JP2002241960A - Lubrication-treated metallic sheet having excellent formability and slidability, and in which horizontal slippage when stacked and collapse of coil are hard to occur - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubrication treated metallic sheet which has excellent formability and slidability, and has no problem in handling such as horizontal slippage of the sheets when stacked and the collapse of a coil, and in which the elution of hexavalent chromium as an environmental load substance is extremely little or zero. SOLUTION: One side or both sides of the metallic sheet are provided with a mixed film (R) containing a resin used as a binder (a), a lubricating component (b) reducing the coefficient of dynamic friction, and (c) a slippage suppressing component increasing the coefficient of static friction as essential components. The metallic sheet has excellent formability and slidability, and horizontal slippage of the stacked sheets and the collapse of a coil are hard to occur.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is widely applicable to home appliances, building materials, automobiles, etc., and is excellent in moldability and slidability, but hardly causes problems such as side slip at the time of lamination and coil collapse. Also, the present invention relates to a lubricated metal sheet that has little elution of hexavalent chromium, which is an environmentally hazardous substance, or does not contain hexavalent chromium.

[0002]

2. Description of the Related Art Metal sheets for home appliances, building materials and automobile parts, such as steel sheets, various types of plated steel sheets, stainless steel sheets, aluminum sheets, titanium sheets, and the like, are often processed in some manner, such as bending, press forming, and the like. It becomes a product after being subjected to roll forming, etc., but it may be damaged or fall off due to galling at the time of processing, or even in severer processing, the base material may crack due to insufficient slidability and it may not even be possible to mold . To solve this problem, 1) molding while applying a lubricating liquid (press oil, quick-drying oil, forming liquid, etc.) to the metal plate at the time of molding 2) Excellent slidability as a surface treatment layer of the metal plate Two measures are taken: providing a coating. These may be used together, but it is desirable from the viewpoint of improving workability of material assembling manufacturers and protecting the global environment that the measures in 2) should be mainly implemented and the measures in 1) should be omitted or simplified.

As a metal surface treatment capable of eliminating press oil, a method in which a resin layer to which a lubricant is added is provided as a second layer on a chromate film as a general method is disclosed in, for example, JP-A-6-57441. JP-A-6-145559, JP-A-7-34260, JP-A-8-267
No. 003 can be exemplified. As a specific film configuration, as a chromate film, any one of an electrolytic type, a reaction type, and a coating type chromate, and a water-dispersible or solvent type urethane resin, an acrylic resin, an epoxy resin, a polyester resin, and the like as a resin, and as a lubricant. Typically, polyethylene wax, Teflon (registered trademark), paraffin wax, or the like is used. In addition, although a similar two-layer structure is used, there is an example as disclosed in Japanese Patent Application Laid-Open No. 1-130762 in which the upper organic film is discontinuous by electrostatic coating in order to improve the conductivity of the film.

On the other hand, a technique for forming a chromate film having lubricity on a metal plate in one step has also been disclosed, for example, in JP-A-7-216555 and JP-A-8-176845.
JP, JP-A-8-333688, JP-A-9-1
No. 57893, JP-A-9-291370 and the like can be exemplified. These are prepared by modifying the lubricant surface with a surfactant or colloidal silica, or stabilizing it by copolymerization with an acrylic monomer, dispersing it in a chromic acid bath, and coating or electrolyzing it on a metal plate. A chromate film having lubricity is formed in one process.
There are types that contain resin components other than lubricants and types that do not.

[0005]

However, there are problems with these prior arts. On top of the chromate film,
A method of providing a resin layer to which a lubricant is added as a second layer is as follows.
Certainly, it can exhibit good lubrication, but because of good lubrication, it is easy to cause side slip when laminating with cutting plates, and the coil is liable to collapse or loose winding even in the coil state during transportation In addition, there is room for improvement in handling properties after production, such as the need for caution during storage.

