JP4157491B2 - Non-delaminating lubricated plated steel plate with excellent workability - Google Patents

Description

  The present invention relates to a non-delaminating type lubricated plated steel sheet having excellent workability for use in parts such as home appliances, building materials and automobiles that are used without removing the lubricating film after press working.

  Conventional parts are processes in which press oil is applied, and after press forming, the oil is removed. However, there is a need for surface-treated steel sheets that have lubrication performance that can eliminate press oil and surface characteristics (appearance, corrosion resistance, paint adhesion, etc.) that have excellent surface properties after press, as the use of degreasing solvents is restricted and costs are reduced. It is getting stronger. Especially in the case of parts that are strongly processed, the organic film and plating film are likely to be damaged, and corrosion resistance deterioration after processing due to this film damage is likely to occur. Therefore, there is a need for a surface-treated steel sheet that has both good lubrication performance and post-processing corrosion resistance. Is strong.

As one means for solving such a problem, a chromate film having a Cr adhesion amount of 200 mg / m ² or less is formed on the surface of a zinc-based or aluminum-based alloy-plated steel sheet, and a resin having 0.3 to 3.0 g / m ² is formed thereon. Lubricating resin excellent in moldability having a film and having a resin film of 100 parts by mass of a hydroxyl group and / or carboxyl group-containing resin, 10 to 80 parts by mass of silica, and 20 parts by mass or less of a polyolefin wax having an average particle diameter of 1 to 7 μm A treated steel sheet has been proposed (see, for example, Patent Document 1). This lubricated steel sheet is disclosed as being applicable to a wide variety of resin types.

  However, it is not satisfactory and insufficient in terms of actual high-speed continuous crank press workability and reduced film deterioration after processing, and is stable only by optimizing the film composed of resin, silica and lubricant. An operational lubricated steel sheet is obtained. In particular, the appearance and performance after processing are important for non-delaminating type lubricated steel sheets, and the uniformity and extension of the thickness of the lubricating film, compression, and sliding wear must be taken into consideration.

  In order to solve this problem, press oil with excellent lubricity is obtained by applying chemical conversion treatment to the surface of the plated steel sheet and coating it with an optimized coating of ether / ester urethane resin, epoxy resin, polyolefin wax, and silica. An omissible non-delaminating lubricated plated steel sheet has been proposed (see, for example, Patent Document 2).

  However, in each of the above-described lubricated plated steel sheets, the corrosion resistance of the processed part after severe press working is not sufficiently ensured.

  In order to improve the corrosion resistance of such a lubricated plated steel sheet, the present inventors have proposed a non-delaminating lubricated plated steel sheet capable of omitting press oil and having excellent lubricity and corrosion resistance of a processed part (for example, Patent Document 3). reference).

  Further, it is disclosed that a good surface appearance can be obtained by adding Ti, B, and Si to a molten Zn—Al—Mg plated steel sheet (see, for example, Patent Document 4).

Japanese Patent Laid-Open No. 3-16726 JP-A-6-173037 Japanese Patent Laid-Open No. 2002-302776 JP 2001-295015 A

  A Zn-Mg-Al ternary alloy has a ternary eutectic point in 3 mass% Mg-4 mass% Al-93 mass% Zn, and when the Al concentration is higher than that, an Al phase is crystallized as the primary crystal. To do.

  If the plating solidification rate at the time of hot dipping is sufficiently secured, the surface smoothness does not matter because the plating solidifies before the Al phase grows greatly, but if the plating solidification rate is low, this Al phase However, there is a problem that unevenness is formed on the plating surface and the surface smoothness deteriorates.

  For this reason, when a lubrication plated steel sheet is manufactured with such a steel sheet with low surface smoothness, the unevenness of the plating surface cannot be completely covered with a relatively thin coating film having a thickness of about 0.2 to 5 μm. Sometimes only the convex part is deformed, and the appearance after processing is deteriorated and the lubricity is lowered.

  However, the technique disclosed in Patent Document 3 does not consider the problem that the appearance after processing deteriorates and the lubricity decreases.

In the technique disclosed in Patent Document 4, Ti and B are added for the purpose of suppressing the formation / growth of the Zn ₁₁ Mg ₂ phase which deteriorates the surface appearance, but the appearance after processing deteriorates and lubrication. The problem that the property is lowered is not taken into consideration, and no mention is made of an intermetallic compound.

  Then, this invention is made | formed in view of the said problem, and it aims at providing the lubrication plating steel plate which was excellent in workability enough also in the case of high Al concentration which exceeds 4 mass%.

  As a result of intensive research on the development of a lubricated plated steel sheet having excellent workability, the inventors have performed a base treatment after forming a zinc-based plating with an optimized amount of additive elements on the surface of the steel sheet. It was found that a lubricating plated steel sheet having excellent workability can be produced by coating a coating optimized on the aqueous resin (a), silica particles (b) and solid lubricant (c). Invented.

  That is, the gist of the present invention is as follows.

(1) on one or both sides of the steel sheet, Al: 4 to 10 mass%, Mg: 1 to 5 mass%, Ti: Ri Na than 0.1 wt% content and balance zinc and inevitable impurities or less, [Al / Zn / Zn ₂ Mg phase ternary eutectic structure] [Al phase] and [Zn ₂ Mg phase], [Zn phase] one or two or more metal structure mixed Furthermore, a zinc-based plating layer containing a Ti—Al-based intermetallic compound in one or more of the above [Al phase], [Zn ₂ Mg phase] and [Zn phase] is used as a lower layer , Further, it has a base treatment layer, and further 5 to 50% by mass of silica particles (b) and 1 of the solid lubricant (c) with respect to 100% by mass of the solid content of the aqueous resin (a). the aqueous lubricant coating containing 40 wt% coating, the film obtained by drying at a coverage of 0.2-5 g / m ² Non removal membrane lubricating plated steel sheet excellent in workability characterized by being made.

(2) On one or both sides of the steel sheet, Al: 4 to 22% by mass, Mg: 1 to 5% by mass, Ti: 0.1% by mass or less, Si: 0.5% by mass or less, with the balance being zinc and [Mg ₂ Si phase] and [Al phase] and [Zn ₂ Mg phase], [Zn phase] in the base of [Al / Zn / Zn ₂ Mg ternary eutectic structure] consisting of inevitable impurities In addition, one or more of the above-mentioned [Al phase], [Zn ₂ Mg phase] and [Zn phase] include one or more of Ti-Al based metals. A zinc-based plating layer containing an intermetallic compound is used as a lower layer, and further, 5 to 50% by mass of silica particles (b) with respect to 100% by mass of the solid content of the aqueous resin (a), solid lubricant ( The coating obtained by applying and drying an aqueous lubricating paint containing 1 to 40% by weight of c) is 0.2 to 5 g / Non removal membrane lubricating plated steel sheet with excellent workability, characterized in that it is formed at a coverage of ^2.

  (3) The aqueous resin (a) is at least one selected from the group consisting of an aqueous epoxy resin, an aqueous phenol resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous polyolefin resin. (1) or (2) a non-delaminating lubricated plated steel sheet having excellent workability;

  (4) The non-demembrane having excellent processability according to any one of (1) to (3), wherein the aqueous resin (a) is a polyurethane resin having a polyester skeleton portion and a polyether skeleton Lubricating plated steel sheet.

  (5) The processability according to (4) above, wherein the mass ratio of the polyether skeleton to the polyester skeleton of the polyurethane resin having a polyester skeleton portion and a polyether skeleton is 10:90 to 70:30. Excellent non-delaminating lubricated plated steel sheet.

  (6) The glass transition temperature (Tg) of the aqueous resin (a) is 70 ° C. or higher and 200 ° C. or lower, and is excellent in processability according to any one of (1) to (5) above Film-type lubricated steel sheet.

  (7) The non-film removal type excellent in processability according to any one of (1) to (6), wherein the solid lubricant (c) is a polyolefin wax having a particle size of 0.1 to 5 μm Lubricated steel sheet.

  (8) The water-based lubricating paint further comprises at least one cross-linking agent (d) selected from the group consisting of amino resins, polyisocyanate compounds, block bodies thereof, epoxy compounds and carbodiimide compounds. The non-delaminating lubricated plated steel sheet having excellent workability according to any one of (1) to (7), wherein the content is 1 to 40% by mass with respect to 100% by mass.

(9) The non-delaminating lubrication excellent in workability as described in any one of (1) to (8) above, wherein the base treatment layer has a chromate film with a Cr adhesion amount of 5 to 100 mg / m ^2. Plated steel sheet.

(10) The workability as described in any one of (1) to (8) above, wherein the base treatment layer has a chemical conversion film of a phosphate film having an adhesion amount of 0.2 to 5.0 g / m ² . Non-delaminating lubricated plated steel sheet with excellent performance.

(11) It has a resin-type film layer formed by applying and drying a base treatment liquid containing an aqueous resin (e) as a base treatment layer, and the coating amount after drying of the film layer is 10 to 3000 mg / The non-delaminating lubricated plated steel sheet having excellent workability according to any one of (1) to (8), wherein m ² is m ² .

  (12) The aqueous resin (e) is at least one selected from the group consisting of an aqueous epoxy resin, an aqueous phenol resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous polyolefin resin. A non-delaminating lubricated plated steel sheet having excellent workability as described in (11).

