JP2004232085A - Surface-treated metal plate, method for producing the same, lubricating resin and lubricating resin coating composition used in the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable and inexpensive material having high slipperiness to slide PET bottles, press formability to withstand multi-step ironing, paper abrasion resistance, snow sliding property, and the like.
SOLUTION: A solid lubricant (B) having a continuous film (A) having an average film thickness of 20 μm or less on one or both surfaces of a metal plate, and having a major axis three times or more the average film thickness in the film. Surface treated metal plate contained. As a solid lubricant, a surface-treated metal plate containing at least 10 fluorocarbon resins per mm ² having a major axis of more than 20 μm when viewed from a direction perpendicular to the film, and the components of the continuous film (A) and the film A surface treatment in which a solid lubricant (B) having a major axis longer than three times the thickness is mixed and applied to a metal plate, and the solid lubricant is flattened using the surface pressure at the time of application to maintain the solid lubricant in the coating. Manufacturing method of metal plate.
[Selection diagram] Fig. 1

Description

  The present invention relates to a metal plate having a continuous film containing an additive on the surface and a method for producing the same. In particular, the present invention relates to a lubricating metal plate containing a solid lubricant as an additive. INDUSTRIAL APPLICABILITY The present invention is excellent in slipperiness as compared with a conventional lubricating metal plate, and therefore is suitably used particularly for applications in which articles and the like are slid and moved. Further, since it has excellent durability against repeated sliding, it can be applied to press molding, particularly to multi-stage molding. Furthermore, since it is excellent in abrasion resistance, it can be applied to abrasion resistance applications such as a paper passing portion of a copying machine. Further, since it has water repellency, it can be applied as an outdoor metal material having snow sliding properties and stain resistance.

  In the automatic logistics, the movement of articles by hoppers, shooters, etc. has been widely performed, but in recent years, the efficiency has been increased, that is, the opportunity loss due to traffic congestion during the transfer, or the device by lowering the slope of the transfer plate. There is an increasing demand for miniaturization as a whole. On the other hand, taking vending machines as an example, in addition to conventional products in cans and bottles, the penetration rate of PET bottle products, which are less slippery, will increase, and the use of transfer plates with high lubricity will increase. Needs are growing.

  As a material which has been used as a transfer plate for a long time, there is a composite plated metal plate in which a fluorine-based resin is codeposited on Ni-based plating as disclosed in JP-A-6-325255. However, this method cannot provide a high degree of lubricity because the cost is high and the amount of eutectoid fluorine resin is limited.

  A conventional technique that can improve this is a coated metal plate that contains a fluorine-based resin such as polytetrafluoroethylene (PTFE) as a solid lubricant in the coating film in order to improve lubricity and press moldability. Can be For example, Japanese Patent No. 3071376 discloses an organic composite steel sheet in which polytetrafluoroethylene resin particles having an average particle diameter of 0.1 to 5 μm are contained as a solid lubricant in an epoxy resin and applied to the surface of a galvanized steel sheet. ing. JP-A-8-174758 discloses that a hydrophilic resin contains a water-dispersible polyolefin resin or a water-dispersible fluorine resin having an average particle diameter of 0.05 to 7 μm as a lubricant, and is applied to a zinc-based plated steel sheet. A dried organically coated plated steel sheet is disclosed. Japanese Patent No. 2617837 discloses that a polyolefin wax and a polytetrafluoroethylene (Teflon wax (trade name)) each having a particle diameter of 3 μm or less are mixed with an aqueous resin, coated, and dried on the surface of a plated steel sheet. A method for producing a lubricated plated steel sheet is disclosed. The reason for limiting the particle size of the fluororesin in these technologies is that if the particle size is too small, the lubricating properties are inferior.If the particle size is too large, the protrusion from the resin film is too large to be easily retained in the film. If it is too large, it is difficult to be uniformly dispersed in the resin. In Japanese Patent Application Laid-Open No. 2-92536, this relationship is quantified, and when the film thickness is T and the particle size of the fluororesin is R, T / R = 0.6 to 2 is a preferable range.

  Since a fluorine-based resin is a resin having a low surface free energy, when it is mixed with another resin, it tends to concentrate on the surface layer of the film when dried. As prior arts related to this, Japanese Patent Application Laid-Open No. 2-92536 and Japanese Patent No. 3075117 can be cited. Japanese Patent Application Laid-Open No. 2-92536 discloses a technique for selecting a fluorine-based resin powder having a particle diameter suitable for the thickness of a dried coating film in order to positively perform layer separation by surface concentration of the fluorine-based resin. I have. On the other hand, in Japanese Patent No. 3075117, when the surface concentration is too high, the lubricating property is lost at the stage where the surface layer is worn, so that the drying conditions are rather set so that the fluororesin remains on the side closer to the metal plate in the coating. A technique of optimizing is disclosed. Layer separation due to the surface concentration of the fluororesin is a technical problem caused by the relative small particle size of the fluororesin powder compared to the dry coating thickness of the base resin, and these known examples solve it. Is what I tried.

  On the other hand, there is a conventional technique using a fluororesin having a larger particle diameter. Japanese Patent Application Laid-Open No. 2001-198522 discloses that, based on an acrylic resin, 3 to 30% by mass of a polytetrafluoroethylene powder having a particle diameter of 0.1 to 5 μm is added to improve lubricity, and a polytetrafluoroethylene having a particle diameter of 7 to 20 μm is further added. There is a technique in which 1 to 10% by mass of fluoroethylene powder is added to give a matte appearance. Here, the reason why the powder having a particle diameter of 7 to 20 μm is limited to 10% by mass or less is that if added in excess of this, the abrasion resistance is rather lowered. Japanese Unexamined Patent Publication (Kokai) No. 62-179936 discloses a precoated steel sheet having a dry film thickness of 5 to 200 μm, in which a fluorinated resin powder having a particle diameter of 1 to 110 μm is added to a bake-hardening resin.

  As a prior art in which a fluorine-based resin is applied to abrasion resistance, there is JP-A-2003-33995. This means that a fluororesin powder having an average particle diameter of 1 μm or less is mixed with a scaly inorganic additive in a heat-resistant paint such as polyether sulfone, applied to a metal plate, heated to the melting temperature of the fluororesin, and then fired. Thus, a thin film of a single fluororesin is formed on the outermost layer of the film. The presence of this fluororesin thin film imparts initial abrasion and non-adhesiveness. Japanese Patent Application Laid-Open No. Hei 8-57413 discloses a method for imparting abrasion resistance to a metal plate by concentrating the surface of a fluororesin by thermal melting by thermal fusion.

  There are a number of conventional techniques that make use of the water repellency and stain resistance of fluororesins. Japanese Patent Application Laid-Open No. Hei 7-90691 discloses a technique in which the surface of hard base particles made of metal or ceramics is coated with a fluorine-based resin, and this is co-deposited during plating of a metal such as nickel. Japanese Patent Application Laid-Open No. 9-141780 discloses that a steel sheet excellent in environmental pollution resistance can be obtained by laminating a fluorine-based resin film on the steel sheet surface via a chemical conversion treatment layer.