On the other hand, a method of forming a lubricating chromate film on a metal plate in one step is more advantageous in terms of cost than two-layer processing, but is described in Japanese Patent Application Laid-Open No. 9-291370. As described above, in order to prevent the side slip in the lamination of the cut plate, the dynamic friction coefficient is set to a critical value (in the publication, 0.
12) There is a restriction that it must be above. More recently, due to growing awareness of environmental issues,
Japanese Patent Application Laid-Open No. 7-21655 discloses that while the use of materials suspected of eluting hexavalent chromium, which is suspected of carcinogenicity, is being restricted.
No. 5, JP-A No. 8-176845, JP-A No. 9-176845
In the case of a coating composition consisting only of a chromic acid compound and a lubricant as disclosed in Japanese Patent No. 157893, elution of chromium cannot be suppressed to a high degree.
No. 6,555, the alkali-insoluble content in chromate is 70%.
%, And in Japanese Patent Application Laid-Open No. 9-157893, the chromium fixation rate in boiling water immersion is at most 80%. Such a metal plate having a chromate film with a large amount of soluble components has an industrial problem that hexavalent chromium is eluted into a forming solution during, for example, roll forming, thereby shortening the solution life.

The present invention can be widely applied to home appliances, building materials, automobiles, and the like, and is excellent in moldability and slidability, hardly causes problems such as side slip at the time of lamination and coil collapse, and has a low environmental load. It is an object of the present invention to provide a lubricated metal plate that has little elution of hexavalent chromium as a substance or does not contain hexavalent chromium, and a method for obtaining the metal plate.

[0008] The present inventors have proposed that any of the conventional known examples include:
It has been developed only from the viewpoint of improving lubricity and moldability, and it has been noticed that there is no clear guideline for improving the handling properties after production. For example, JP-A-9
As described in JP-A-157893 and JP-A-4-44840, in order to improve slidability, lubricant particles are largely projected from the coating regardless of whether the coating is a one-step coating or a two-step coating. It has been considered that the lubrication performance is poor if the lubricant is covered by the film.

On the other hand, the present inventors have found that under conditions where a lubricant is required, for example, at the time of molding, the surface pressure on the film is somewhat applied, and the film is deformed. The inventors have noticed that the above problems can be solved by adopting a film structure in which the lubricant is less likely to act at a low surface pressure.

A lubricating film having such a structure can be obtained by applying a proper amount of a film containing no lubricant particles on a known lubricating film in which lubricating particles are largely projected from the film. Process processing is not economical.
Therefore, as a result of intensive studies, a lubricating component (b) acting at a high surface pressure and a slip suppressing component (c) that stops slipping at a low surface pressure and does not affect molding at a high surface pressure are found in the coating. The above problem can be solved economically by the combined addition. When both (b) and (c) are fine particles, an appropriate relationship between the addition ratio of both, the particle diameter of both, and the film thickness of the film, etc. By keeping the above, it was found that both moldability and handleability could be highly compatible, and the present invention was completed.

Regarding the suppression of dissolution of hexavalent chromium, 1) a method of increasing the chromium reduction rate in the coated chromate and further adding a reducing resin to the bath, 2) a method of applying an electrolytic type chromate, and 3) a non-chromium treatment How to apply, solved.

[0012]

The present invention provides the following (1).
To (8). (1) A mixed film (R) containing, as essential components, a resin (a) serving as a binder, a lubricating component (b) for decreasing the coefficient of dynamic friction, and a slip suppressing component (c) for increasing the coefficient of static friction, on one side of a metal plate or A lubricated metal plate with excellent moldability and slidability on both sides, which is less likely to cause side slip and coil collapse during lamination.

(2) The slip-suppressing component (c) for increasing the coefficient of static friction is an elastomer, which is excellent in moldability and slidability as described in (1) above, and has side slip and coil collapse during lamination. Lubricated metal plate that is unlikely to cause cracks.