  (13) The base treatment layer further contains 1 to 300% by mass of a silane coupling agent (f) with respect to 100% by mass of the aqueous resin (e). Non-delaminating lubricated plated steel sheet with excellent workability

  (14) The processability as described in (13) above, wherein the silane coupling agent (f) contains at least one selected from the group consisting of an epoxy group and an amino group as a reactive functional group. Excellent non-delaminating lubricated plated steel sheet.

  (15) The base treatment layer further comprises 1 to 300% by mass of a polyphenol compound (g) based on 100% by mass of the solid content of the aqueous resin (e). A non-delaminating lubricated plated steel sheet excellent in workability described in any one of the above.

  (16) The base treatment layer further contains at least one (h) selected from the group consisting of phosphoric acid and hexafluorometal acid in an amount of 0.1 to 100 mass with respect to 100 mass% of the solid content of the aqueous resin (e). % Non-delaminating type lubricating plated steel sheet excellent in workability according to any one of the above (11) to (15).

  (17) Hexafluorometal acid contains at least one element selected from the group consisting of Ti, Si, Zr, and Nb, and has excellent workability as described in (16) above Film-type lubricated steel sheet.

  (18) The base treatment layer further contains 0.1 to 100% by mass of the phosphate compound (i) with respect to 100% by mass of the solid content of the aqueous resin (e). (18) A non-delaminating lubricated plated steel sheet excellent in workability according to any one of (18).

  (19) The phosphate compound (i) contains at least one element selected from the group consisting of Mg, Mn, Al, Ca, and Ni as a cation component. Non-delaminating lubricated steel sheet with excellent workability.

  (20) The metal oxide particles (j) made of at least one metal element selected from the group consisting of Si, Ti, Al, and Zr are further added to the base treatment layer at a solid content of 100% by mass of the aqueous resin (e). The non-delaminating type lubricated plated steel sheet excellent in workability according to any one of the above (11) to (19), characterized by containing 1 to 300% by mass.

  (21) The non-delaminating lubricated plated steel sheet excellent in workability according to any one of (1) to (20), wherein the surface has a dynamic friction coefficient of 0.09 or less.

(22) wherein (1) to TiAl-based intermetallic compound according to any one of (21), non-film removal type lubricant coated steel sheet with excellent workability, characterized in that the TiAl _3.

( 23 ) The Ti—Al intermetallic compound according to any one of (1) to ( 21 ) is Ti (Al _1-X Si _x ) ₃ (where X = 0 to 0.5). A non-delaminating lubricated plated steel sheet with excellent workability characterized by being.

( 24 ) The Ti—Al intermetallic compound contained in the [Al phase] in the plating layer is present in a Zn—Al eutectoid reaction structure enriched in the Zn phase. (1) thru | or the non-delaminating lubrication plating steel plate excellent in workability in any one of ( 23 ).

( 25 ) The non-de-filming excellent in workability according to any one of (1) to ( 24 ), wherein the size of the [Al phase] dendrite in the plating layer is 500 μm or less Lubricating plated steel sheet.

According to the present invention, it is possible to produce a lubricated plated steel sheet that can be subjected to severe press work without applying press oil and sufficiently ensure the corrosion resistance of the processed part, and can exhibit extremely excellent industrial effects. .

The present invention is described in detail below.
In the present invention, the lubricating plated steel sheet is obtained by sequentially providing a zinc-based plating layer, a base treatment layer, and a lubricating film layer on the steel sheet. As the base steel sheet of the present invention, both hot-rolled steel sheets and cold-rolled steel sheets can be used. Various materials such as high-strength steel and stainless steel to which is added can be applied.

  The lower zinc-based plating layer in the present invention is Al: 4 to 10% by mass, Mg: 1 to 5% by mass, Ti: 0.1% by mass or less, the balance being Zn and inevitable impurities, or Al: 4 to 22% by mass, Mg: 1 to 5% by mass, Ti: 0.1% by mass or less, Si: 0.5% by mass or less, the balance being Zn and inevitable impurities.

  In the Zn-Al-Mg-Ti plating layer, the reason why the Al content is limited to 4 to 10% by mass is that when the Al content exceeds 10% by mass, the plating adhesion is reduced. This is because the content of Al in the plating to which no is added needs to be 4 to 10% by mass. In addition, when the amount is less than 4% by mass, the Al phase does not crystallize as the primary crystal, so there is no problem of smoothness.

  Therefore, in the lubricated plated steel sheet according to the present invention, it is essential to add Si during plating in order to ensure plating adhesion, particularly when the Al concentration is high such that the Al concentration exceeds 10% by mass.

  On the other hand, in the Zn-Al-Mg-Ti-Si-based plating layer, the reason that the Al content is limited to 4 to 22% by mass is that the Al phase does not crystallize as a primary crystal if the content is less than 4% by mass, so that smoothness is achieved. This is because there is no problem of reduction, and when it exceeds 22% by mass, the effect of improving the corrosion resistance is saturated.

The reason why the content of Si is limited to 0.5% by mass or less (excluding 0% by mass) is that Si has an effect of improving adhesiveness, but if it exceeds 0.5% by mass, an effect of improving adhesiveness. This is because is saturated. Desirably, it is 0.00001-0.5 mass%, More desirably, it is 0.0001-0.5 mass%. The addition of Si is essential for plating layers with an Al content of more than 10% by mass. However, even in plating layers with an Al content of 10% or less, the effect of improving plating adhesion is great, so the parts are severely processed. It is effective to add Si when high plating adhesion is required. Moreover, [Mg ₂ Si phase] crystallizes in the solidified structure of the plating layer by addition of Si. Since this [Mg ₂ Si phase] is effective in improving the corrosion resistance of the processed part, it is desirable to increase the amount of Si added and prepare a metal structure in which [Mg ₂ Si phase] is mixed in the solidified structure of the plating layer. .

The reason why the Mg content is limited to 1 to 5% by mass is that if the content is less than 1% by mass, the effect of improving the corrosion resistance is insufficient, and if it exceeds 5% by mass, the plating layer becomes brittle and the adhesion is reduced. It is because it falls. Since [Mg ₂ Si phase] is more easily crystallized as the amount of Mg added is larger, the content of Mg is preferably 2 to 5% by mass for the purpose of improving the corrosion resistance of the processed part.

  The reason why the content of Ti is limited to 0.1% by mass or less (excluding 0% by mass) is that Ti has the effect of crystallizing the Ti—Al intermetallic compound and improving the surface smoothness. If the content exceeds 0.1% by mass, the appearance after plating becomes rough, resulting in poor appearance. Moreover, when Ti-Al type intermetallic compound exceeds 0.1 mass% by Ti content, it will concentrate on the plating surface and will reduce surface smoothness. Desirably, it is 0.00001-0.1 mass%, More desirably, it is 0.00001-0.01 mass%.

This plating layer is a kind of [Zn phase], [Al phase], [Zn ₂ Mg phase], [Mg ₂ Si phase] in a [Al / Zn / Zn ₂ Mg ternary eutectic structure] substrate. Alternatively, a Ti-Al intermetallic compound contained in one or more of a metal structure containing two or more and a [Zn phase], [Al phase], and [Zn ₂ Mg phase] can be formed.

Here, [Al / Zn / Zn ₂ Mg ternary eutectic structure] is a ternary eutectic structure of an Al phase, a Zn phase and an intermetallic compound Zn ₂ Mg phase, and this ternary eutectic structure. For example, the Al phase forming the quaternary layer corresponds to the "Al" phase "(Al solid solution that dissolves the Zn phase in a solid solution and contains a small amount of Mg) in the ternary equilibrium diagram of Al-Zn-Mg. To do. The Al ″ phase at high temperature usually appears separated into a fine Al phase and a fine Zn phase at room temperature. The Zn phase in the ternary eutectic structure dissolves a small amount of Al, and in some cases The Zn ₂ Mg phase in the ternary eutectic structure exists in the vicinity of Zn: about 84% by mass in the Zn-Mg binary equilibrium diagram. As seen from the phase diagram, Si and Ti are not dissolved in each phase. Therefore, the ternary eutectic structure composed of these three phases is expressed as [Al / Zn / Zn ₂ Mg ternary eutectic structure] in this specification.

  In addition, the [Al phase] is a phase that looks like an island with a clear boundary in the ternary eutectic structure, which is, for example, at a high temperature in an Al—Zn—Mg ternary equilibrium diagram. "Al" phase "(Al solid solution in which Zn phase is dissolved, and contains a small amount of Mg). The Al ″ phase at this high temperature differs in the amount of Zn and Mg dissolved depending on the Al and Mg concentrations in the plating bath. The Al ″ phase at this high temperature is usually fine Al phase and fine Zn at room temperature. Although it is separated into phases, it can be seen that the island-like shape seen at room temperature is the one that retains the shape of the Al ″ phase at high temperature. It is thought that it is very small even if it is dissolved, but it cannot be clearly distinguished by ordinary analysis. Therefore, it is derived from the Al ″ phase at this high temperature, and the shape of the Al ″ phase in terms of shape. In the present specification, the phase holding the “.” Is called “Al phase.” This [Al phase] can be clearly distinguished from the Al phase forming the ternary eutectic structure by microscopic observation.