Fluorine-based resins are also used as surface treatments for metal sheets having excellent snow sliding properties. In JP-A-63-268636 and JP-A-64-58539, a fluorine-based resin layer containing no pigment is provided on the surface layer for improving snow sliding property, and the second layer is provided for improving durability. A metal plate provided with a fluororesin layer containing a pigment is disclosed.
JP-A-6-325255 Japanese Patent No. 3071376 JP-A-8-174758 Japanese Patent No. 2617837 JP-A-2-92536 Japanese Patent No. 3075117 JP 2001-198522 A JP-A-62-179936 JP 2003-33995 A JP-A-8-57413 JP-A-7-90691 JP-A-9-141780 JP-A-63-268636 JP-A-64-58539 JP-A-7-90620 JP-A-4-341375

However, these conventional techniques have problems.
A fluororesin having a particle diameter of several μm or less can be obtained by emulsion polymerization. Further, an aqueous dispersion of a fluororesin is commercially available as a concentrate obtained by adding a surfactant to a latex of a fluororesin obtained by emulsion polymerization, and then concentrating and stabilizing the resultant. This is excellent in dispersion stability in a coating composition as described in JP-A-7-90620. However, when a fluorine-based resin having a particle size of several μm or less obtained by emulsion polymerization is mixed with another resin and applied to a metal plate, winding of the fluorine-based resin on an application roll easily occurs. This is considered to be due to the fact that, as a characteristic of the fluorine-based resin, it becomes easy to fibrillate when subjected to a shearing force. Japanese Patent Application Laid-Open No. 4-341375 discloses that when fluorine-based resin particles having a particle diameter of 0.01 to 2 μm coated with an acrylic or polyethylene-based resin are used, the fluorine-based resin particles are peeled off from the film and wound around a roll during production. It is disclosed that this problem can be solved. However, since this is exfoliation from the film after the application and drying, it is only possible to avoid winding around the transport roll in a process below the application roll, and directly solve the problem of fiberization on the application roll. It is not a solution.

  Another problem when using a fluorine-based resin having a particle diameter of several μm or less is the above-described layer separation due to the surface concentration of the fluorine-based resin. In order to solve this problem, according to the method disclosed in Japanese Patent Application Laid-Open No. 2-92536, it is necessary to prepare a fluororesin having a very narrow particle diameter distribution (the particle diameter is more than 1/2 of the film thickness, 5/5). 3 or less). For that purpose, it is necessary to separate a fluororesin having a wide particle size distribution synthesized by an ordinary method with a filter or the like, which is troublesome and costly. On the other hand, the method of Japanese Patent No. 3075117 attempts to control the surface concentration of the fluororesin only by the drying conditions. However, to control the surface concentration, the viscosity of the base resin changes depending on the ambient temperature. It is also difficult to obtain a desired layer separation structure stably.

  JP-A-2003-33995 and JP-A-8-57413 are techniques for thickening a surface by melting a fluororesin, and are advantageous in that the surface can be thickened regardless of the particle diameter of the original fluororesin. It is. However, it is necessary to raise the temperature of the drying plate to a temperature at which the fluororesin melts, and then to calcine for several minutes to tens of minutes. This is not possible with lines having a line speed of several tens mpm or more. Further, it is necessary to use a base resin having heat resistance even at a temperature at which fluorine melts, but such a resin is expensive.

  On the other hand, when the particle size of the fluororesin is sufficiently larger than the coating film thickness, specifically, when the particle size is three times or more the coating film thickness, instead of the problem of the layer separation, the coating is performed. There is a risk of falling off the membrane.

  That is, in the prior art, 1) the fluororesin subjected to the shearing force on the application roll during production becomes fiberized and winds around the application roll. 2) The fluororesin powder is compared with the dry coating thickness of the base resin. If the particle diameter is relatively small, the fluororesin concentrates on the surface and separates layers. 3) If the particle diameter of the fluororesin powder is relatively large compared to the dry coating thickness of the base resin, the fluororesin powder will There is no inexpensive material that has solved all the problems of falling off from the coating film.

  SUMMARY OF THE INVENTION An object of the present invention is to solve the above three problems and to stably supply a material for a transfer plate having a high degree of slipperiness for slipping a PET bottle at low cost. The present invention also contemplates a lubricating metal plate applicable for press forming, abrasion resistance, snow and stain resistance.

  The present inventors have intensively studied to solve the above-mentioned problems. As a result, in the prior art, the relationship between the wrapping of the fluororesin around the application roll and the structure and properties of the fluororesin has not been clarified. On the premise that the fluororesin has a spherical shape or a shape close thereto, it has been found that there is only a viewpoint to optimize the relationship between the particle diameter and the dry film thickness.

  Therefore, when a method of suppressing winding around the coating roll was examined first, it was found that fluoropolymer as-emulsion-polymerized was easy to wind around the roll regardless of its particle diameter, but this was irradiated with radiation to obtain C. It has been found that a material having a reduced molecular weight by breaking the -F bond is hard to wind around a roll. In addition, fluororesins synthesized by suspension polymerization, which is another polymerization method, have less of a problem of winding around a roll than those synthesized by emulsion polymerization. It was also found that the material having a reduced molecular weight by breaking the bond was hardly wound around a roll.

  Next, regarding the problem of layer separation and falling off, the problem of layer separation in the film thickness direction is eliminated by using a fluorine resin powder having a particle diameter larger than the dry film thickness, and the fluorine resin is controlled by the roll surface pressure during coating. A method was devised to avoid the problem of falling off by crushing the portion protruding from the film. Then, they intensively studied measures for realizing it.

  First, a fluororesin synthesized by suspension polymerization was granulated (fired) for molding powder, and the molecular weight was reduced by irradiation with radiation. When a surface pressure was applied to this with a rubber roll for application, the particles collapsed. On the other hand, a fluororesin synthesized by emulsion polymerization was used as a fine powder having a particle diameter of several hundred microns, and without being granulated (fired), the one reduced in molecular weight by irradiation was plastically deformed by roll surface pressure. . Although the reason is not clear, the ones that were irradiated after granulating molding powder were `` hard and brittle '', whereas those irradiated without granulating fine powder were submicron. It is presumed that the primary particles were loosely combined to form "soft and easily deformable" secondary particles having a size of several tens of microns as a whole.

  On the other hand, the fluororesin synthesized by suspension polymerization also reduced its molecular weight by irradiation without granulation, and applied surface pressure with a rubber roll for application. In this case, plastic deformation also occurred. . That is, it was found that the particles whose molecular weight had been reduced by irradiation without irradiation of heat, such as granulation, undergo plastic deformation regardless of emulsion polymerization or suspension polymerization.

  In addition, we examined ways to develop a high degree of slipperiness for sliding PET bottles, press formability to withstand multi-stage molding, and high levels of abrasion resistance, snow sliding and stain resistance. By increasing the content of the fluororesin, which has a longer diameter than the film thickness and which has a flat shape, it is likely that this acts as a lubricating point due to surface contact, resulting in slipperiness, moldability, and abrasion resistance. The present inventors have found that the snow sliding property and the stain resistance are greatly improved, and have completed the present invention.