(3) Both the lubricating component (b) for reducing the dynamic friction coefficient and the slip suppressing component (c) for increasing the static friction coefficient are fine particles, and the particle size Rb of (b) and the particle size of (c) R
c, the following equation between the thickness T _R of the mixed film (R) (I) ~ ( III)
A lubricated metal sheet having excellent formability and slidability according to the above item (2), which is less likely to cause side slip and coil collapse during lamination, wherein _{0.1 ≦ Rb / T R ≦ 4.0} (I) 0.2 ≦ Rc / T R ≦ 6.0 (II) 0.9 ≦ Rc / Rb (III)

(4) Between the addition rate Xb (% by weight) of the lubricating component (b) and the addition rate Xc (% by weight) of the anti-slip component (c) in the mixed film (R), the following formula (IV) A lubricated metal sheet having excellent moldability and slidability according to the above item (2), which is less likely to cause side slip or coil collapse during lamination, which has the relationship of (1) to (V). 2 ≤ Xb + Xc ≤ 25 (IV) 0.9 ≤ Xc / Xb ≤ 3.0 (V)

(5) The lubricated metal sheet according to the above (2) to (4), wherein the mixed film (R) having a thickness of 0.3 to 8 μm (per one side) is coated with Cr as an upper layer. 5-100m
A two-layer chromate-based lubricated metal sheet having a g / m ² (per side) chromate film in the lower layer.

(6) The lubricated metal sheet according to (2) to (4), wherein the mixed film (R) having a thickness of 0.3 to 8 μm (per one side) is formed on the upper layer, A two-layer type non-chromium-based lubricated metal sheet having a non-chromium-based undercoating film of 0.1 to 1 micron (per side) as a lower layer.

(7) The lubricated metal sheet according to the above (2) to (4), wherein the mixed film (R) further contains a water-soluble chromium compound and a mineral acid compound. (1) A single-layer type chromate-based lubricated metal sheet characterized in that the film thickness per side is 0.3 to 8 microns.

(7) The lubricated metal sheet according to the above (2) to (4), wherein the mixed coating (R) further contains a non-chromium-based antirust inhibitor. A one-layer non-chromium-based lubricated metal sheet having a thickness of 0.3 to 8 microns per side.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First,
The above (1) shows the characteristics of the film structure that the mixed film (R) is excellent in moldability and slidability, and hardly causes side slip and coil collapse during lamination. The above (2)
Shows that an elastomer can be suitably used as the slip-reducing component (c), which is a particularly important requirement in the above (1).

The term "elastomer" as used herein refers to a polymer which exhibits rubber elasticity at room temperature, and includes, for example, vulcanized rubber (natural rubber, synthetic rubber), thermoplastic elastomer,
Elastic fibers (e.g., spandex) and elastic foams belong to this category. Among them, those which can be called fine-particle elastomers as described in (3) above have an average particle diameter of about 0.
They range from 1 micron to about 10 microns. The elastic fiber is not a particle, but if the size (length, thickness) is in this range, the same effect as the fine particles can be obtained by adding the elastic fiber to the film. It is not clear why the elastomer exerts a slip-suppressing effect, but it is thought to be due to the fact that the elastomer has some tackiness as well as rubber elasticity.

In the present invention, among the above elastomers,
Vulcanized rubber and thermoplastic elastomers can be used particularly preferably. Examples of the vulcanized rubber include an acrylic rubber (A), a butadiene rubber (B), a chloroprene rubber (C), an isoprene rubber (I), an acrylonitrile rubber (N), a styrene rubber (S), and a carboxylated product thereof (X ), Copolymers thereof, copolymers thereof with olefins such as ethylene (E) and propylene (P), and the like. That is, if R is added at the end, AR, B
Examples include R, CR, IR, NR, SR, NBR, SBR, XSBR, EAR, EPR, and the like. Further, those further halogenated (especially fluorinated), sulfonated, and those containing silicone in the main chain thereof can be applied.