  In addition, the [Zn phase] is a phase that looks like an island with a clear boundary in the ternary eutectic structure, and actually contains a small amount of Al and a small amount of Mg as a solid solution. There is also. As far as the phase diagram is concerned, it is considered that Si and Ti are not dissolved in this phase, or even if they are dissolved in a very small amount. This [Zn phase] can be clearly distinguished from the Zn phase forming the ternary eutectic structure by microscopic observation.

The [Zn ₂ Mg phase] is a phase that looks like an island with a clear boundary in the ternary eutectic structure, and a small amount of Al may be actually dissolved. As far as the phase diagram is concerned, it is considered that Si and Ti are not dissolved in this phase, or even if they are dissolved in a very small amount. This [Zn ₂ Mg phase] can be clearly distinguished from the Zn ₂ Mg phase forming the ternary eutectic structure by microscopic observation.

The [Mg ₂ Si phase] is a phase that looks like an island with a clear boundary in the solidified structure of the plating layer. As can be seen from the phase diagram, Zn, Al, and Ti are not dissolved or are considered to be extremely small even if they are dissolved. This [Mg ₂ Si phase] can be clearly distinguished in microscopy in the plating.

Further, the Ti—Al intermetallic compound is a phase that looks like an island with a clear boundary in the solidified structure of the plating layer. From the viewpoint of the phase diagram, it is considered to be TiAl ₃ . However, when a Ti—Al intermetallic compound in a plating to which Si is added is analyzed, Si is observed. Therefore, the Ti—Al intermetallic compound in such a plating layer is TiAl ₃ or Al in which Si is dissolved. It is thought that Ti (Al _1-X Si _x ) ₃ partially substituted with Si (where X = 0 to 0.5).

In the hot-dip galvanized steel material of the present invention, this Ti—Al intermetallic compound is present in [Al phase], [Zn ₂ Mg phase], and [Zn phase]. The reason why the content of the Ti-Al intermetallic compound is limited to [Al phase], [Zn ₂ Mg phase], and [Zn phase] is that the Ti—Al intermetallic compound present at other positions This is because the workability cannot be improved. [Al phase], [Zn ₂ Mg phase], why Ti-Al system intermetallic compound present in the [Zn phase] is to improve the workability, Ti-Al system intermetallic compound is [Al phase], It is considered that this is because the crystallization of these crystals is promoted by forming the nuclei of [Zn ₂ Mg phase] and [Zn phase] to form a fine and numerous structure. That is, when the crystal becomes finer, unevenness on the surface of the plating layer is suppressed, the plating surface becomes smooth, and the part where the surface pressure is locally increased due to the metal mold uniformly contacting the plating surface during processing does not occur, It is thought that the workability of the lubricated steel sheet is improved.

  This effect is particularly remarkable in the [Al phase]. By controlling the size of the [Al phase] dendrites to 500 μm or less, the surface becomes smooth and the friction coefficient decreases. Desirably, it is 400 micrometers or less. More desirably, it is 300 μm or less.

  As a result of the inventors investigating a number of metal structures in plating, an intermetallic compound having a size of several μm was observed from most of the metal structures. An example of an intermetallic compound present in the [Al phase] is shown in FIG. The upper diagram (a) in FIG. 1 is a micrograph (magnification 1000 times) of the plating layer of the plated steel material in the present invention, and the lower diagram (b) illustrates the distribution state of each structure in the photograph. It is. As can be seen from this figure, each structure can be clearly identified by a micrograph of the plated layer of the plated steel material in the present invention.

  In FIG. 1, Ti—Al intermetallic compounds are observed in the one corresponding to the “Al ″ phase” at a high temperature in the Al—Zn—Mg ternary equilibrium diagram. This Al ″ phase at high temperature usually appears separated into a fine Al phase and a fine Zn phase at room temperature by a eutectoid reaction occurring at 277 ° C. in the binary equilibrium diagram of Al—Zn. In the hypoeutectoid reaction, the Al "phase crystallized at a high temperature starts to precipitate the Zn phase from the ternary eutectic temperature in the Al-Zn-Mg ternary equilibrium diagram, and the Al-Zn binary system. The Al ″ phase remaining at the temperature corresponding to the eutectoid reaction in the equilibrium diagram becomes a eutectoid structure of the fine Al phase and the fine Zn phase.

  The upper diagram (a) in FIG. 2 is a micrograph (magnification of 3500 times) of the Al ″ phase in FIG. 1, and the lower diagram (b) illustrates the distribution of each tissue in the photograph. When the Al ″ phase is observed in detail, it is observed that a Zn—Al eutectoid reaction structure enriched in the Zn phase exists around the outside of the Al ″ phase and around the Ti—Al intermetallic compound. The

In the present invention, the size of the intermetallic compound is not particularly limited, but what the inventors have observed is a size of 10 μm or less. Further, the proportion of the intermetallic compound in the plating structure is not particularly limited, but it is desirable that 10% or more exists in any one of [Al phase], [Zn ₂ Mg phase], and [Zn phase].

  In the present invention, the method for producing a plated steel sheet is not particularly limited, and a normal non-oxidizing furnace type hot dipping method can be applied.

There are no particular restrictions on the method of adding the intermetallic compound, and a method in which the fine powder of the intermetallic compound is turbid in the bath or a method in which the intermetallic compound is dissolved in the bath can be applied. When manufacturing with a continuous line using a plating method, a method of dissolving Ti in the plating bath is appropriate. As a method of dissolving Ti in the plating bath, a method of adding a Ti-Zn intermetallic compound Is efficient because it can be dissolved at low temperature in a short time. Examples of Ti—Zn-based intermetallic compounds to be added include Zn ₁₅ Ti, Zn ₁₀ Ti, Zn ₅ Ti, Zn ₃ Ti, Zn ₂ Ti, and ZnTi. When these intermetallic compounds are added alone or mixed in a Zn, Zn-Al, Zn-Al-Mg alloy and added to the plating bath, the dissolved Ti crystallizes as a Ti-Al intermetallic compound during plating, and the surface Improves smoothness and workability.

There are no particular restrictions on the amount of plating deposited, but it is preferably 10 g / m ² or more from the viewpoint of corrosion resistance and 350 g / m ² or less from the viewpoint of workability.

  In addition to this, the galvanized layer may contain Fe, Sb, Pb, and Sn alone or in combination within 0.5% by mass. Moreover, even if it contains a total of 0.5% by mass or less of group III elements such as Ca, Be, Cu, Ni, Co, Cr, Mn, P, B, Nb, Bi, V, Nb and lanthanoids There is a case where the effect of the invention is not impaired and the corrosion resistance is further improved depending on the amount thereof, which is preferable.

  As the base treatment layer, a chromate film, a phosphate film, or a resin-based film formed by applying a treatment liquid containing an aqueous resin to the plating surface and then drying it is used. The ground treatment layer is located between the plated surface and the lubricating film, and contributes to improvement in adhesion and corrosion resistance during processing.

It does not specifically limit as a chromate film | membrane used for a surface treatment, The chromate film | membrane formed from a well-known processing agent and a processing method can be used. For example, a post-water-washing electrolytic reduction chromate film, a reactive chromate film mainly composed of trivalent chromium hydrated oxide, a chromate liquid mainly composed of trivalent chromium and hexavalent chromium hydrated oxide is applied and dried. An anhydrous chromate coating chromate film can be used. Further, the chromate film may be a composite chromate film containing phosphoric acid, etching fluoride, fine silica and the like. The amount of adhesion is 5 to 100 mg / m ² in terms of Cr. Less than 5 mg / m ² is not preferable because corrosion resistance cannot be obtained. If it exceeds 100 mg / m ² , the chromate film itself is prone to cohesive failure and adhesion cannot be obtained. It is desirable that the chromate film has a high trivalent chromium / 6 hexavalent chromium ratio and is difficult to dissolve in the water-based lubricating paint.

The phosphate film used for the base treatment is composed of phosphates such as zinc, iron, nickel, manganese, calcium, and magnesium. It does not specifically limit as a processing agent and a processing method, A well-known processing agent and a processing method can be used. For example, any processing such as reactive processing, coating processing, and electrolytic processing may be used as the processing method. Although it does not specifically limit as a process process, after giving the zinc plating of this invention etc. to a steel plate, it processes through each process of phosphate pre-processing (surface adjustment), phosphate processing, water washing, and drying. Is common. There is no particular limitation on the above-mentioned phosphate pretreatment (surface conditioning) method. For example, an aqueous zinc phosphate solution or a colloidal Ti solution is generally used, and acts as a precipitation site for phosphate crystals. It is carried out to form a dense film. The adhesion amount is preferably in the range of 0.2 to 5 g / m ² for the reasons of corrosion resistance and adhesion. If it is less than 0.2 g / m 2, corrosion resistance cannot be obtained. If it exceeds 5 g / m ² , adhesion cannot be obtained by severe processing due to cohesive failure of the phosphate film.

  As the water-based resin (e) of the resin-based film used for the base treatment, in addition to the water-soluble resin, a resin (water dispersibility) that is inherently insoluble in water but can be finely dispersed in water like an emulsion or suspension. Including resin). The type of the aqueous resin (e) is not particularly limited, and examples thereof include an aqueous epoxy resin, an aqueous phenol resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous polyolefin resin.

