maximum plate temperature (PMT) of the material at this time is 70~
Preferably, the temperature is in the range of 230°C.

By applying and drying the lubricating functional coating composition in this manner, a lubricated steel sheet with excellent press workability is manufactured.

(Actions and Effects of the Invention) The lubricating film obtained from the composition of the present invention uses an epoxy resin with a high glass transition point as an organic resin component, so it has good adhesion to metal plates, and Even if there is heat generation or temperature rise during continuous high-speed processing such as press working, the film strength will not deteriorate (in addition, since it contains organosilica sol, it can improve adhesion and disperse corrosion current. In addition, the lubricity imparting agent containing polyolefin wax with a melting point of 90″C or higher exists uniformly on the coating surface and has good lubricity, so it can be used as a liquid lubricant etc. Since it is possible to press as is without applying liquid lubricant, it is possible to omit the liquid lubricant application process and degreasing process during processing, which not only improves the working environment (but also reduces costs). Even during processing, the lubricity agent becomes liquid and can effectively exert its lubrication function without adhering or depositing on the mold and damaging the workpiece.At the same time, it is difficult to get fingerprints or other stains during handling. A lubricious coating can be provided.

<Examples> The present invention will be described in more detail below with reference to Examples. Note that hereinafter, "parts" and "%" mean "parts by weight" and "% by weight," respectively.

Example 1 100 parts of Phenotote YP-50 (Note 1) was blended into a mixed solvent consisting of 116.5 parts of cyclohexanone and 116.5 parts of ethylene glycol monobutyl ether,
The mixture was stirred and dissolved to obtain a resin solution a having a solid content of 30%.

Organosilica sol dispersion liquid MS-BE-30 (
67 parts (solid content: approximately 20 parts) of Note 2) and 10 parts of polyethylene wax A (Note 3) were mixed and uniformly stirred to obtain a composition liquid.

(Note 1) Phenotote YP-50: A solid resin manufactured by Tobu Kasei ■, a polyhydroxypolyether resin without epoxy groups obtained by the reaction of a polyphenol compound and epichlorohydrin, with a number average molecular weight of 11,800.
゜Glass transition point approximately 100℃.

(Note 2) Applied MS-BE-30: Trade name, organosilica sol manufactured by Kadenka Kogyo ■ with a solid content of about 30%, the dispersion medium being ethylene glycol monobutyl ether, and the particle size of the silica sol being about 10 to 20 mμ.

(Note 3) Wax A: polyethylene powder with a weight average molecular weight of about 9000, a melting point of 127°C, and a particle size of 2 to 5p7n.

Example 2 100 parts of Evotot YD-7020 (Note 4) was blended into a mixed solvent consisting of 116.5 parts of methyl ethyl ketone and 116.5 parts of ethylene glycol monobutyl ether, stirred, and dissolved to form a resin solution with a solid content of approximately 30%. I got it.

A composition liquid was obtained in the same manner as in Example 1 except that the above resin solution was used and the formulation shown in Table 1 was adopted.

(Note 4) Evototo YD-7020: Manufactured by Tobu Kasei ■, solid epoxy resin of bisphenol A type. Number average molecular weight: 5200, glass transition point: approximately 90°C.

Examples 3 to 15 and Comparative Examples 3 to 7 Composition liquids were obtained in the same manner as in Example 1, except that resin solutions a or b were used and the formulations shown in Table 1 were used.

Comparative Example 1 VB200OL (Note 12) in 567 parts of isopropanol
Mix 1,000 parts of the mixture and stir until dissolved to obtain a solid content of approximately 15%.
A resin solution C was obtained.

A composition liquid (for comparison) was obtained in the same manner as in Example 1 except that the resin solution C was used and the formulation shown in Table 1 was used.

(Note 12) VB2000L: Manufactured by Denki Kagaku Kogyo, polyvinyl butyral resin, product name “Denka Butyral ■B2”
o00L”.

Comparative Example 2 A composition liquid (for comparison) was obtained in the same manner as in Example 1, except that 820C (note 13) with a solid content of 40% was used and the formulation shown in Table 1 was adopted.

(Note 13) 820C: Manufactured by Mitsui Toatsu Chemical ■, solid content 40%
urethane-modified epoxy resin solution. Product name: “Evokey 8”
20CJ. Number average molecular weight: 9000, glass transition temperature: 66°C.

In Table 1, all formulations in Examples and Comparative Examples are expressed in terms of solid content.

(Note 5) to (Note) in Table 1 are as follows.

(Note 5) Oscar 1432: Product name. Particle size of 10 to 20 mμ using isopropanol manufactured by Catalyst Kasei ■ as a dispersion medium
silica sol dispersion.

(Note 6) Applied ES-30: Product name. Asahi Denka Kogyo■
An organosilica sol dispersion with a solid content of approximately 30%. The dispersion medium is ethylene glycol monoethyl ether, and the particle size of the silica sol is approximately 10 to 20 ue (Note 7) H-1: Dainippon Ink & Chemicals Co., Ltd., butylated urea resin. Solid content approximately 60%, product name "Beccamin P-1"
964° (Note 8) H-2: Manufactured by Takeda Pharmaceutical ■, a block polyisocyanate that is an adduct type of isophorone diisocyanate and Bo1 heol. Solid content 60%, trade name [Takenate B-87NJ.