The present invention includes the following (1) to (15).
(1) A solid lubricant having a continuous film (A) having an average film thickness of 20 μm or less on one or both surfaces of a metal plate, and having, as an additive, a solid lubricant having a major axis of at least three times the average film thickness ( A surface-treated metal plate containing B).
(2) The surface-treated metal sheet according to the above (1), which contains a fluorine-based resin as a solid lubricant.
(3) The continuous film has a film thickness of 0.5 μm or more and contains, as a solid lubricant, a fluorine-based resin having a major axis of more than 20 μm when viewed from a direction perpendicular to the film. (2) The surface-treated metal plate according to (2).
(4) The surface-treated metal sheet according to the above (3), wherein the number of fluororesins having a major axis of more than 20 μm is 10 or more per 1 mm ² .
(5) The method according to any one of (2) to (4), wherein the continuous film does not contain fluorine, and the amount of the fluorine-based resin deposited on the metal plate is 20 mg / m ² or more in terms of F. The surface-treated metal plate according to any one of the above.
(6) The surface-treated metal sheet according to any one of (2) to (5), wherein the continuous film further contains a fluorine-free wax as a solid lubricant.
(7) The surface-treated metal sheet according to any one of the above (2) to (6), further comprising a base treatment layer between the continuous film and the metal sheet.
(8) In a method of mixing the components of the continuous film (A) and the additive and applying the mixture to the metal surface in order to form a continuous film containing the additive on the surface of the metal plate, the average film of the continuous film is formed. The manufacture of a surface-treated metal sheet characterized by containing an additive having a major axis longer than three times the thickness and flattening it by utilizing the surface pressure at the time of application, thereby holding the additive in the continuous film. Method.
(9) The method for producing a surface-treated metal sheet according to the above (8), wherein the additive is a solid lubricant (B).
(10) The method for producing a surface-treated metal sheet according to the above (9), wherein the solid lubricant contains a fluorine resin.
(11) The solid lubricant is obtained by irradiating radiation to a fluororesin fine powder synthesized by emulsion polymerization to reduce the molecular weight, and this is mixed with the components of the continuous film and stirred. The method for producing a surface-treated metal sheet according to the above (10), wherein the method is applied to a metal sheet and dried.
(12) The solid lubricant is a fluororesin synthesized by suspension polymerization, which is irradiated with radiation to reduce the molecular weight without heat treatment, and is mixed with a component of a continuous film. The method for producing a surface-treated metal plate according to the above (10), wherein the method is applied to a metal plate with stirring and dried.
(13) A fluorine-based resin whose molecular weight has been reduced by irradiation with radiation is converted into an aqueous dispersion with a surfactant, and this is mixed with the aqueous component of the continuous film, applied to a metal plate with stirring, and dried. The method for producing a surface-treated metal sheet according to the above (11) or (12).
(14) The fluorine-based resin water used in the method for producing a surface-treated metal plate according to the above (13), wherein the fluorine-based resin reduced in molecular weight by irradiation with radiation is converted into an aqueous dispersion with a surfactant. Dispersion.
(15) The surface-treated metal sheet according to (13), which is obtained by forming a water-dispersed fluororesin, which has been reduced in molecular weight by irradiation with a surfactant, into an aqueous dispersion, and mixing this with an aqueous component of a continuous film. A coating composition used in a production method.

  The present invention solves the three manufacturing problems of the prior art using a fluororesin as a solid lubricant, and has a highly slippery material for a transfer plate that can slide a PET bottle. Can supply a lubricating metal plate excellent in press formability and ironing workability, a paper passing member capable of withstanding paper abrasion, a material for a snowy roof, and the like inexpensively and stably. Therefore, it can be said that it has extremely high industrial value.

Hereinafter, the present invention will be described in detail.
First, (1) defines the basic concept of the present invention. The subject of the present invention is a metal material having on one or both sides a non-uniform surface-treated film having additives in a continuous film. Here, a continuous film is defined as a case where a film component is intentionally dispersed and coated on a metal plate, and a portion without a film occupies a considerable proportion, for example, tens of percent, of the entire surface of the metal plate. This is to exclude. Therefore, if the film is formed for the purpose of continuous coating, but the film thickness changes depending on the location or there is a portion where the metal is partially exposed, it is called a continuous film. The reason why the average film thickness is set to 20 μm or less is to target so-called post-treated metal plates and painted metal plates. The average film thickness is determined by a method described later. The continuous film may be a single layer or a multilayer film of two or more layers. The main component may be an organic substance or an inorganic substance.

  Examples of usable additives include solid lubricants, rust inhibitors, coloring materials, metal powders, fibers, foil pieces, and magnetic substances. A feature of the present invention is that, among the additives, the major axis of the solid lubricant is at least three times the average film thickness of the continuous film, that is, the additive contains a flat solid lubricant. Those having a major axis of less than three times the average film thickness are not referred to herein as flat lubricants.

  In the prior art, the long diameter of the solid lubricant has been considered to be easy to fall off from the continuous film unless it is up to about twice the film thickness. In contrast, in the present invention, the long diameter of the solid lubricant is three times or more the film thickness. It is characterized in that a solid lubricant is contained in the continuous film. When the major axis is at least three times the average film thickness, a lubricating function by surface contact is exhibited, and high slip and abrasion resistance can be obtained. More preferably, it is 5 times or more. On the other hand, when the major axis of the solid lubricant is less than three times the average film thickness, the point contact becomes dominant, and the level of slipperiness and abrasion resistance decreases.

  There is no particular limitation on the type of organic substance that can be applied as a component of the continuous film. For example, olefin resins, acrylic resins, ionomer resins, epoxy resins, urethane resins, polyester resins, vinyl acetate resins, or Examples thereof include ether sulfone, polyphenyl sulfide, and polyamide imide. These may be used alone, or two or more kinds may be used as a mixture, or a copolymer (eg, ethylene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid Ester copolymers), modified with each other (for example, epoxy-modified urethane resin, acrylic-modified ionomer resin, etc.), or modified with another organic substance (for example, amine-modified epoxy resin) may be used. Further, the resin may be a solvent-based resin or an aqueous resin. Further, the resin itself may be one or two or more of the fluorine-based resins described below.

  Examples of inorganic substances applicable as a component of the continuous film include silicon compounds such as lithium silicate and sodium silicate (water glass), metal oxides such as vanadic acid, titanic acid, zirconic acid, molybdic acid, and chromic acid; Examples thereof include acids such as phosphoric acid and nitric acid.

  Examples of solid lubricants that can be used include, in addition to the fluorine-based resins described in the following section, fluorine-free waxes such as polyolefin wax, paraffin wax, microcrystalline wax, natural wax, stearic acid ester, melamine cyanurate, Examples include molybdenum sulfide, graphite, tungsten disulfide, and boron nitride.

The above (2) uses a fluororesin as an essential component as a flat solid lubricant. Fluorinated resin is one of the most excellent slipperiness as a solid lubricant.
Examples of the fluorine resin used for the solid lubricant include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), and polychloroethylene. Trifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc. can be used. is there. One of these may be used alone, or two or more may be used in combination.

  The above (3) defines the minimum film thickness of the continuous film and the minimum major axis of the flat fluororesin contained as the solid lubricant. The minimum thickness of the continuous film is preferably 0.5 μm or more in order to utilize the size and form of the fluororesin described below. Here, the film thickness was determined by SEM observation of the cross section of the test material at an appropriate magnification. Take at least 10 samples from a sufficiently distant position on the metal plate, measure the film thickness by cross-sectional observation at 3 to 5 locations that are not unique to each sample, and calculate the average value of the obtained total 30 to 50 measurements as the film thickness. did.

  The form of the fluororesin (B) in the continuous film will be described with reference to the SEM photograph of FIG. When the fluororesin (B) contained in the film is classified by size and form, as shown in FIG. 1, those having a major axis of 1 μm or less (B-1), those having a major axis of more than 1 μm and 20 μm or less (B-2) ), Having a major axis of more than 20 μm when viewed from a direction perpendicular to the film (B-3). The SEM photograph in FIG. 1 was taken from a direction perpendicular to the film at an acceleration voltage of 20 kV and a magnification of 500 times. “Viewing from the direction perpendicular to the film” means that the sample was not intentionally tilted when taking the SEM photograph. Although many whitish particles are visible, it can be confirmed that this is a fluororesin by elemental analysis (area analysis) using EDX. The acceleration voltage was set high at 20 kV to clarify the fluorocarbon resin. When the acceleration voltage was lowered, the overall picture became darker. In the present invention, the content of (B-1) is desirably as small as possible, and is preferably 10% by weight or less based on the entire fluororesin (B). The type (B-2) is included as a main component. The type (B-3) is the greatest feature in the configuration of the present invention. The above (3) specifies that the type (B-3) is contained in the continuous film. Even if only (B-2) having a smaller major axis than (B-3) is contained, as long as the above (1) is satisfied, a higher degree of slipping property can be exhibited as compared with the conventional method, but a higher level of slipping property can be achieved. When moldability, abrasion resistance and the like are required, it is an essential requirement to include the type (B-3) having a major axis of more than 20 μm.