  The aqueous epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, resorcin type epoxy resin. In the presence of an epoxy resin such as a novolac-type epoxy resin, which is obtained by reacting with an amine compound such as diethanolamine or N-methylethanolamine and neutralizing with an organic acid or an inorganic acid, or in the presence of the epoxy resin, a high acid value Examples thereof include those obtained by radical polymerization of an acrylic resin, neutralized with ammonia or an amine compound, and dispersed in water.

  The aqueous phenol resin is not particularly limited. For example, a methylolated phenol resin obtained by addition reaction of aromatics such as phenol, resorcin, cresol, bisphenol A, paraxylylene dimethyl ether and formaldehyde in the presence of a reaction catalyst. And the like obtained by reacting the phenol resin with amine compounds such as diethanolamine and N-methylethanolamine and neutralizing with an organic acid or inorganic acid.

  The aqueous polyester resin is not particularly limited. For example, ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylol ethane, trimethylol propane. Dehydration condensation of polyhydric alcohols such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, sebacic acid, maleic anhydride, itaconic acid, fumaric acid, and hymic anhydride And those obtained by neutralizing with ammonia or amine compound and dispersing in water.

  The aqueous urethane resin is not particularly limited. For example, ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylol ethane, trimethylol propane. And polyhydric alcohols such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and the like, and chain extension with diamine or the like, followed by water dispersion.

  The aqueous acrylic resin is not particularly limited, and examples thereof include unsaturated monomers such as styrene, alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylates, and alkoxysilane (meth) acrylates. Can be obtained by radical polymerization in an aqueous solution using a polymerization initiator. The polymerization initiator is not particularly limited, and for example, persulfates such as potassium persulfate and ammonium persulfate, and azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile can be used.

  The aqueous olefin resin is not particularly limited. For example, after radical polymerization of ethylene and an unsaturated carboxylic acid such as methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid under high temperature and pressure, ammonia is used. And a compound obtained by neutralizing with an amine compound, a metal compound such as KOH, NaOH, LiOH or the like, ammonia or an amine compound containing the above metal compound, and dispersing in water.

The aqueous resin (e) may be used alone or in combination of two or more. One or more aqueous composite resins obtained by modifying at least one other aqueous resin in the presence of at least one aqueous resin may be used. Furthermore, if necessary, a crosslinking agent may be added to the aqueous resin, or a crosslinking agent may be introduced into the resin skeleton. The crosslinking agent is not particularly limited, and examples thereof include melamine, epoxy, carbodiimide, blocked isocyanate, oxazoline and the like.

  The resin-based film used for the base treatment preferably further contains a silane coupling agent (f). Silane coupling agents are known to chemically bond to both metals and organics. By blending such a silane coupling agent, the adhesion with the plating of the resin film is dramatically improved, and as a result, the corrosion resistance of the processed part is improved.

  The silane coupling agent is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ sold by Shin-Etsu Chemical, Nippon Unicar, Chisso, Toshiba Silicone, etc. -Aminopropylethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Methyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3 4- Poxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ -Aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be mentioned. From the viewpoint of adhesion to the resin film, it is more preferable to use a silane coupling agent containing an epoxy group and / or an amino group as the reactive functional group. The said silane coupling agent may be used independently and may use 2 or more types together. In consideration of the stability of the treatment liquid, an organic acid such as acetic acid can be added.

  The silane coupling agent is desirably contained in an amount of 1 to 300% by mass with respect to 100% by mass of the aqueous resin. If the amount is less than 1% by mass, the amount of the silane coupling agent is insufficient, so that sufficient adhesion cannot be obtained during processing, resulting in poor corrosion resistance. If it exceeds 300% by mass, the effect of improving the adhesion may be saturated and uneconomical, or the stability of the treatment liquid may be reduced.

  It is preferable that the resin-based film used for the base treatment further contains a polyphenol compound (g). Polyphenol compounds produce chelating action on metals and hydrogen bonding with hydrophilic groups of aqueous resins. By blending such a polyphenol compound, the adhesion between the plating and the resin-based film, and between the resin-based film and the lubricating film is dramatically improved, and as a result, the corrosion resistance of the processed part is improved.

The polyphenol compound is a compound having two or more phenolic hydroxyl groups bonded to a benzene ring or a condensate thereof. Examples of the compound having two or more phenolic hydroxyl groups bonded to the benzene ring include gallic acid, pyrogallol, catechol and the like. The condensate of the compound having two or more phenolic hydroxyl groups bonded to the benzene ring is not particularly limited, and examples thereof include polyphenol compounds that are widely distributed in the plant kingdom, usually called tannic acid. Tannic acid is a general term for aromatic compounds having a complex structure having a large number of phenolic hydroxyl groups widely distributed in the plant kingdom. The tannic acid may be hydrolyzable tannic acid or condensed tannic acid. The tannic acid is not particularly limited, and examples thereof include hameli tannin, oyster tannin, chatannin, pentaploid tannin, gallic tannin, milobalan tannin, dibidi tannin, argarovira tannin, valonia tannin, catechin tannin and the like. . Examples of the tannic acid include commercially available ones such as “tannic acid extract A”, “B tannic acid”, “N tannic acid”, “industrial tannic acid”, “purified tannic acid”, “Hi tannic acid”, "F tannic acid", "local tannic acid" (all manufactured by Dainippon Pharmaceutical Co., Ltd.), "tannic acid: AL" (manufactured by Fuji Chemical Industry Co., Ltd.) and the like can also be used. The said polyphenol compound may be used by 1 type, and may use 2 or more types together.

The polyphenol compound is desirably contained in an amount of 1 to 300% by mass with respect to 100% by mass of the aqueous resin. If the amount is less than 1% by mass, the amount of the polyphenol compound is insufficient, so that sufficient adhesion cannot be obtained during processing, resulting in poor corrosion resistance. On the other hand, if it exceeds 300% by mass, the adhesion and corrosion resistance may be lowered, and the stability of the treatment liquid may be lowered.

  It is desirable that the resin-based film used for the base treatment further contains at least one (h) selected from the group consisting of phosphoric acid and hexafluorometal acid. The phosphoric acid and hexafluorometal acid may be used alone or in combination. These acids activate the plating surface by etching and promote the action of silane coupling agents and polyphenol compounds on plating.

  The phosphoric acid is not particularly limited, and examples thereof include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid. In addition to the above action, phosphoric acid has the effect of forming a phosphate layer on the plating surface to passivate it, thereby improving the corrosion resistance. The said phosphoric acid may be used by 1 type, and may use 2 or more types together.

  The hexafluorometal acid is not particularly limited, and examples thereof include hexafluorophosphoric acid, hexafluorotitanic acid, hexafluorozirconic acid, hexafluorosilicic acid, hexafluoroniobic acid, hexafluoroantimonic acid, and ammonium salts and potassium salts thereof. Sodium salt, calcium salt, magnesium salt and the like. In addition to the above action, hexafluorometal acid improves the corrosion resistance because a stable metal oxide film layer is formed on the plating surface by the metal supplied from hexafluorometal acid. In particular, a metal containing Ti, Zr, Si, or Nb is preferable. The said hexafluoro metal acid may be used by 1 type, and may use 2 or more types together.

As for at least 1 sort (s) selected from the group which consists of phosphoric acid and hexafluoro metal acid, it is desirable to contain 0.1-100 mass% with respect to 100 mass% of solid content of aqueous resin (e). If the amount is less than 0.1% by mass, the amount of these acids is insufficient, and the corrosion resistance may be lowered. When it exceeds 100% by mass, the resin-based film becomes brittle, and the adhesiveness may be lowered due to film cohesive failure.

  It is desirable that the resin-based film used for the base treatment further contains a phosphate compound (i). By blending this phosphate compound, a hardly soluble phosphate film is formed on the plating surface during the formation of the resin film. That is, as the plating is dissolved by the phosphate ions of the phosphate, the pH rises on the plating surface, and as a result, a phosphate precipitation film is formed and the corrosion resistance is improved.

  The phosphate compound is not particularly limited, and examples thereof include metal salts such as orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, and polyphosphoric acid, and organic metal salts such as phytic acid and phosphonic acid. The cation species is not particularly limited, and examples thereof include Cu, Co, Fe, Mn, Sn, V, Mg, Ba, Al, Ca, Sr, Nb, Y, Ni, and Zn. As the cation species, it is more preferable to use Mn, Mg, Al, Ca, Ni. The said phosphate compound may be used by 1 type, and may use 2 or more types together.

  It is preferable to contain 0.1-100 mass% of phosphate compounds with respect to 100 mass% of solid content of aqueous resin (e). If it is less than 0.1% by mass, the amount of the phosphate compound is insufficient, so that the corrosion resistance may be lowered. When it exceeds 100% by mass, the resin-based film becomes brittle, and the adhesiveness may be lowered due to film cohesive failure.

  The resin-based film used for the base treatment preferably further contains metal oxide particles (j) made of at least one metal element selected from the group consisting of Si, Ti, Al, and Zr. By adding these metal oxide particles, the corrosion resistance can be further increased.

  The metal oxide particles are not particularly limited, and examples thereof include silica particles, alumina particles, titania particles, and zirconia particles. As said metal oxide particle, a thing with an average particle diameter of about 1-300 nm is suitable. These may be used alone or in combination of two or more.

  The metal oxide particles are preferably contained in an amount of 1 to 300 parts by weight based on 100% by mass of the solid content of the aqueous resin (e). If the amount is less than 1% by mass, the amount of the metal oxide particles is insufficient, so that the effect of improving the corrosion resistance may not be obtained. If it exceeds 300% by mass, the resin-based film becomes brittle, and the adhesion may be lowered due to the film cohesive failure.