(Note 9) Wax B: Polyethylene powder with a weight average molecular weight of about 5000, a melting point of about 120°C, and a particle size of 2 to 5 pM.

(Note 10) Wax C: polyethylene powder with a weight average molecular weight of about 2000, a melting point of about 100°C, and a particle size of 2 to 5V1n.

(Note 11) PTFE powder: Polytetrafluoroethylene resin powder with a particle size of 2 to 5 pM.

The composition liquids obtained in the above Examples and Comparative Examples were mixed in a mixed solvent of cyclohexanone: ethylene glycol monobutyl ether = 1 = 1 for about 22 seconds (Ford Cup N
The mixture was made viscous at 4/25 °C) and used for coating on metal plates. As the metal plates to be coated, the following metal materials were used, which were subjected to the following chemical conversion treatment, and those which were not treated.

(1) Types of metal materials - Electrogalvanized steel sheet (EG) Thickness: 0.8 mm Galvanized coating amount: 20 g/m2 Thickness: 0.8 mm Sheet thickness: 0.8 mm Nickel content: 12% Hot-dip galvanized steel sheet (HDG) Plate thickness: 0.8mm Zinc plating coverage: 120g/rrl' (2) Chemical conversion treatment/Chromate treatment: Coated type consisting of chromium hydrate with a ratio of (:tr":Cr" of approximately 0.65:0.35) The chromate treatment solution was applied to electrogalvanized steel sheets and cold-rolled steel sheets using a rubber roll, and then dried in a hot air drying oven.The amount of chromate film deposited was 30.50 and 100 mg/rr in terms of chromium element content.
There were three levels of r.

- Iron phosphate treatment: The cold-rolled steel sheet described above was spray treated with Parphos 1077, an iron phosphate treatment agent manufactured by Nippon Parr Ising ■. Is the coating weight 500mg/rr? And so.

An example of producing a metal plate coated with a composition will be shown in the following application examples and comparative application examples. The baking conditions for the composition are PMT
The temperature was 120°C or 220°C. For PMT 120°C, bake at an ambient temperature of 180°C for 30 seconds, PMT 2
In the case of 20°C, baking was performed at an ambient temperature of 250°C for 60 seconds.

Application example 1 Chromate treatment (deposition amount is 50mg/r of Cr element)
rf) on an electrolytic galvanized steel sheet, the active part liquid of the composition liquid obtained in Example 1 was coated with a bar coater to form a dry coating with a weight of 1.4 g.
/rr? Paint it so that it becomes
It was dried at MT (120'C) to obtain a lubricating steel plate. Table 2 shows the test results for the obtained lubricating steel sheets.

Application Examples 2 to 29 and Comparative Application Examples 1 to 5 Using the composition liquids obtained in the Examples and Comparative Examples, a lubricating steel plate was obtained in the same manner as in Application Example 1, except for the conditions shown in Table 2. Ta.

Table 2 shows the test results for the obtained lubricating steel sheets.

The tests in Table 2 were conducted according to the following.

(1) Continuous workability The two test pieces were subjected to a cup deep drawing test using a thin metal plate deep drawing tester Model 142 manufactured by Erichsen, with the lubricating coating of the test piece in contact with the die. The drawing conditions were as follows.

a. Conditions for low speed machining - Seat holder pressure 1000Kg - Punch diameter
50mm・Blank diameter 1
10mm/Aperture speed 5mm/
5ecb, conditions for high-speed machining, seat holder pressure 3200Kg, punch diameter
50mm・Blank diameter 1
10mm? Aperture speed 500 mm/
5ee (Evaluation Criteria) Evaluation was made based on the presence or absence of a lubricating film composition that adhered to the die by a cup deep drawing test.

0: No adhesion on the die O: A small amount of adhesion on the die Δ: Slightly large amount of adhesion on the die ×: A large amount of adhesion on the die (2) Corrosion resistance test A salt spray test (JIS-22371) was conducted to determine whether red rust occurred. Evaluated based on time.

Two types of tests were conducted: a flat plate before the processing test and a processed surface (die side) of a cup-shaped product subjected to high-speed deep drawing.

Claims (1)

[Claims] 1. (B) organosilica sol based on 100 parts by weight of an organic resin component (A) consisting of an epoxy resin or having an epoxy resin as a main component and having a glass transition point of 80° C. or higher. 10 to 60 parts by weight in solid content and (C) melting point 90
A composition capable of forming a lubricating film, characterized in that it contains 0.3 to 20 parts by weight of a lubricity imparting agent mainly composed of polyolefin wax having a temperature of 0.3 to 20 parts by weight. 2. The lubricity imparting agent contains a polyolefin wax having a melting point of 110° C. or higher and a fine fluororesin powder, and the amount of the fine fluororesin powder is 100 parts by weight per 100 parts by weight of the polyolefin. 2. The composition of claim 1, wherein the composition is less than parts by weight. 3. A lubricating metal plate obtained by coating a metal plate with the composition according to claim 1 or 2 at a dry coating weight of 0.2 to 5.0 g/m^2 to form a coating.