The above (4) defines the minimum content of the fluorine-based resin of the type (B-3) in the above (3). Even if the content of (B-3) is less than this, a more excellent sliding property than before can be exhibited. However, in order to improve the lubricating property with a non-slip material such as a PET bottle, a film having a thickness of 1 mm is required. It is necessary to contain 10 or more per ² If less than 10, the improvement effect is small. When the major axis is 20 μm or less, the improvement effect is still small.

The number of (B-3) types was determined by taking SEM photographs at an accelerating voltage of 20 kV and a magnification of 500 times from a direction perpendicular to the film, that is, without intentionally tilting the sample, and within the field of view of the fluororesin. (B) The operation of measuring the major axis and counting the ones that meet the conditions was performed for at least 40 visual fields per sample, and the total was converted to 1 mm ² . For the selection of 40 fields of view, a method of cutting out 10-20 small pieces from a sufficiently distant position in the sample and taking SEM photographs of 2-4 fields selected at random for each small piece, so that there is as little bias as possible. I went to.

  The size and form of the fluorine-based resin (B-3) are important, and it is determined whether the fluorine-based resin is exposed on the surface of the lubricating film or whether it is buried up to the position in contact with the base metal. Not necessarily important. As shown in FIG. 2, some of the (B-3) types are considered to have their surfaces covered by the components of the continuous film when crushed by the surface pressure of the roll, but are completely exposed. This is because it can function as a lubricating point for cleaving roller lubrication as long as the lubricating film has a slightly raised shape from the lubricating film. Conversely, some particles are not buried up to the position where they come into contact with the base metal. However, since these particles also have swelling from the lubricating film, they can function as lubrication points.

The above (5) specifies the components constituting the continuous film and the adhesion amount of the fluororesin. The fact that fluorine is not contained as a component of the continuous film is a requirement in the case where it is necessary to exhibit high slip properties at low cost. That is, if a fluorocarbon resin is used for both the continuous film (A) and the solid lubricant (B), high slip and abrasion resistance can be certainly obtained, but the total cost is high because the fluorocarbon resin is expensive. Get higher. On the other hand, the continuous film (A) does not contain fluorine, has low slipperiness, but is inexpensive, and uses the flat fluororesin of the present invention as the solid lubricant (B). , Greatly improving the slipperiness. However, if the amount of the fluorine-based resin adhered is less than 20 mg / m ^{2 in} terms of F, the slipperiness improving effect is insufficient.

The amount of F attached to the test material was measured by X-ray fluorescence after preparing a calibration curve by a gravimetric method. The procedure is as follows. Prepare approximately 10 sheets of 0.8 mm thick galvanized steel sheet cut into 140 mm × 140 mm, and accurately measure the weight of each sheet with an analytical balance to the order of 0.1 mg. Next, a composition is prepared by mixing the component (A) of the continuous film containing no fluorine and the fluorine-based resin (B). This is uniformly applied to one surface of the galvanized steel plate whose weight has been measured. At this time, by changing the ratio of the fluororesin (B) in the composition, the water dilution ratio, the coating conditions, and the like, the total adhesion amount is in the range of about 1 to ² g / m ² , and the level is 10 to 15 levels (hereinafter, referred to as Create each sample). The weight of the galvanized steel sheet after coating and drying is measured again with an analytical balance, and the total weight of the composition (g / m ² ) is calculated for each sample from the weight increase.

Here, in consideration of the ratio of the fluororesin (B) in the composition and the molecular structure of the fluororesin (B) (for example, CF ₂ -CF _{2 in the} case of PTFE), the weight ratio of F to the total attached amount is considered. (Wt%) and multiplying this value by the total adhesion amount (g / m ² ) of each sample determined above, the adhesion amount of F (mg / m ² ) in each sample was calculated. You.

  Next, each sample is cut into 35 mm × 35 mm to obtain 16 small piece samples. This is analyzed with a fluorescent X-ray analyzer (RIX2000, manufactured by Rigaku Corporation). The target of the X-ray tube was Rh, the application conditions were 50 kV, 50 mA, and the measurement area was 20 mmφ. The element to be measured is F, and its X-ray intensity (kcps) is measured. The average value of 16 small piece samples was used as the F intensity (kcps) of each sample.

Finally, the X-ray fluorescence was obtained by linearly approximating the F intensity (kcps) of each sample obtained above and the F adhesion amount (mg / m ² ) of each sample calculated earlier. Is the calibration curve of F in. Thereafter, using this calibration curve, the amount of F attached (mg / m ² ) was determined by converting from the fluorescent X-ray intensity (kcps) of F of the unknown sample.

If the total amount exceeds ² g / m2, the fluorine X-ray dose reaching the surface decreases as the amount increases, so a calibration curve of fluorine is required for each total amount. become. For example, when the total amount of coating is 4 g / m ² , to accurately measure the amount of F contained, unify the total amount of coating to 4 g / m ² and create a sample in which the fluorine addition rate is changed, In the same manner as described above, a “fluorine calibration curve for a total attached amount of 4 g / m ² ” must be prepared from the gravimetric method and the fluorescent X-ray intensity.

  In the above (6), in addition to the above-mentioned fluorine-based resin as a solid lubricant, a wax containing no fluorine is used in combination, thereby exhibiting higher lubricity. Here, waxes that can be used as waxes containing no fluorine include polyolefin wax, paraffin wax, microcrystalline wax, natural wax, stearic acid ester, melamine cyanurate, molybdenum disulfide, graphite, tungsten disulfide, boron nitride, and the like. Is raised. The wax containing no fluorine may or may not be flat as long as the fluororesin is a flat solid lubricant satisfying the above (1).

  The above (7) uses an undercoating layer between the metal plate and the continuous film in order to improve the adhesion between the continuous film and the metal plate. As the base treatment layer, a chemical conversion treatment layer and / or a primer layer is preferably used. Examples of chemical conversion treatment layers include zinc phosphate treatment layers, chromate treatment layers, non-chromate treatment layers, anodization treatment layers, and the like, which can be formed by immersion treatment, electrolytic treatment, coating / drying, and the like. As the layer, various resins including an epoxy resin, a coupling agent such as a silane coupling agent, and the like can be applied.

  The above (8) defines the basic concept regarding the manufacturing method of the product of the present invention. An object of the present invention is a metal material having a non-uniform surface treatment film having a flat additive and having a long diameter of three times or more the average film thickness of the continuous film in one or both surfaces in the continuous film. In manufacturing this, the components of the continuous film and the additives are mixed and applied to a metal plate. The feature of the present invention is that the additive having a longer diameter of at least three times the average film thickness of the continuous film. Is to be flattened using the surface pressure at the time of application, and to be kept in a continuous film.

  That is, in the prior art, it has been considered that an additive having a particle diameter exceeding twice the film thickness cannot be used because of the risk of falling off from the film. Therefore, in order to use such an additive, it has been customary to flatten it by pulverizing it in advance with a ball mill or the like, then mix it with a continuous film component and apply it. Examples of this are found in, for example, JP-A-01-170666 and JP-A-63-303001. On the other hand, in the present invention, even if the additive exceeds three times the film thickness, the protruding portion is crushed by the surface pressure at the time of coating so that the additive does not fall off the film. Therefore, the most suitable coating method is a roll coating method that can be directly contacted. However, if a sufficient surface pressure can be applied, a non-contact method, for example, an air wiping method may be used.