Moreover, you may add an organic solvent, surfactant, an antifoamer, etc. to the process liquid containing the aqueous resin used for forming a resin-type membrane | film | coat as needed. The adhesion amount after drying of the ground treatment layer is preferably 10 to 3000 mg / m ² . If it is less than 10 mg / m < ² >, adhesiveness is inferior and the corrosion resistance of a processed part is inadequate. On the other hand, when it exceeds 3000 mg / m ² , not only is it uneconomical, but also the workability is lowered and the corrosion resistance is inferior.

  The method for applying the ground treatment layer is not particularly limited, and generally known coating methods such as roll coating, air spray, airless spray, and immersion can be applied. Drying and baking after coating may be performed by a known method such as a hot air furnace, an induction heating furnace, a near infrared furnace, or a combination of these in consideration of the polymerization reaction and curing reaction of the resin.

  Next, the lubricating film of the present invention will be described below. As a result of intensive studies, the present inventors have found that the silica particles (b) are 5 to 50% by mass and the solid lubricant (c) is 1 to 40 with respect to 100% by mass of the solid content of the aqueous resin (a). It has been found that by using a film obtained by applying and drying a water-based lubricating paint containing 5% by mass, it is possible to simultaneously satisfy performances such as lubricity, workability, adhesion, and corrosion resistance. In addition, the above-described zinc-based plated layer of the present invention is hard and has excellent corrosion resistance, and the lubricated plated steel sheet has a combined effect that the base treatment layer of the present invention contributes to a high degree of adhesion between the plating and the lubricating film. It has been found that it is possible to simultaneously satisfy the performances such as the best lubricity, workability, adhesion, and corrosion resistance.

  As the water-based resin (a) of the lubricating film, in addition to the water-soluble resin, a resin (water-dispersible resin) that is essentially water-insoluble but can be finely dispersed in water like an emulsion or a suspension is included. . The type of the aqueous resin (a) is not particularly limited, and examples thereof include an aqueous epoxy resin, an aqueous phenol resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous polyolefin resin. The aqueous resin (a) may be used alone or in combination of two or more. One or more aqueous composite resins obtained by modifying at least one other aqueous resin in the presence of at least one aqueous resin may be used. Among the aqueous resins (a), in particular, when emphasizing the balance of adhesion, elongation, shear strength, corrosion resistance, wear resistance, and chemical resistance, a polyurethane resin having a polyester skeleton portion and a polyether skeleton portion is used. It is preferable to select.

Generally, the physical properties of the polyurethane resin are controlled by the balance between the hard segment and the soft segment and the crosslink density, so that a wide range of properties can be controlled by the type of the skeleton and isocyanate. The elongation and tensile strength adjustment of the polyurethane resin used in the present invention are controlled by the content of the polyester skeleton showing flexibility and the polyether skeleton showing the toughness and the content of the urethane bond, and if the latter content increases, A tough characteristic with low elongation but high tensile strength can be obtained.

The polyester skeleton can be obtained from a polyester polyol compound, and the polyether skeleton can be obtained from a polyether polyol compound.
Examples of the polyester polyol compound include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1 , 4-butylene glycol, 3-methylpentanediol, hexamethylene glycol, hydrogenated bisphenol A, trimethylolpropane, and glycerin and other low molecular weight polyols such as succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, Obtained by reaction with polybasic acids such as isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and hexahydrophthalic acid, Selected from those having a hydroxyl group at the end.
Examples of the polyether polyol compound include bisphenol skeleton-containing glycols such as methylene bisphenol, ethylidene bisphenol, butylidene bisphenol, and isopropylidene bisphenol, and alkylene oxides having 2 to 4 carbon atoms (for example, ethylene oxide, propylene oxide, butylene). Oxides) are preferred, and those having 1 to 10 moles of alkylene oxide added are preferred.

The mass ratio of the polyether skeleton and the polyester skeleton is more preferably in the range of 10:90 to 70:30. When the ratio of the polyether is larger than the above range, it is tough but has a low elongation, so it is inferior in a high degree of moldability.

  Examples of the isocyanate group that bonds the ester skeleton and the ether skeleton of the polyurethane resin include monomers, dimers, trimers of aromatic diisocyanates such as tolylene diisocyanate, diphenyl meta diisocyanate, and xylylene diisocyanate, and polyethers thereof. Reactants with polyols and polyester polyols, and their hydrogenated derivatives, alicyclic isocyanates such as alicyclic isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and aliphatic isocyanate monomers, dimers, 3 A reaction product of a monomer and a polyether polyol or polyester polyol, or a mixture thereof can also be used. The blending amount depends on the polyester polyol and polyether polyol to be used, but 5 to 20% by mass of the polyurethane resin in terms of NCO can provide optimum processing characteristics as the resin physical properties.

  The aqueous epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, resorcin type epoxy resin. In the presence of an epoxy resin such as a novolac-type epoxy resin, which is obtained by reacting with an amine compound such as diethanolamine or N-methylethanolamine and neutralizing with an organic acid or an inorganic acid, or in the presence of the epoxy resin, a high acid value Examples thereof include those obtained by radical polymerization of an acrylic resin, neutralized with ammonia or an amine compound, and dispersed in water.

  The aqueous phenol resin is not particularly limited. For example, a methylolated phenol resin obtained by addition reaction of aromatics such as phenol, resorcin, cresol, bisphenol A, paraxylylene dimethyl ether and formaldehyde in the presence of a reaction catalyst. And the like obtained by reacting the phenol resin with amine compounds such as diethanolamine and N-methylethanolamine and neutralizing with an organic acid or inorganic acid.

  The aqueous polyester resin is not particularly limited. For example, ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylol ethane, trimethylol propane. Dehydration condensation of polyhydric alcohols such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, sebacic acid, maleic anhydride, itaconic acid, fumaric acid, and hymic anhydride And those obtained by neutralizing with ammonia or amine compound and dispersing in water.

  The aqueous acrylic resin is not particularly limited, and examples thereof include unsaturated monomers such as styrene, alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylates, and alkoxysilane (meth) acrylates. Can be obtained by radical polymerization in an aqueous solution using a polymerization initiator. The polymerization initiator is not particularly limited, and for example, persulfates such as potassium persulfate and ammonium persulfate, and azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile can be used.

  The aqueous olefin resin is not particularly limited. For example, after radical polymerization of ethylene and an unsaturated carboxylic acid such as methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, and crotonic acid under high temperature and pressure, ammonia is used. And a compound obtained by neutralizing with an amine compound, a metal compound such as KOH, NaOH, LiOH or the like, ammonia or an amine compound containing the above metal compound, and dispersing in water.

  The glass transition temperature (Tg) of the aqueous resin (a) is more preferably 70 ° C. or higher and 200 ° C. or lower. When the temperature is lower than 70 ° C, sufficient lubrication characteristics may not be obtained when the temperature rises due to deformation heat of the material or frictional heat between the material and the mold during processing, and the temperature exceeds 200 ° C. In some cases, the film formability of the lubricating film is lowered and corrosion resistance cannot be obtained.

  Fine silica (b) is added to improve corrosion resistance and toughen the film. The fine silica (b) is not particularly limited and is preferably a silica fine particle such as colloidal silica or fumed silica having a primary particle diameter of 3 to 50 nm because the lubricating film is a thin film. Commercially available products include, for example, Snowtex O, Snowtex N, Snowtex C, Snowtex IPA-ST (Nissan Chemical Industry), Adelite AT-20N, AT-20A (Asahi Denka Kogyo), Aerosil 200 (Nippon Aerosil) Etc.

The amount of fine silica (b) is 5 to 50% by mass based on 100% by mass of the aqueous resin (a). If it is less than 5%, the effect of improving the corrosion resistance and workability is small, and if it exceeds 50%, the binder effect of the resin is reduced, the corrosion resistance is lowered and the elongation and strength of the resin are lowered, and the workability is lowered.

The solid lubricant (c) is not particularly limited, and examples thereof include known fluorine-based, hydrocarbon-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based and inorganic lubricants. As a selection criterion for lubricating additives for improving processability, it is necessary to select a material that exists on the surface of the resin film rather than being dispersed in the resin film on which the added lubricant is formed. This is necessary in order to reduce the friction between the surface of the object and the mold and maximize the lubrication effect. That is, when the lubricant is dispersed in the formed resin film, the surface friction coefficient is high, the resin film is easily broken, and powdery substances are peeled and deposited, resulting in poor appearance and reduced workability called powdering phenomenon. Arise. As the substance that exists on the surface of the resin film, a substance that is incompatible with the resin and has a small surface energy is selected.
It is more preferable to select a solid lubricant having a surface dynamic friction coefficient of 0.09 or less.

  As a result of investigations by the present inventors, it has been found that the use of polyolefin wax is more preferable because the dynamic friction coefficient of the surface is lowered, the workability is greatly improved, and the performance such as corrosion resistance and chemical resistance after processing is improved. It was. Examples of the wax include hydrocarbon waxes such as paraffin, microcrystalline, and polyethylene. At the time of processing, since the film temperature rises due to the deformation heat and frictional heat of the material, the melting point of the wax is more preferably 70 to 160 ° C. If it is less than 70 degreeC, it may soften and melt at the time of a process, and the outstanding characteristic as a solid lubricant may not be exhibited. In addition, when the melting point exceeds 160 ° C., hard particles are present on the surface and the friction characteristics are deteriorated, so that high moldability may not be obtained.