The thermoplastic elastomer has rubber elasticity at normal temperature, but can be processed as a thermoplastic at high temperature. This is because the thermoplastic elastomer is a composition having a multi-phase structure. One of the phase components is called a soft segment (rubber-like portion) and behaves like a vulcanized rubber at room temperature, and the other phase component. Is called a hard segment (crosslinked portion) and is hard at normal temperature and shows thermoplasticity at high temperature. The above-described vulcanized rubber or the like is used for the soft segment, and polyolefin, polystyrene, polyester, polyamide, polyurethane, or the like is used for the hard segment.

As the lubricating component (b) in the above (1), ordinary solid lubricants, ie, fluororesin waxes such as polyethylene wax, polyolefin wax, paraffin wax, microwax, oxidized polyolefin wax, Teflon, and zinc stearate are used. Stearic acid compounds such as and ethylenebisstearylamide, molybdenum disulfide, tungsten disulfide, graphite,
Lubricants exemplified by boron nitride, graphite fluoride, cerium fluoride, melamine cyanurate and the like are applicable.

The binder resin (a) in the above (1)
Is not particularly limited as long as it can hold the lubricating component (b) and the slip suppressing component (c). Examples thereof include polyolefin resins such as polyethylene, polypropylene, and ionomer, acrylic resins, epoxy resins, and nylon resins (polyamide). Resins), polycarbonate resins, polyurethane resins, Teflon and other fluorine resins, and polyester resins such as polyethylene terephthalate.

The above (3) is to maintain an appropriate relationship between the particle diameter of the lubricating component (b) and the thickness of the mixed coating (R) when both the lubricating component (b) and the anti-slip component (c) are fine particles. so,
This shows that both moldability and handleability can be highly compatible.

[0027] formula (I) shows the relationship between the particle diameter and film thickness of the lubricating component (b), the lubricating effect is not sufficient for Rb / T _R is less than 0.1, it exceeds 4.0, the slip suppressing component ( The effect of c) is impaired. Equation (II) shows the relationship between the particle size of the slip-reducing component (c) and the film thickness, and Rc / T
_{If R} is less than 0.2, the effect of suppressing the slip is not sufficient, and if _R exceeds 6.0, the effect of the lubricating component (b) is impaired. Equation (III) shows the relationship between the particle size of the lubricating component (b) and the particle size of the slip suppressing component (c). If Rc / Rb is less than 0.9, the slip suppressing effect becomes insufficient.

In the above (4), when the lubricating component (b) and the anti-slip component (c) are both fine particles, by maintaining an appropriate relationship between the addition ratios of the two, the moldability and the handleability are enhanced. It is shown that the corrosion resistance and the paintability, which are the basic characteristics of the film, can be ensured.

Equation (IV) indicates the range of the addition ratio of the lubricating component (b) and the slip suppressing component (c), and Xb + Xc is 2 wt%.
If the amount is less than 25%, the effects are small. If the amount exceeds 25% by weight, the corrosion resistance of the film and the adhesion of the top coat are impaired. More preferably, the content is 5 wt% or more and 20 wt% or less. Equation (V) indicates the range of the ratio of the addition ratio of the lubricating component (b) to the slip inhibiting component (c). When Xc / Xb is less than 0.9, the effect of the slip inhibiting component (c) is small, and exceeds 3.0. And lubricating component (b)
Is less effective.

Here, the particle size of each fine particle is an arithmetic average particle size measured by a particle size distribution analyzer using a fine particle emulsion. If the particle size is about several microns, it can be confirmed also by electron microscopic observation of the surface of the lubricating film. On the other hand, the thickness of the mixed film (R) was determined by embedding and polishing the cross section of the lubricated metal plate in a resin sample (minimum of 5 samples), and measuring the film thickness of at least 10 randomly selected visual fields with an electron microscope. The average value was obtained.
The film thickness was measured at a magnification such that the length of one visual field in the surface direction was about 10 times the film thickness, and the film thickness at the center of the visual field was defined as the representative film thickness of the visual field. In addition, the film thickness of the base treatment of the above (6) was obtained in the same manner.