  The above (9) uses a solid lubricant as an essential component as an additive. In the prior art, the major axis of the solid lubricant has been limited to about twice the film thickness, whereas in the present invention, the solid lubricant having the major axis of three times or more the film thickness is applied to the surface pressure at the time of application. It is characterized in that it is flattened with the aid of and is contained in a continuous film. With regard to solid lubricants, there is no conventional technology of flattening by previously grinding with a ball mill or the like as described above, and the size of usable solid lubricants is necessarily limited by the thickness of the continuous film. It has been. The present invention is a breakthrough of this.

  The method (10) uses a fluororesin as an essential component as a solid lubricant, and is the production method of the method (2). Fluorine-based resins are one of the most slippery solid lubricants. However, compared to polyethylene, paraffin and the like, it is difficult to obtain a resin having a uniform particle size. That is, it is usually submicron fine particles or mixed powder of several tens to several hundreds of microns. Therefore, in the prior art, when adding to a continuous film having a film thickness of 20 μm or less, the fine particle type was necessarily selected. The present technology breaks through this point. In addition, a significant feature is that the fluororesin, which is considered to be relatively "hard and brittle", can be flattened by the surface pressure of the application roll.

  The above (11) is one of the metal plate manufacturing methods of the present invention. A commercially available aqueous dispersion of a fluororesin is obtained by adding a surfactant to a latex of a fluororesin obtained by emulsion polymerization, and then concentrating and stabilizing the latex. However, when this is mixed with an aqueous resin as it is and applied to a metal plate, or when a so-called fine powder obtained by drying and coagulating it is added to a solvent-based resin as it is and applied to a metal plate, it is coated on the coating roll. The wrapping of the fluororesin easily occurs. Further, the formed lubricating film does not include a film having a major axis of more than 20 μm (B-3) when viewed from a direction perpendicular to the film described above, and cannot exhibit a high degree of slipperiness. On the other hand, when the latex of the fluororesin obtained by emulsion polymerization is coagulated and dried to obtain a fine powder, pulverized if necessary, and then used to reduce the molecular weight by irradiation, a coating roll is used. There is no problem of the above winding, and the type of (B-2) or (B-3) is included in the lubricating film.

  Here, fine powder obtained by reducing the molecular weight with radiation is used. In this case, the particle diameter means a secondary particle diameter, and it is sufficient that this exceeds 20 μm. The primary particle size is 1 μm or less. The reason that the low-molecular-weight fine powder after the irradiation can be flattened by the surface pressure of the application roll is considered to be because the primary particles are appropriately bonded to each other and are in a state capable of plastic deformation.

  As the fine powder, those having a secondary particle diameter of usually 300 to 600 μm (primary particle diameter is submicron) can be used. The molecular weight is reduced by irradiating this with radiation. The radiation used here refers to an electron beam, γ-ray, X-ray, or the like.

  Since it is difficult to accurately measure the molecular weight of the fluorine-based resin, the degree of decrease in the melting point as compared with fine powder as-manufactured can be used as a measure of the molecular weight reduction. When the degree of decrease in the melting point is 0.8 ° C. or more, there is an effect of suppressing winding around the application roll. The melting point referred to here is the value obtained when the calcined product that has been melted and then cooled is melted again, and melted at a heating rate of 10 ° C./min using differential thermal analysis (DSC), cooled, When re-melted.

  The above (12) is also one of the metal plate manufacturing methods of the present invention. The fluorinated resin synthesized by suspension polymerization is not heat-treated such as granulation (firing) for molding powder, but is ground if necessary, and then irradiated with radiation to reduce the molecular weight. In the first place, a fluororesin synthesized by suspension polymerization has little problem of winding around an application roll, and the main purpose of irradiating radiation here is to make plastic deformation easier. If it is easy to plastically deform, it can be flattened by the surface pressure at the time of application, and as a result, the film contains (B-2) and (B-3) types of fluororesins. If the degree of decrease in the melting point is 0.8 ° C. or more as compared with that before irradiation, the effect can be seen.

  In addition, since the particle diameter is large, it is necessary to continuously stir the mixture when mixing with the component of the continuous film (A) and applying the mixture to the metal plate. Insufficient stirring causes sedimentation. In order to suppress sedimentation, it is preferable to stir at least 50 rpm or more. If it is equal to or more than 100 rpm, sediment hardly occurs.

  The above (13) is a production method when the present invention is applied to a continuous film (A) composed of an aqueous component. The continuous film composed of an aqueous component is an aqueous resin, that is, a water-soluble resin or a water-dispersible resin, or an aqueous inorganic compound such as water glass or an aqueous metal oxide. The fluororesin whose molecular weight has been reduced by irradiation with radiation used in the above (11) and (12) is further converted into an aqueous dispersion with a surfactant. This is mixed with the aqueous component of the continuous film (A), applied to a metal plate and dried. In order to suppress the formation of sedimentation, it is also preferable to stir at least 50 rpm or more.

  In the above (14), a fluororesin whose molecular weight has been reduced by irradiation with radiation is further converted into an aqueous dispersion with a surfactant, and is used in the above (13). In order to enhance the dispersion stability of the aqueous dispersion itself, the solid content concentration is preferably about 30% by weight or more. On the other hand, from the viewpoint of ease of handling, the solid content concentration is desirably set to about 60% by weight or less. When used after long-term storage, it is preferable to store it as an aqueous dispersion, stir well before use, and then mix it with the aqueous component of the continuous film (A).

  The above (15) is an aqueous coating composition obtained by mixing an aqueous dispersion of a fluororesin with the aqueous component of the continuous film (A), and is used in the production method of the above (13).

Next, other raw materials and materials that can be used in the present invention will be described.
Various additives can be added to the continuous film as long as the slip property is not impaired. For example, various inhibitors can be added as organic compounds and silica, titania, zirconia, etc. can be added as inorganic compounds to improve corrosion resistance. If coloring is required, various organic and inorganic pigments can be added. A leveling agent or an antifoaming agent may be added to improve the applicability.

  The composition used in the present invention can be obtained only by mixing the above-mentioned components (A) and (B) and various additives at a predetermined ratio. The order of mixing is not particularly limited, but in order to stably obtain the composition on a large scale, a predetermined amount of the solid lubricant (B) is measured in advance and the solid lubricant (B) is measured with the components of the continuous film (A). It is preferable to dilute the mixture by a factor of 2 to 3 and stir well, and to mix the mixture with a mixture of a composition obtained by mixing the components, additives, solvents and the like of the continuous film (A) with slow stirring. The resulting composition is preferably agitated constantly.

  The coating may be carried out by a usual method, for example, a method using a roll coater, spray + roll drawing, dipping + roll drawing, bar coater, roller coating, brushing, etc. Need to be added. Therefore, in the case of performing air knife drawing in which the amount of adhesion is controlled in a non-contact manner, it is necessary to check whether a sufficient surface pressure is applied to flatten the additive. Drying depends on the type of the continuous film (A), but it is generally sufficient that the solvent or moisture is sufficiently removed, that is, the drying plate temperature is about 100 ° C. or more. The drying method can also be selected from ordinary methods such as a direct fire oven, an induction heating oven, an electric resistance oven, and a hot air drying oven.

  Examples of the metal plate to which the present invention can be applied include a steel plate, aluminum and its alloy plate, magnesium and its alloy plate, titanium and its alloy plate, copper and its alloy plate, nickel and its alloy plate. Examples of the steel sheet include a hot-rolled steel sheet, a cold-rolled steel sheet, a plated steel sheet, and a stainless steel sheet.