The particle diameter of these waxes is more preferably 0.1 to 5 μm. If it exceeds 5 μm, the distribution of the solidified wax may be non-uniform, or the lubricant film may fall off. Moreover, when it is less than 0.1 μm, the workability may be insufficient.

The amount of the solid lubricant (c) is 1 to 40% by mass with respect to 100% by mass of the aqueous resin (a). If it is less than 1%, the effect of improving the workability is small, and if it exceeds 40%, the workability and the corrosion resistance are lowered.

  The lubricating film preferably further contains at least one (d) crosslinking agent selected from the group consisting of amino resins, polyisocyanate compounds, block bodies thereof, epoxy compounds, and carbodiimide compounds. By blending these crosslinking agents, the crosslinking density of the lubricating film can be increased, and the corrosion resistance and workability are improved. These crosslinking agents may be used alone or in combination of two or more.

It does not specifically limit as said amino resin, For example, a melamine resin, a benzoguanamine resin, a urea resin, a glycoluril resin etc. can be mentioned.

It does not specifically limit as said polyisocyanate compound, For example, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate etc. can be mentioned. The blocked product is a blocked product of the polyisocyanate compound.

The epoxy compound is not particularly limited as long as it is a compound having a plurality of oxirane rings. For example, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether Glycerin polyglycidyl ether, trimethylpropane polyglycidyl ether, neopentyl glycol polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol glycol diglycidyl ether, polypropylene glycol glycol diglycidyl ether, 2,2-bis -(4'-glycidyloxyphenyl) propane, tris (2,3-epoxypropyl) isocyanurate DOO, bisphenol A diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether and the like.

As the carbodiimide compound, for example, after synthesizing an isocyanate-terminated polycarbodiimide by a condensation reaction involving decarbonization of a diisocyanate compound such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, the reactivity with an isocyanate group is further increased. Examples thereof include compounds to which a hydrophilic segment having a functional group is added.

  As for the quantity of these hardening | curing agents, 1-40 mass% is preferable with respect to 100 mass% of solid content of aqueous resin (a). If the amount is less than 1%, the amount may be insufficient and the effect of addition may not be obtained. If the amount exceeds 40%, the lubricating film becomes brittle due to excessive curing, and the workability and corrosion resistance deteriorate.

The lubricating film of the present invention may be added with a conductive material for improving weldability or a colored pigment material for improving design. Moreover, even if various additives, such as a sedimentation inhibitor, a leveling agent, and a thickener, are added, the effect of this invention is not impaired.

  Since the present invention is a water-based paint, the surface tension is high and the surface wettability is inferior to that of a solvent system, and a uniform coating property may not be obtained when a predetermined amount is applied to the surface to be coated. However, in order to ensure performance such as high workability and corrosion resistance, it is indispensable that uniform coating is performed on the surface to be coated. For this reason, it is known to add a wetting agent or thickener. Examples of the wetting agent include known surfactants for reducing the surface tension, such as fluorine-based and silicon-based reducing surface tension. In particular, among these compounds, it is preferable to contain 0.05 to 0.5% of an acetylene glycol / alcohol surfactant having 0 to 20 moles of added ethylene oxide based on the water-based lubricating coating composition. The acetylene glycol / alcohol surfactant is characterized by a high wetting rate and a defoaming effect at the same time. On the other hand, fluorine-based and silicon-based surfactants are excellent in surface tension reducing ability, but are not suitable because the wetting speed is small and the defoaming property is poor, and furthermore, the adhesion of top coating is also poor.

  In addition, as a countermeasure for thickeners, when sufficient surface coverage cannot be ensured with only a wetting agent on the surface of the surface to be coated, or when the coating thickness is not ensured by a coating method typified by a roll coater. May be added. Since the coating material of the present invention is usually applied to an object to be coated at a high speed, a thixo type thickener typified by a cellulose type has little effect under coating conditions that receive high-speed shear stress. Under such coating conditions, it is known that a Newtonian type thickener is suitable. As the thickener used in the present invention, a thickener having an ether / urethane skeleton having a molecular weight of 1000 to 20000 is particularly preferred.

  Normally, when additives are added to paints, the original performance is often lowered, but this thickener has a very low impact when it remains in the coating because it is a skeleton that is difficult to hydrolyze. It is a feature. The addition amount is 0.01 to 0.2% with respect to the resin solid content of the water-based lubricating coating composition, and is usually determined by the coating conditions. If the amount is less than 0.01%, the thickening effect is small. If the amount exceeds 0.2%, the viscosity becomes too large, which may cause problems in coating properties and deteriorate high workability and excellent corrosion resistance. .

The coating composition of the present invention composed of the compounds described above varies depending on the application and coating conditions, but generally it is desirable to adjust the non-volatile content concentration to 15 to 30%, the viscosity to 10 to 50 cps, and the surface tension to 80 dyne / cm or less. . The reason is that it is easy to control the target film thickness, and to obtain a uniform film thickness with no unevenness in appearance and no repelling of the paint. The existing coating methods such as roll coating method, dipping method, air knife drawing, groove roll method, and curtain coating method can be adopted as the coating method, but the reverse roll is easy to obtain film thickness control, film thickness accuracy, and non-uniform appearance. Coat application is most desirable. The coating amount was 0.2 to 5 g / m ² as a dry film thickness. Immediately after coating, the plate temperature was baked to 80 to 200 ° C., preferably 120 to 160 ° C. by hot air, far-infrared furnace, electric furnace, combustion furnace, induction heating. After that, the film is forcedly cooled by a method such as water cooling and dried to form a film.

Lubricating reason for limiting the range of film thickness 0.2-5 g / m ² is that the present invention is less than 0.2 g / m ² is intended, workability, corrosion resistance is insufficient. If it exceeds 5 g / m ² μm, welding cannot be performed, and problems such as blocking tend to occur. The reason for limiting the baking plate temperature is that the resin reflow and crosslinking reaction are insufficient when the temperature is less than 80 ° C., resulting in a film with many defects on the rough surface. to degrade. The most desirable uniform and smooth defect-free film by melting and crosslinking of the resin and moderate surface concentration of the lubricant and dispersion in the film are obtained in the range of 120 to 160 ° C.

  Hereinafter, the present invention will be described specifically by way of examples.

(Example 1)
First, prepare the cold-rolled steel plate having a thickness of 0.8 mm, this for 3 seconds dip plating in a plating bath was varied amount of additive element in the bath at 400 to 600 ° C., the coating weight in N ₂ wiping The temperature was adjusted to 70 g / m ² on one side and cooled at a cooling rate of 10 ° C./s or less. Table 1 shows the plating composition of the obtained plated steel sheet. Moreover, the result of having observed the plated steel plate from the cross section by SEM and observing the metal structure of a plating layer is similarly shown in Table 1.

Ti-Al intermetallic compounds were observed with EPMA after the plated steel sheet was polished at an inclination of 10 degrees, and those existing in [Al phase], [Zn ₂ Mg phase], and [Zn phase] were observed. .

  The size of the [Al phase] dendrites in the plating layer was determined by mapping the surface of the plated steel plate with CMA and measuring the major axis of the resinous crystals using the resulting Al mapping. The measurement was performed in a range of 5 × 5 cm, the major diameters of five resinous crystals were measured in order from the largest, and the average value was used as the size of the [Al phase] dendrites.

Next, after degreasing the plated steel sheet, a coating-type chromate treatment with a Cr adhesion amount of 50 mg / m ² was performed, and on that, 100% by mass of the polyurethane resin produced according to Production Example 1 was added to fine silica (Snowtex-N ： Nissan Chemical Co., Ltd.) 30%, 15μm polyethylene wax (Chemical Pearl WF640: Mitsui Chemicals Co., Ltd.) with 15% particle size is applied, and baked to reach 150 ° C. Then, a lubricating plated steel sheet having a lubricating film with an adhesion amount of 1.0 g / m ² was produced.

Polyurethane resin production example 1
80 parts of a polyester polyol having an average molecular weight of 900 synthesized from adipic acid having a hydroxyl group at the terminal and 1,4-butylene glycol, 120 parts of a 3 mol adduct of bisphenol A propylene oxide having an average molecular weight of 700, 2,2-bis (hydroxy 12 parts of methyl) propionic acid is added to 100 parts of N-methyl-2-pyrrolidone and heated to 80 ° C. to dissolve. Thereafter, 100 parts of dicyclohexylmethane diisocyanate is added, heated to 110 ° C. and reacted for 2 hours, and 11 parts of triethylamine is added for neutralization. This solution was dropped into an aqueous solution obtained by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to obtain an aqueous urethane resin. The Tg of this resin is 85 ° C., and the weight ratio of the polyester skeleton to the polyether skeleton is polyester skeleton: polyether skeleton = 40: 60.