The above (5) to (8) correspond to the above (1) to
It is a specific example of a lubricated metal plate having the mixed film (R) described in (4) on its surface. First, (5) is an example in which the mixed film (R) of (1) to (4) is provided via a chromate treatment layer as a base treatment. If electrolytic chromate is used as the chromate, elution of hexavalent chromium can be suppressed. If the Cr adhesion amount is less than 5 mg / m ² , the underlying metal is not uniformly coated, and if it exceeds 100 mg / m ² , the cohesive strength is inferior and the adhesion to the underlying substrate is reduced. If the thickness is less than 0.3 μm, a continuous film cannot be obtained, and if the thickness exceeds 8 μm, the effect is saturated.

The above (6) is an example in which the mixed film (R) of the above (1) to (4) is provided via a non-chromium-based treatment layer as a base treatment. The thickness of the non-chromium treatment layer is
If it is less than 0.1 μm, a continuous film cannot be obtained, and if it exceeds 1 μm, the cohesive strength is inferior and the adhesion to the base decreases. When the thickness of the mixed film (R) is less than 0.3 μm, a continuous film cannot be obtained, and when the thickness exceeds 8 μm, the effect is saturated. Examples of non-chromium-based treatments that can be used include phosphate treatment and coupling agent treatment.

In the above (7), a water-soluble chromium compound and a mineral acid compound are further contained in the mixed film (R) of the above (1) to (4). By increasing the chromium reduction rate of the water-soluble chromium compound or adding a resin in the bath,
The elution of hexavalent chromium can be reduced. The film thickness is 0.3
If it is less than micron, a continuous film cannot be obtained, and the performance is not stable. If the film thickness exceeds 8 microns, the effect is saturated.

In the above (8), the mixed coating (R) of the above (1) to (4) further contains a chromium-free rust inhibitor. Examples of the non-chromium rust inhibitor include polyphenols such as tannic acid and phytic acid, nitrogen-containing compounds, sulfur-containing compounds, molybdic acid, tungstic acid, phosphoric acid compounds, and silicate compounds. If the film thickness is less than 0.3 microns, a continuous film cannot be obtained.
Performance is not stable. If the film thickness exceeds 8 microns, the effect is saturated.

The metal plate to which the present invention can be applied is not particularly limited, and examples thereof include a steel plate, an aluminum alloy plate, a titanium alloy plate, a magnesium alloy plate, and a zinc alloy plate. More specifically about steel sheets, hot rolled steel sheets, cold rolled steel sheets, silicon steel sheets, stainless steel sheets, and electroplated steel,
Various types of plated steel sheets prepared by methods such as hot-dip plating, vapor deposition plating, electroless plating, and hot-dip electrolytic plating are exemplified. The details of various types of coated steel sheets include, for example, galvanized steel sheets, zinc and nickel, iron, aluminum, chromium, titanium, magnesium, manganese, cobalt, tin,
Alloy plated steel sheet with one or more metals such as lead, and further intentionally contain other metals and / or inorganic substances such as silica, alumina, titania, zirconia, and / or organic compounds in these plated layers. Or a plated steel material contained as an impurity,
There is a plated steel sheet having a plurality of types of plating in multiple layers.

[0036]

The present invention will now be described by way of non-limiting examples. (1) Tested metal sheet GI (hot-dip galvanized steel sheet): A steel sheet obtained by applying a hot-dip galvanization of 60 g / m ² per side to a mild steel sheet of 0.8 mm thickness EG (electro-galvanized steel sheet): 0.8 mm thickness Steel sheet with 20g / m ² galvanized per side on mild steel sheet