  Among them, examples of the plated steel sheet include various plated steel sheets prepared by a method such as electroplating, hot dipping, vapor deposition plating, electroless plating, and molten salt electroplating. For example, there are steel sheets plated with pure metals such as galvanized steel sheets, aluminum-plated steel sheets, chrome-plated steel sheets, nickel-plated steel sheets, and copper-plated steel sheets. Further, for example, alloy-plated steel sheets of one or more metals such as zinc and nickel, iron, aluminum, chromium, titanium, magnesium, manganese, cobalt, tin, lead, etc. And / or a plated steel sheet intentionally containing an inorganic substance such as silica, alumina, titania, zirconia, and / or an organic compound, or containing an impurity as an impurity, and further, a plated steel sheet having two or more of the above-mentioned two or more types of plating. and so on.

Next, the present invention will be described by way of non-limiting examples.
(1) Tested metal plate The following metal plate was used.
GI (hot-dip galvanized steel sheet): A steel sheet with a thickness of 0.8 mm and a hot-dip galvanized coating of 60 g / m ² per side.
EG (Electro-galvanized steel sheet): A steel sheet with a thickness of 0.8 mm and galvanized at 20 g / m ² per side.
SUS (stainless steel plate): SUS304 with 1.2mm thickness
(2) Continuous films Six types of continuous films shown in Table 1 were used.
(3) Solid lubricant The following two types shown in Table 2 were used.
PTFE polytetrafluoroethylene
Application and drying of PE polyethylene wax (4) The components of the continuous film and the solid lubricant were mixed, applied to a metal plate with a roll coater, and dried in a direct fire type drying furnace.
(5) Measurement of Maximum Length of Solid Lubricant The surface and cross section of the coating were observed with a scanning electron microscope, and a flat solid lubricant was selected and its maximum length was measured.
(6) Measurement of the slide-out angle The test plate is cut into a large plate of about 100 mm square and a small piece of about 20 mm square, and the small piece is placed on the large plate, and then the slide-out angle of the small plate when the large plate is tilted I asked. The measurement was performed 10 times, and eight data except for the maximum and minimum were averaged.

  Table 2 shows the results. Regardless of the combination of the continuous film and the solid lubricant, the case where the solid lubricant contains a flat lubricant having a major axis of at least three times the film thickness is superior to the case where the solid lubricant is fine particles, in terms of slipperiness. You can see that it is.

(1) Tested metal plate The following metal plate was used.
GI (hot-dip galvanized steel sheet): A steel sheet with a thickness of 0.8 mm and a hot-dip galvanized coating of 60 g / m ² per side.
EG (Electro-galvanized steel sheet): A steel sheet with a thickness of 0.8 mm and galvanized at 20 g / m ² per side.
AL (Hot-dip aluminized steel sheet): A steel sheet with a thickness of 1.6 mm and a hot-dip aluminum coating of 50 g / m ² per side.
The plating contains 8 wt% of silicon as an alloy element.
HR (Hot rolled steel sheet): Hot rolled steel sheet (440MPa) with a pickling thickness of 2.3mm
SUS (stainless steel plate): SUS304 with 1.2mm thickness
Ti (titanium plate): Pure titanium plate with a thickness of 1.0 mm Al (aluminum plate): JIS3004 with a thickness of 1.0 mm
(2) Base treatment The following various base treatments were performed according to the type of the metal plate.
1) Chromate treatment: A mixture of partially reduced chromic acid and colloidal silica was applied and dried.
2) Zinc phosphate treatment: The treatment was performed using a commercially available zinc phosphate treatment solution.
3) Non-chromate treatment: A mixture of tannic acid and a silane coupling agent was applied and dried.
4) Primer treatment: An epoxy primer was applied and dried.
5) Anodizing treatment: Anodizing treatment with phosphoric acid was performed for an aluminum plate, and anodizing treatment with hydrogen peroxide was performed for a titanium plate.
(3) Aqueous resin Any of the following was used as the aqueous resin.
1) Urethane resin: 1: 1 mixture of ether / ester urethane resin and ester urethane resin
2) Ionomer resin: Na neutralized ionomer resin
3) Acrylic resin: copolymer of methacrylic acid, butyl acrylate, hydroxyethyl acrylate, and styrene
4) Olefin resin: ethylene-methacrylic acid copolymer
5) Polyester resin: linear saturated polyester resin (4) Aqueous dispersion of fluorine resin As the fluorine resin, PTFE, PFA, and FEP latex obtained by emulsion polymerization are coagulated and dried, and then irradiated with radiation. (Electron beam used here) The molecular weight was reduced so that the degree of reduction of the melting point became 0.8 ° C. or more, and this was mainly used as a water dispersion with a surfactant or the like. In some examples (Nos. 23, 25, and 30), the fluoropolymer obtained by suspension polymerization was irradiated with radiation (using gamma rays here) without heat treatment to lower the melting point. After reducing the molecular weight so that the temperature became 0.8 ° C. or higher, a water dispersion obtained by using a surfactant was used. For comparison, a commercially available aqueous dispersion obtained by adding a surfactant to a latex of PTFE obtained by emulsion polymerization and then concentrating and stabilizing the same (No. 34) was also used.
(5) Other Lubricants For some examples, each of polyethylene wax (PE), microcrystalline wax (MC), and paraffin wax (PAR) was added at 16% by weight of resin solids.
(6) Other additives In some cases, colloidal silica was added at 20% by weight of the resin solids. In all cases, a slight amount of a leveling agent was added to prevent repelling of the resin.
(7) Coating and drying The composition obtained by mixing the above (3) to (6) is applied to a metal band with a roll coater while stirring, and the plate temperature is set to 100 to 100 in a direct-fired drying furnace. Dried at 150 ° C. In addition, it was confirmed whether or not winding of the resin occurred on the roll coater.
(8) Evaluation test (8-1) Slipperiness Hold the test plate at a fixed angle to the horizontal, and put a commercially available PET bottle (with 500CC) with a film wrapped around it sideways on it. When it was allowed to stand, it was examined how many angles it would slide when held.
：: Sliding at less than 7 °.
：: Slippage occurred at 7 ° or more and less than 9 °.
Δ: Sliding occurred at 9 ° or more and less than 11 °.
X: Slip did not occur unless it was 11 ° or more.
(8-2) Abrasion resistance Place the above PET bottle sideways on the test agent, slide at a speed of 60 reciprocations per minute, and damage the surface of the test material after 100,000 reciprocations. I checked the condition.
A: No noticeable scratch is seen on the sliding portion.
：: Scratches are observed only at both ends of the sliding portion.
Δ: A shallow scratch is also observed at the center of the sliding portion.
X: Many deep scratches are also observed at the center of the sliding portion.
(8-3) Slip property after abrasion After completion of the abrasion resistance test of (8-2), the slip property test of (8-1) was performed.
：: Sliding at less than 7 °.
：: Slippage occurred at 7 ° or more and less than 9 °.
Δ: Sliding occurred at 9 ° or more and less than 11 °.
X: Slip did not occur unless it was 11 ° or more.
(8-4) Coating Adhesion A cross cut was made on the lubricating coating surface of the test plate with a cutter knife in the shape of a 1 mm gobang, and the tape was peeled off.
：: No peeling of the film was observed. Δ: Film peeling was less than 5%. X: Film peeling was more than 5%.

  Table 3 shows the results. All of the products of the present invention do not have a resin wound around a roll at the time of application, and the metal plate after application has excellent sliding properties, abrasion resistance, sliding properties after abrasion, and film adhesion. It is applicable as a material for a top tray.