  The workability was evaluated using a pull-out test using a square bead with a shoulder R of 1 mmR (the convex part is 4 × 4 mm) and using the apparent friction coefficient at that time. In the pull-out test, a sample having a width of 30 mm and a length of 300 mm was sandwiched between bead dies, and then pulled out by changing the pressing load at 1000 to 1500 kgf, and the pull-out load at that time was measured. Ratio of linear function (Δ pull-out load / Δ push-weight) when the measured pressing load and pull-out load are plotted on the horizontal and vertical axes, respectively, with an apparent friction coefficient of 0.09 or less Was passed.

Corrosion resistance after processing was evaluated for corrosion resistance after a deep drawing test. A blank plate having a diameter of 115 mmφ was used, and a cylindrical deep drawing test was performed under the conditions of punch diameter = 50 mmφ, wrinkle holding pressure = 3 t, and deep drawing speed = 30 m / min. Corrosion resistance was determined by scoring as shown below for the occurrence of white rust after SST120hr for the side surface after deep drawing. A score of 3 or more was accepted.
10: No white rust generation 9: less than 1% 8: 1% or more but less than 3% 7: 3% or more but less than 5% 6: 5% or more but less than 7% 5: 7% or more but less than 10% 4: 10% or more but 15% Less than 3: 15% or more but less than 20% 2: 20% or more but less than 30% 1: 30% or more

  The evaluation results are shown in Table 1. Table 1 shows the results of investigating the influence of the plating composition. No. 16 did not contain a Ti—Al intermetallic compound, so the appearance after processing deteriorated, and the workability and post-processing corrosion resistance were rejected. Except this, all showed good workability and post-processing corrosion resistance.

(Example 2)
First, a cold-rolled steel sheet having a thickness of 0.8 mm is prepared, and this is hot-plated for 3 seconds in a Zn-Mg-Al-Si-Ti plating bath at 470 ° C., and the amount of plating adhesion is 70 g / side by N ₂ wiping. It was adjusted to m ^2, and then cooled below the cooling rate of 10 ° C. / s. The composition in the plated layer of the obtained plated steel sheet was Mg 3%, Al 11%, Si 0.2%, Ti 0.009%. Further, when the obtained plated steel sheet was polished at an inclination of 10 degrees and observed with EPMA, a Ti—Al intermetallic compound was observed in the [Al phase].

Next, after these galvanized steel sheets were degreased, the applied chromate treatment or zinc phosphate treatment with the adhesion amount shown in Table 2 was performed, and then the fine particles were added to 100% by mass of the polyurethane resin produced in Production Example 1. Lubricating paint containing 30% silica (Snowtex-N: manufactured by Nissan Chemical Industries, Ltd.) and 15% polyethylene wax (Chemical WF640: manufactured by Mitsui Chemicals) with a particle size of 1.0 μm is applied, and the ultimate plate temperature is 150. A lubricating plated steel sheet having a lubricating film with an adhesion amount of 1.0 g / m ² was produced by baking to a temperature of 0 ° C.

  For evaluation of adhesion, the Erichsen tester was used to reduce the thickness by 7 mm, peel off the convex portion, pass the case where the peeling did not peel, and make the case where the peeled portion failed.

Corrosion resistance after processing was evaluated for corrosion resistance after deep drawing test. A blank plate having a diameter of 115 mmφ was used, and a cylindrical deep drawing test was performed under the conditions of punch diameter = 50 mmφ, wrinkle holding pressure = 3 t, and deep drawing speed = 30 m / min. Corrosion resistance was determined by scoring as shown below for the occurrence of white rust after SST120hr for the side surface after deep drawing. A score of 3 or more was accepted.
10: No white rust generation 9: less than 1% 8: 1% or more but less than 3% 7: 3% or more but less than 5% 6: 5% or more but less than 7% 5: 7% or more but less than 10% 4: 10% or more but 15% Less than 3: 15% or more but less than 20% 2: 20% or more but less than 30% 1: 30% or more

  The evaluation results are shown in Table 2. Table 2 shows the results of applying a chromate film and a zinc phosphate film as the base treatment layer. No. 28 was out of the scope of the present invention because there was no undercoat layer, and the adhesion and post-processing corrosion resistance were rejected. Other than these, good adhesion and post-processing corrosion resistance were obtained.

(Example 3)
First, a cold-rolled steel sheet having a thickness of 0.8 mm is prepared, and this is hot-plated for 3 seconds in a Zn-Mg-Al-Si-Ti plating bath at 470 ° C., and the amount of plating adhesion is 70 g / side by N ₂ wiping. It was adjusted to m ^2, and then cooled below the cooling rate of 10 ° C. / s. The composition in the plated layer of the obtained plated steel sheet was Mg 3%, Al 11%, Si 0.2%, Ti 0.009%. Further, when the obtained plated steel sheet was polished at an inclination of 10 degrees and observed with EPMA, a Ti—Al intermetallic compound was observed in the [Al phase].

  Next, after these galvanized steel sheets were degreased, a base treatment agent having the composition shown in Tables 4 to 6 was applied using the chemicals shown in Table 3 and dried in a hot air drying furnace. The ultimate plate temperature during drying was 150 ° C.

Polyethylene wax (Chemical Pearl WF640: Mitsui) having 30% fine silica (Snowtex-N: manufactured by Nissan Chemical Industries Co., Ltd.) and 100% by mass of the polyurethane resin produced in Production Example 1 on this ground treatment. A lubricating paint containing 15% of Chemical Co., Ltd. was applied and baked so that the ultimate plate temperature was 150 ° C., thereby producing a lubricating plated steel sheet having a lubricating film with an adhesion amount of 1.5 g / m ² .

  For evaluation of adhesion, the Erichsen tester was used to reduce the thickness by 7 mm, peel off the convex portion, pass the case where the peeling did not peel, and make the case where the peeled portion failed.

Corrosion resistance after processing was evaluated for corrosion resistance after deep drawing test. A blank plate having a diameter of 115 mmφ was used, and a cylindrical deep drawing test was performed under the conditions of punch diameter = 50 mmφ, wrinkle holding pressure = 3 t, and deep drawing speed = 30 m / min. Corrosion resistance was determined by scoring as shown below for the occurrence of white rust after SST120hr for the side surface after deep drawing. A score of 3 or more was accepted.
10: No white rust generation 9: less than 1% 8: 1% or more but less than 3% 7: 3% or more but less than 5% 6: 5% or more but less than 7% 5: 7% or more but less than 10% 4: 10% or more but 15% Less than 3: 15% or more but less than 20% 2: 20% or more but less than 30% 1: 30% or more

  The evaluation results are shown in Tables 4-6. Tables 4 to 6 show the effects of the resin film composition applied to the resin film as the base treatment layer. No. 85 was out of the scope of the present invention because there was no undercoat layer, and the adhesion and post-processing corrosion resistance were rejected. Other than these, good adhesion and post-processing corrosion resistance were obtained. In addition, as a kind of silane coupling agent (f), numbers 32, 33, and 35 in which f1 having an epoxy group and f2 having an amino group are used alone or in combination among numbers 32 to 35 are relatively good. It showed corrosion resistance after processing.

Example 4
First, a cold-rolled steel sheet having a thickness of 0.8 mm is prepared, and this is hot-plated for 3 seconds in a Zn-Mg-Al-Si-Ti plating bath at 470 ° C., and the amount of plating adhesion is 70 g / side by N ₂ wiping. It was adjusted to m ^2, and then cooled below the cooling rate of 10 ° C. / s. The composition in the plated layer of the obtained plated steel sheet was Mg 3%, Al 11%, Si 0.2%, Ti 0.009%. Further, when the obtained plated steel sheet was polished at an inclination of 10 degrees and observed with EPMA, a Ti—Al intermetallic compound was observed in the [Al phase].

Next, after these galvanized steel sheets were degreased, the coating chromate treatment with a Cr adhesion amount of 50 mg / m ² , or the composition of No. 32 (Table 4), the composition of No. 51 (Table 5), and No. 73 of Example 3 The same ground treatment as that of the composition (Table 5) is performed at an adhesion amount of 200 mg / m ² , and the lubricant treatment paint having the composition shown in Tables 8 to 11 is applied using the chemicals shown in Table 7 so that the ultimate plate temperature becomes 150 ° C. The lube-plated steel sheet having the lubricating film with the adhesion amount shown in Tables 8 to 11 was produced.

Polyurethane resin production example 2
40 parts of a polyester polyol having an average molecular weight of 900 synthesized from adipic acid having a hydroxyl group at the terminal and 1,4-butylene glycol, 160 parts of a 3-mol adduct of bisphenol A propylene oxide having an average molecular weight of 700, 2,2-bis (hydroxy 10 parts of methyl) propionic acid is added to 100 parts of N-methyl-2-pyrrolidone and heated to 80 ° C. to dissolve. Thereafter, 120 parts of dicyclohexylmethane diisocyanate is added, heated to 110 ° C. and reacted for 2 hours, and neutralized with 10 parts of triethylamine. This solution was dropped into an aqueous solution obtained by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to obtain an aqueous urethane resin. The weight ratio of the polyester skeleton to the polyether skeleton of this resin is polyester skeleton: polyether skeleton = 20: 80.