(2) Mixed film (R) Those having bath symbols A-1 to D-3 shown in Table 1 were used. As comparative examples, those shown in X-1 to Y-3 were used. In order to obtain these films, the following (2-1) to
A treatment liquid was prepared by dispersing or dissolving a predetermined amount of the component (2-4) in water. (2-1) Types of Resin (a) The following four types were used. Both are emulsion resins,
The particle size is between 50 and 200 nm. Acrylic: Ethylene-acrylic acid copolymer Urethane: Carbonate urethane resin Acrylic: Acrylic ester copolymer dispersible in acidic bath Ionomer: Na neutralized ionomer resin (2-2) Types of lubricating component (b) Three types were used. The particle size is as described in Table 1. PE: polyethylene wax PAR: paraffin wax PTFE: Teflon wax (2-3) Types of slip-inhibiting component (c) The following four types were used. The particle size is as described in Table 1. T-EBR: Ethylene-butene-based thermoplastic elastomer SBR: Styrene-butadiene-based elastomer NBR: Acrylonitrile-butadiene-based elastomer T-PU: Urethane-based thermoplastic elastomer (2-4) Other components The following five types shown in Table 1 Was used. Silica: Colloidal silica dispersed in alkali type Silica: Colloidal silica dispersed in acidic type Reduced chromic acid: Chromium reduction rate of 70% Phosphoric acid: orthophosphoric acid Organic inhibitor: tannic acid

(3) Lubricating film treatment Samples 1 to 28 shown in Table 2 were prepared in a laboratory. As the metal plate, EG is used for 1 to 6 and 16 to 28.
And GI was used for 7 to 15. All the metal plates were alkali-degreased. For 1 to 6, 21, and 23 to 25, electrolytic chromate treatment was performed as a base treatment. The chromium adhesion amount is as shown in the table. For 7 to 9, immersion-drying with a silane coupling agent was performed, and for 10 to 11, zinc phosphate treatment was performed. 1
No base treatment was performed on 2 to 20, 22, and 26 to 28. Next, the treatment liquid for a lubricating film shown in Table 1 was applied to both sides of a test plate by a roll coater, and dried in a hot-air drying oven to reach a plate temperature of 90 to 100 ° C. However, 21, 2
In the case of No. 2, paraffin as a lubricating component was completely melted at a dry plate temperature of 150 ° C. At this time, it was confirmed by an electron microscope that the slip suppressing component was kept in a particle state.

(4) Performance Evaluation Test (4-1) Static Friction Coefficient A Heidon 10 type testing machine was used for measuring the static friction coefficient.
The test material was a large plate with a width of 120mm and a length of 280mm, and a width of 35mm and a length of 35mm.
A 70 mm piece was cut out so that the longitudinal direction was the line direction. After removing the burrs on all four sides of the small piece, a flat Cr-plated steel flat indenter (weight 200g,
(A bottom area of 35 mm x 70 mm). The large plate is fixed horizontally to the tester so that there is no warp, the indenter to which the small pieces are adhered is placed along the longitudinal direction, and then tilted in the longitudinal direction at a speed of 0.5 ° C / sec. The sensor was stopped at the time of sliding, and the static friction coefficient was calculated from the sliding angle θ as μ = tan θ. The combination of the large plate and the small piece was performed twice in a combination in which the front surface of the large plate and the back surface of the small piece overlapped, and twice in a combination in which the back surface of the large plate and the small piece overlapped. I asked. In each experiment, seven repeated measurements were performed, and the five measured values excluding the maximum and the minimum were averaged. That is, a total of 20
The measurements were averaged.

(4-2) Dynamic friction coefficient The dynamic friction coefficient was determined by a so-called flat plate sliding method. The test material was cut out to a width of 30 mm and a length of 300 mm so that the longitudinal direction was the line direction. This is pressed from both sides by a flat Cr indenter made of Cr-plated steel (bottom area: 30 mm x 20 mm) with a holding pressure of 5 kgf / cm ² (98 kgf converted to holding load P because the hydraulic cylinder diameter is 50 mm), and withdrawal speed. Average pulling load (F) when pulling out the central part 80mm of the test material at 20mm / min
Was measured, and the dynamic friction coefficient was calculated as μ = F / 2P. The measurement was performed three times while changing the test material, and the average value was obtained.