  A cylindrical forming test was performed on 18 (Example) and 35 (Comparative Example) plated steel sheets shown in Table 3. When the limiting aperture ratio was determined, 18 was 2.7 and 35 was 2.2, and 1 was excellent. Therefore, the product of the present invention exhibits excellent slidability applicable to molding applications.

  The hot-rolled steel sheets 30 (Example) and 39 (Comparative Example) shown in Table 3 were iron-formed. In each case, when the plate thickness reduction rate was 15%, 1000 samples were tested in separate molds, and the damages of the respective molds were compared. As a result, the damage using 30 was overwhelmingly slight. Therefore, the present invention is also effective as a measure against mold damage.

(1) Aqueous Dispersion of Fluorinated Resin As shown in Table 4, aqueous dispersions of a fluorinated resin having different resin types, polymerization methods, post-polymerization treatment methods, heat treatments, and low molecular weight reduction methods were prepared. For dispersion in water, a fluorocarbon surfactant having a polar group was used. With respect to those having a reduced molecular weight, the degree of lowering of the melting point with respect to the high molecular weight substance was determined by the differential thermal analysis (DSC) described above. Further, the particle size of the aqueous dispersion was measured by a light scattering method.
Note that H and K in Table 4 are commercially available aqueous dispersions that were concentrated and stabilized as they were in emulsion polymerization, and are comparative examples of the present invention. C and G are compounds obtained by stopping the reaction in the course of synthesizing the fluorine-based resin by emulsion polymerization to reduce the molecular weight, and these are also comparative examples. Furthermore, B does not have a low molecular weight and D has undergone heat treatment, so these are also comparative examples.
(2) Aqueous resin urethane resin: 1: 1 mixture of ether / ester urethane resin and ester urethane resin (3) Metal sheet GI (hot-dip galvanized steel sheet): 0.8 mm thick mild steel sheet A steel sheet coated with 60 g / m ² of molten zinc per side.
(4) Base treatment Non-chromate treatment: A mixture of tannic acid and a silane coupling agent (5) Coating and drying The above (4) is coated and dried so that the total adhesion amount is 100 to 150 mg / m ^2, and then dried on a metal plate ( In 3), (1) and (2) were mixed at a solid content ratio of 20:80, and the mixture was applied with stirring, and the mixture was heated at a plate temperature of 100 to 150 ° C. in a direct fire type drying furnace. Dried. The film thickness after drying was adjusted to 3 to 4 μm.
(6) Evaluation Test of Aqueous Dispersion and Metal Plate (6-1) Dispersion Stability of Aqueous Resin + Aqueous Dispersion The mixture of (1) and (2) used in the above (5) was subjected to a total solid content concentration of 25 wt%. The mixture was placed in a 500 cc beaker, a metal stirring blade was set near the water surface, and the mixture was stirred at 50 rpm or 100 rpm. This was stopped for 18 hours, and the amount of sediment accumulated on the bottom of the beaker was measured.
：: No precipitation generated
：: Precipitation amount is less than 10% of solid content of fluororesin
△: Precipitation amount is more than 10% and less than 30% of fluorine resin solids
X: Precipitation amount exceeds 30% of the solid content of the fluororesin (6-2) Wrapping of the aqueous resin + aqueous dispersion around the application roll 1 L of the same mixture as in the above (6-1) was prepared, and placed in a laboratory roll coater. A roll rotation test simulating the application was performed. The roll type is a natural coater of 2 rolls (pickup roll is a metal roll, applicator roll is a rubber roll), and has a roll width of 300 mm and a roll diameter of 120 mm. When the pan is filled with 1 L of the above mixture and the applicator roll is rotated at 15 mpm, the pick-up roll is rotated at 10 mpm, and the linear pressure is 200 g / mm, the resin is wound around the roll continuously for 2 hours. Was observed. The roll coater was rotated while keeping the GI plate in constant contact with the applicator roll in order to make the conditions closer to the actual operation.
：: No resin winding on the roll
：: Resin winding is slightly observed on a part of the roll
△: Remarkable resin winding occurs within 1 hour
×: Remarkable resin winding occurred within 15 minutes (6-3) Number of (B-3) in lubricating film As described above, the form of fluororesin (B) in the lubricating film was determined by SEM. It was confirmed by observation, and it was confirmed whether or not 10 or more fluororesins of the type (B-3) having a major axis longer than 20 μm were contained per 1 mm ^{2 when} viewed from the direction perpendicular to the film.
：: 10 or more (B-3) type fluororesins are contained per 1 mm ² .
×: 10 or more (B-3) type fluororesins are not contained per 1 mm ² . (6-4) Slip property of metal plate The test plate is held at a fixed angle to the horizontal, and a commercially available PET bottle (500 cc) with a film wrapped around the whole body is placed on it horizontally. Then, it was examined how many angles it would slide when held.
：: Sliding at less than 7 °.
：: Slippage occurred at 7 ° or more and less than 9 °.
Δ: Sliding occurred at 9 ° or more and less than 11 °.
X: Slip did not occur unless it was 11 ° or more.

  Table 4 shows the results. Both of the aqueous dispersions of the present invention hardly cause the resin to be wound around the application roll, have little precipitation when stirred at a rotation speed of 100 rpm, and exhibit excellent slip properties by being applied to a metal plate. Can be. That is, the present invention can be manufactured stably and has a stable quality.

(1) Tested metal sheet A hot-rolled steel sheet (440 MPa class) with a thickness of 2.3 mm was used.
(2) Types of continuous film and solid lubricant A hot-rolled steel sheet treated with Bonde Bonda Lube (Nippon Parkerizing), which is a lubricant of Example 3 and Comparative Example 3 shown in Table 5, and a commercially available lubricant was used. Here, in Example-2 and Comparative Example-2, since a solvent-based resin was used as the continuous film, an aqueous dispersion of E in Table 4 and a commercially available polyethylene wax were used as solid lubricants, respectively. However, it was added as powder.
(3) Application and drying The mixture of Table 5 was applied to a pickled hot-rolled steel sheet with a roll coater, and dried in a hot-air oven. (4) Continuous sliding property of metal plate A 20 mm x 360 mm test piece was cut out from a sample that had been applied and dried, and a continuous pulling test was performed. The die was SKD11, shoulder R2.5, width 5 mm, surface pressure was 40 kgf / mm ² , the length was 260 mm at a pulling speed of 3.3 mm / sec, and the dynamic friction coefficient was determined from the average value of the pulling load. The pull-out test was repeated 30 to 50 times to check whether the dynamic friction coefficient increases.

  The results are shown in FIG. In the comparative example, when the number of slides is small, the dynamic friction coefficient is lower than that of the commercially available bond processing, but when the number of slides is increased, the dynamic friction coefficient tends to increase. On the other hand, the product of the present invention has a lower coefficient of kinetic friction than the comparative example, and is stable at the same value even when the number of times of sliding is increased, and is excellent in continuous sliding property at a high surface pressure. ing.