(4-3) Formability A cylindrical drawing test with a bead was performed on the test material under the following conditions.
The molding height was examined. In addition, the material of each test material is P2
Class. Punch diameter 50mm (shoulder 9mmR) Die diameter 68mm (shoulder 1mmR) Blank diameter 130mm Wrinkle pressure 2ton ◎: Molding height 40mm or more (drawing out) ○: 35mm ≤ Molding height <40mm △: 25mm ≤ Molding height <35mm ×: Molding height <25mm

(4-4) Laminated slip property The test material was cut into a piece of 300 mm x 300 mm, and 30 pieces of the material were piled on a trolley, pushed down at a speed of 30 m / min, and then suddenly stopped. The state was evaluated as follows. ◎: No collapse of the load at all ○: Less than 2 plates collapsed by skidding △: 3 or more, 7 or less plates collapsed by skidding ×: 8 or more plates collapsed by skidding

(4-5) Corrosion Resistance After the end face and the back face of the sample were tape-sealed, a salt spray test was carried out, and the following ranks were classified according to the time until the occurrence of white rust. ◎: 240 hours or more until white rust occurs ○: 168 hours or more and less than 240 hours until white rust occurs △: 120 hours or more and less than 168 hours until white rust occurs ×: less than 120 hours until white rust occurs

(4-6) Coating Adhesion A melamine alkyd paint was applied to the test material in a thickness of 25 μm and the temperature was 130 ° C.
And then immersed in boiling water for 30 minutes. By pressing a 15 mm diameter steel hemispherical projection from the back side, so-called Erichsen extrusion processing is applied to a height of 6 mm, the coating film of the processed part is peeled off with Cellotape (registered trademark), and the peeling area ratio is examined. Was. ◎: No coating film peeling ○: Film peeling rate <5% △: 5% ≦ film peeling rate <20% ×: 20% ≦ film peeling rate

(4-7) Chromium elution rate Of the test materials, 1 to 6, 12 to 1 containing chromium
For 5, 21, 23 to 25, the amount of Cr attached was measured by X-ray fluorescence, then immersed in boiling water for 30 minutes, and the amount of residual Cr was measured again by X-ray fluorescence to obtain Cr by boiling water immersion.
The elution rate (decrease rate) was determined by the following equation. Cr elution rate = 100 × (Cr decrease amount by immersion in boiling water) / (Initial Cr adhesion amount) As a result, electrolytic chromating was performed 1 to 6, 21, and 23
The Cr elution rate was 0.5% or less, and for 12 to 15 coated with reduced chromic acid, the Cr elution rate was 3% or less.

The results of (4-1) to (4-6) are as shown in Table 2. The lubricated metal sheet of the present invention is excellent in formability, but has no handling problem such as lamination side slip, and particularly when the above-mentioned formulas (I) to (V) are satisfied, the formability and handleability are high. It can be seen that they are compatible and have excellent basic performance of the film such as corrosion resistance and paintability.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

According to the present invention, it can be widely applied to home appliances, building materials, automobiles, etc., and has excellent moldability and slidability.
Further, it is possible to provide a lubricated metal material having no handling problems such as side slippage and coil crushing at the time of lamination, and having very little or no elution of hexavalent chromium as an environmentally hazardous substance. Therefore, it can be said that the invention is extremely valuable industrially.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 103/02 C10M 103/02 A 103/06 103/06 BC 105/24 105/24 105/68 105 / 68 105/70 105/70 107/02 107/02 107/18 107/18 107/38 107/38 109/00 109/00 143/02 143/02 143/04 143/04 143/10 143/10 143/12 143/12 145/14 145/14 145/22 145/22 147/02 147/02 149/08 149/08 149/14 149/14 149/18 149/18 173/02 173/02 C23C 22 / 00 C23C 22/00 Z 22/28 22/28 28/00 28/00 ZA // C10N 10:04 C10N 10:04 10:06 10:06 10:12 10:12 30:00 30:00 Z 50:02 50:02 50:08 50:08 80:00 80:00 F term (reference) 4F100 AA20H AB01B AB03 AB13D AB13E AB18 AJ11 AK01A AK01C AK04 AK18 AK25 AK51 AK65 AK70 AK71 AK73 AL05A AL05C AL09A AL09C AS00A AS00BA02 BA05 BA06 BA07 BA10A BA10C BA10D BA10E DE01A DE01C GB07 GB31 GB4 1 JK16 JK16A JK16C JM02A JM02C YY00A YY00C 4H104 AA04A AA05A AA16A AA19A AA26A BB17A BE11A BE28A CA01A CA02A CA02C CA03C CA07C CA12C CA16A CB08C CB12C CB13C CD01C CD02A CD02C CE04C CE13C DA02A DA05A FA02 FA03 FA06 LA20 QA01 QA08 QA12 RA02 4K026 AA02 AA04 AA07 AA08 AA09 AA11 AA12 AA13 BA06 BB04 BB09 CA16 CA18 CA22 CA26 CA39 DA02 4K044 AA01 AA02 AA03 AA06 AB02 BA06 BA10 BA15 BA17 BA21 BB01 BB03 BB11 BC01 BC05 CA11 CA13 CA15 CA16 CA17 CA18 CA53

Claims (8)

[Claims] 1. A mixed film (R) containing, as essential components, a resin (a) serving as a binder, a lubricating component (b) for reducing the coefficient of dynamic friction, and a slip-suppressing component (c) for increasing the coefficient of static friction. Formability on one or both sides
A lubricated metal plate that has excellent slidability and is less likely to cause side slippage and coil collapse during lamination. 2. The method according to claim 1, wherein the anti-slip component (c) for increasing the coefficient of static friction is an elastomer.
A lubricated metal sheet that has excellent moldability and slidability as described, and is less likely to cause side slip and coil collapse during lamination. 3. A lubricating component (b) for reducing the coefficient of dynamic friction,
Slip suppressing component to increase the static friction coefficient (c) is a both a particulate, the following equation between the particle diameter Rb, the particle size Rc of (c), the thickness T _R of the mixed coating (R) of (b) 3. The lubricated metal sheet according to claim 2, which has the relationship of (I) to (III), and is excellent in formability and slidability, and is less likely to cause side slip and coil collapse during lamination. _{0.1 ≦ Rb / T R ≦ 4.0} (I) 0.2 ≦ Rc / T R ≦ 6.0 (II) 0.9 ≦ Rc / Rb (III) 4. A lubricating component (b) occupying in the mixed film (R).
Addition rate Xb (wt%), slip suppression component (c) addition rate Xc
(Weight%), the following formulas (IV) to (V) are satisfied, and the moldability and the slidability are excellent, and side slip and coil collapse at the time of lamination are caused. Difficult lubricated metal plate. 2 ≤ Xb + Xc ≤ 25 (IV) 0.9 ≤ Xc / Xb ≤ 3.0 (V) 5. The lubricated metal sheet according to claim 2, wherein a mixed film (R) having a film thickness of 0.3 to 8 μm (per one side) is formed on the upper layer, and a Cr adhesion amount of 5 to 100 mg. A double-layered chromate-based lubricated metal sheet having a / m ² (per side) chromate film in the lower layer. 6. The lubricated metal sheet according to claim 2, wherein a mixed film (R) having a thickness of 0.3 to 8 μm (per side) is formed on the upper layer, and the thickness of the mixed film is 0.1 to 0.1 μm. A two-layer type non-chromium-based lubricated metal plate having a 1-micron (per side) non-chromium-based undercoat film as a lower layer. 7. The lubricated metal sheet according to claim 2, wherein the mixed film (R) further contains a water-soluble chromium compound and a mineral acid compound, and the mixed film (R) has a thickness. A single-layer chromate-based lubricated metal sheet having a thickness of 0.3 to 8 microns per side. 8. The lubricated metal sheet according to claim 2, further comprising a non-chromium-based rust inhibitor in the mixed coating (R), wherein the mixed coating (R) has a single-sided thickness. A one-layer non-chromium-based lubricated metal sheet having a diameter of 0.3 to 8 microns per one piece.