(1) Tested metal sheet A hot-rolled steel sheet (440 MPa class) with a thickness of 2.3 mm was used.
(2) Type of continuous film and solid lubricant A hot-rolled steel sheet treated with Bonding Bonda Lube (Nippon Parkerizing), which is a level 3 in Example, a level 1 in Comparative Example, and a commercially available lubricant shown in Table 6 was used. In Examples 4 and 5, a zinc phosphate film was deposited by electrolytic treatment as a base treatment for a hot-rolled steel sheet. The processing time is 1-2 seconds.
(3) Application and drying The mixture in Table 6 was applied to a pickled hot-rolled steel sheet by a roll coater and dried in a hot-air oven. (4) Multi-stage moldability of metal plate The coated and dried sample was blanked in a circular shape, and then formed by multi-stage molding so as to have the shape of an automobile transmission part shown in FIG. Oiling was not performed, and the tooth mold portion was subjected to ironing for a total of four times so that the thickness reduction rate was 30%. The molding was performed for 300 pieces, and ranked and evaluated as follows. Bonded products are used as a standard because they are currently widely used for multi-stage molding.
：: Molding was possible without cracking, and dimensional accuracy and product tact time were equivalent to those of the bonded products.
○: Molded without cracks, and dimensional accuracy was equivalent to that of the bonded product, but the knockout was slightly delayed and the tact time was longer.
Δ: Molding was possible without cracking, but dimensional accuracy was inferior to that of the bonded product.
×: Cracks occurred during molding.

  Table 6 shows the results. The product of the present invention exhibited almost the same multi-stage moldability as that of the bond processing. Particularly, the one subjected to the electrolytic bonding as the base treatment was equivalent to the bond processing including the product tact time. Therefore, the product of the present invention can also be applied to the case where mission parts and the like are manufactured by multi-stage pressing.

(1) Metal sheet EG (Electro-galvanized steel sheet): Steel sheet obtained by depositing 20 g / m ² per side of zinc on a 0.8 mm thick mild steel sheet (2) Type of continuous coating and solid lubricant Example 3 shown in Table 7 and Comparative Example 1 were used.
(3) Coating and drying The mixture shown in Table 7 was applied to EG with a roll coater and dried in a direct fire furnace.
(4) Paper passing suitability test The suitability of the test material as a paper passing member of a copying machine was examined by the following method.
(4-1) Paper slippage
A 30 mm × 30 mm KB sheet was placed on a metal plate and slid at a load of 250 g at a sliding speed of 150 mm / min to determine the dynamic friction coefficient.
(4-2) Paper abrasion resistance KB paper is wrapped around a φ50 mm cylinder, and pressed against a metal plate with a load of 500 g, with an amplitude of 30 mm. Was determined as follows.
：: Almost no scratches on the surface of the metal plate, and almost no stain on the paper.
Δ: Shallow abrasion (scratch of continuous film) is observed on the surface of the metal plate, and slight stain on the paper is also observed.
X: Deep scratches (scratch on the metal surface) were observed on the metal plate surface, and the paper was very dirty.
(4-3) Chargeability
The test material is rubbed with KB paper, and the potential difference before and after friction is measured and used as a measure of charging.
: 10V or less △: Over 10V, 100V or less ×: Over 100V

  Table 7 shows the results. INDUSTRIAL APPLICABILITY The present invention is excellent in paper-passing suitability, and can be applied as a paper-passing member of a copying machine or a printer.

(1) Tested metal plate SUS (stainless steel plate): SUS304 with a thickness of 1.2 mm
(2) Kinds of continuous film and solid lubricant The levels of Example 2 and Comparative Example 1 shown in Table 8 were used. Here, three layers of organic films (undercoat, intermediate coat, and overcoat) are formed on the metal plate, and the present invention is applied to the overcoat resin. In addition, since a solvent-based resin was used as the continuous coating of the top coat, E in Table 4 and a commercially available polyethylene wax were added as powders without forming an aqueous dispersion, respectively, as a solid lubricant.
(3) Coating and Drying Both the base treatment, the intermediate coating, and the top coating were performed on a metal plate with a roll coater and dried in a hot air oven, so-called three-coat, three-bake methods.
(4) Snow Sliding Test Ice was allowed to stand on a test plate, and a force was applied in a horizontal direction to determine a dynamic friction coefficient.
(5) Weather resistance test A weather resistance cycle test consisting of ultraviolet irradiation and repeated drying and drying was performed for 4000 hours in a laboratory, and the presence or absence of peeling of the film and a change in snow sliding property were examined.

  Table 8 shows the results. It can be seen that the product of the present invention has excellent snow sliding properties and weather resistance, and can be applied as a roofing material.

4 is a scanning electron micrograph of the surface of the metal plate of the present invention. B-1 Fluorine resin having a major axis of 1 μm or less B-2 Fluorine resin having a major axis of more than 1 μm and 20 μm or less B-3 Fluorine resin having a major axis of greater than 20 μm when viewed from a direction perpendicular to the coating It is a cross section of a metal plate of the present invention. 5 is a graph showing a change in a coefficient of dynamic friction when a continuous sliding test is performed using the metal plate of the present invention and a comparative material. 3 is a photograph of a multi-stage molded automobile mission component.

Claims (15)

  A solid lubricant (B) having a continuous film (A) having an average film thickness of 20 μm or less on one or both surfaces of a metal plate, and having a major axis of three times or more the average film thickness as an additive in the continuous film. A surface-treated metal plate characterized by being contained.   2. The surface-treated metal sheet according to claim 1, wherein the solid lubricant contains a fluorine resin.   3. The continuous coating according to claim 2, wherein the thickness of the continuous coating is 0.5 μm or more, and the solid lubricant contains a fluororesin having a major axis of more than 20 μm when viewed from a direction perpendicular to the coating. Surface treated metal plate. 4. The surface-treated metal sheet according to claim 3, wherein the number of fluororesins having a major axis of more than 20 μm is 10 or more per 1 mm ² . The surface according to any one of claims 2 to 4, wherein the continuous film does not contain fluorine, and the amount of the fluorine resin adhered on the metal plate is 20 mg / m ² or more in terms of F. Processing metal plate.   The surface-treated metal sheet according to any one of claims 2 to 5, further comprising a wax containing no fluorine as a solid lubricant in the continuous film.   The surface-treated metal plate according to any one of claims 2 to 6, further comprising a base treatment layer between the continuous film and the metal plate.   In order to form a continuous film containing an additive on the surface of a metal plate, the components of the continuous film (A) and the additive are mixed and applied to a metal surface. A method for producing a surface-treated metal sheet, characterized in that an additive having a longer diameter than that of an additive is contained, and the additive is flattened by utilizing the surface pressure at the time of application, so as to be held in the continuous film.   The method for producing a surface-treated metal sheet according to claim 8, wherein the additive is a solid lubricant (B).   The method for producing a surface-treated metal sheet according to claim 9, wherein the solid lubricant contains a fluororesin.   The solid lubricant is a fluororesin fine powder synthesized by emulsion polymerization, which is irradiated with radiation to reduce the molecular weight.This is mixed with the components of the continuous film, and stirred to form a metal plate. The method for producing a surface-treated metal sheet according to claim 10, wherein the method is applied and dried.   Solid lubricant, without heat treatment of the fluororesin synthesized by suspension polymerization, is irradiated with radiation to reduce the molecular weight, and mixed with the components of the continuous film, while stirring The method for producing a surface-treated metal plate according to claim 10, wherein the method is applied to a metal plate and dried.   Irradiating radiation to reduce the molecular weight of the fluorine-based resin to form an aqueous dispersion with a surfactant, mix this with the aqueous component of the continuous film, apply the mixture to a metal plate with stirring, and dry. Item 13. The method for producing a surface-treated metal sheet according to item 11 or 12.   The fluororesin aqueous dispersion used in the method for producing a surface-treated metal plate according to claim 13, wherein the fluororesin whose molecular weight has been reduced by irradiation with radiation is made into an aqueous dispersion with a surfactant.   The fluorine-based resin reduced in molecular weight by irradiation with radiation is used as a water dispersion with a surfactant, and is obtained by mixing this with an aqueous component of a continuous film. Paint composition.