Polyurethane resin production example 3
230 parts of polyester polyol having an average molecular weight of 900 synthesized from adipic acid having a hydroxyl group at the terminal and 1,4-butylene glycol and 15 parts of 2,2-bis (hydroxymethyl) propionic acid were added to 100 parts of N-methyl-2-pyrrolidone. In addition to the part, warm to 80 ° C. to dissolve. Thereafter, 100 parts of dicyclohexylmethane diisocyanate is added, heated to 110 ° C. and reacted for 2 hours, and 11 parts of triethylamine is added for neutralization. This solution was dropped into an aqueous solution obtained by mixing 5 parts of ethylenediamine and 570 parts of deionized water under strong stirring to obtain an aqueous urethane resin. The weight ratio of the polyester skeleton to the polyether skeleton of this resin is polyester skeleton: polyether skeleton = 100: 0.

  For evaluation of adhesion, the Erichsen tester was used to reduce the thickness by 7 mm, peel off the convex portion, pass the case where the peeling did not peel, and make the case where the peeled portion failed.

For evaluation of workability, a square cylinder high-speed crank press with a depth of 60 mm was performed, and the occurrence of galling due to metal contact between the sample and the die was determined by the following ratings.
3: No galling 2: Slight galling is allowed but acceptable level 1: Severe galling

Evaluation of post-processing corrosion resistance was determined by the following rating of the white rust occurrence situation after 10 cycles of CCT for the corner side surface portion of the sample subjected to a 60 mm depth square tube high-speed crank press. For CCT, one cycle was SST6hr → dry 4hr → wet 4hr → freeze 4hr. A score of 3 or more was accepted.
10: No white rust generation 9: less than 1% 8: 1% or more but less than 3% 7: 3% or more but less than 5% 6: 5% or more but less than 7% 5: 7% or more but less than 10% 4: 10% or more but 15% Less than 3: 15% or more but less than 20% 2: 20% or more but less than 30% 1: 30% or more

Weldability was evaluated under the following spot welding conditions.
Applied pressure: 200kgf
Electrode: Cu-Cr alloy, CF type, tip diameter 6mmφ
Energizing time: 10 cycles of continuous welding conditions: nugget forming current I ₀ (when the plate thickness is t, the nugget diameter is 4√t
1.4 times the current value (I _a ), 1 dot / 3
End of continuous welding with a speed of seconds and a pause of 30 seconds every 20 strike points: 0.85 × I _a sample for nugget diameter measurement every 100 strike points
Weld with current value and finish when nugget diameter is less than 4√t
In the end and judgment evaluation, the number of welding points of 500 or more was regarded as acceptable.

  The evaluation results are shown in Tables 8-11. Tables 8 to 11 investigate the influence of the composition of the lubricating film. In Nos. 140 to 142 and 146 to 148, since the addition amount of fine silica was outside the range of the present invention, the post-processing corrosion resistance was rejected. In Nos. 143 to 145 and 149 to 151, the addition amount of the solid lubricant was outside the range of the present invention, so that the workability and post-processing corrosion resistance were rejected. Nos. 152 and 154 were unsatisfactory in workability and post-processing corrosion resistance because the adhesion amount of the lubricating film was less than the lower limit of the present invention. Nos. 153 and 155 failed in weldability because the adhesion amount of the lubricating film exceeded the upper limit of the present invention. Other than these, good adhesion, workability, post-processing corrosion resistance, and weldability were obtained. In addition, as a kind of aqueous resin (a), the polyurethane resin a1 (Tg = 85 degreeC) and the polyurethane resin a2 (Tg = 105 degreeC) which have a polyester frame | skeleton and a polyether frame | skeleton among numbers 86-93 were used. Numbers 86 and 87 showed relatively good post-processing corrosion resistance.

(Example 5)
First, prepare the cold-rolled steel plate having a thickness of 0.8 mm, this for 3 seconds dip plating in a plating bath was varied amount of additive element in the bath at 520 ° C., one surface 70g of the coating weight in N ₂ wiping It adjusted to / m < ² > and it cooled with the cooling rate of 10 degrees C / s or less. Table 11 shows the plating composition of the obtained plated steel sheet. Moreover, the result of having observed the plated steel plate from the cross section by SEM and observing the metal structure of a plating layer is similarly shown in Table 11.

Ti-Al intermetallic compounds were observed with EPMA after the plated steel sheet was polished at an inclination of 10 degrees, and those existing in [Al phase], [Zn ₂ Mg phase], and [Zn phase] were observed. . Moreover, about the Ti-Al type intermetallic compound which exists in [Al phase], it observed by EPMA and the presence or absence in the Zn phase which precipitated by the eutectoid reaction of Zn-Al was observed. Furthermore, EPMA observation of the Ti—Al intermetallic compound was performed, and the presence or absence of Si in the Ti—Al intermetallic compound was observed.

Next, after this galvanized steel sheet was degreased, it was subjected to a coating chromate treatment with a Cr adhesion amount of 50 mg / m ² , and then the fine silica (Snowtex-N: Nissan) was added to 100% by mass of the polyurethane resin produced according to Production Example 1. Apply a lubricating paint containing 15% of polyethylene wax (Chemical Industry Co., Ltd.) and 30% polyethylene wax (Chemical Pearl WF640: Mitsui Chemicals) and baked to reach 150 ° C. A lubricating plated steel sheet having a lubricating film with an amount of 1.5 g / m ² was prepared.

  Adhesiveness is: ○ when the cellophane tape is applied to the hot-dip plated steel sheet after the DuPont impact test and then peeled off, and the plating does not peel, Δ when the plating peels less than 10%, and the plating peels 10% or more The case where it did is made x. The DuPont test was conducted by using a shooting type having a 1/2 inch roundness at the tip and dropping a 1 kg weight from a height of 1 m.

  The workability was evaluated using a pull-out test using a square bead with a shoulder R of 1 mmR (the convex part is 4 × 4 mm) and using the apparent friction coefficient at that time. In the pull-out test, a sample having a width of 30 mm and a length of 300 mm was sandwiched between bead dies, and then pulled out by changing the pressing load at 1000 to 1500 kgf, and the pull-out load at that time was measured. Ratio of linear function (Δ pull-out load / Δ push-weight) when the measured pressing load and pull-out load are plotted on the horizontal and vertical axes, respectively, with an apparent friction coefficient of 0.09 or less Was passed.

The evaluation of post-processing corrosion resistance was determined by the following rating of the occurrence of red rust on the bent part of the sample that had been subjected to 1T bending (180 ° bending with one original sheet sandwiched). A score of 3 or more was accepted.
5: Less than 5% 4: 5% or more but less than 10% 3: 10% or more but less than 20% 2: 20% or more but less than 30% 1: 30% or more

  The evaluation results are shown in Table 12. Table 12 investigates the influence of Si in the plating layer. In No. 157, since the addition amount of Si was outside the range of the present invention with respect to the addition amount of Al, the adhesion was rejected. Other than these, good adhesion and post-processing corrosion resistance were obtained. In particular, the plated steel sheet to which Si was added exhibited good adhesion and post-processing corrosion resistance.

(Example 6)
First, a cold-rolled steel plate having a thickness of 0.8 mm is prepared, and this is hot-plated for 3 seconds in a Zn-Mg-Al-Ti plating bath at 470 ° C., and the amount of plating is 70 g / m ² on one side by N ₂ wiping. And cooled at a cooling rate of 10 ° C./s or less. The composition in the plating layer of the obtained plated steel sheet was Mg 3%, Al 7%, Ti 0.007%. Further, when the obtained plated steel sheet was polished at an inclination of 10 degrees and observed with EPMA, a Ti—Al intermetallic compound was observed in the [Al phase].
Next, after degreasing these plated steel sheets, the same base treatment as the composition of No. 32 (Table 4), the composition of No. 51 (Table 5), and the composition of No. 73 (Table 5) in Example 3 was applied in an amount of 200 mg. / M ² , applying a lubricating treatment paint having the composition shown in Table 13 using the chemicals shown in Table 7, baking it so that the ultimate plate temperature is 150 ° C., and having a lubricating film with an adhesion amount shown in Table 13 Lubricated steel sheet was prepared.
For evaluation of adhesion, the Erichsen tester was used to reduce the thickness by 7 mm, peel off the convex portion, pass the case where the peeling did not peel, and make the case where the peeled portion failed.
For evaluation of workability, a square cylinder high-speed crank press with a depth of 60 mm was performed, and the occurrence of galling due to metal contact between the sample and the die was determined by the following ratings.
3: No occurrence of galling 2: Slight galling is allowed but acceptable level 1: Severe galling Evaluation of corrosion resistance after processing was performed on the corner side surface of a sample subjected to a 60 mm depth square tube high-speed crank press. The white rust generation situation after 10 cycles of CCT was determined by the following scoring. For CCT, one cycle was SST6hr → dry 4hr → wet 4hr → freeze 4hr. A score of 3 or more was accepted.
10: No white rust generation 9: less than 1% 8: 1% or more but less than 3% 7: 3% or more but less than 5% 6: 5% or more but less than 7% 5: 7% or more but less than 10% 4: 10% or more but 15% Less than 3: 15% or more but less than 20% 2: 20% or more but less than 30% 1: 30% or more The weldability was evaluated under the following spot welding conditions.
Applied pressure: 200kgf
Electrode: Cu-Cr alloy, CF type, tip diameter 6mmφ
Energizing time: 10 cycles of continuous welding conditions: nugget forming current I ₀ (when the plate thickness is t, the nugget diameter is 4√t
1.4 times the current value (I _a ), 1 dot / 3
End of continuous welding with a speed of seconds and a pause of 30 seconds every 20 strike points: 0.85 × I _a sample for nugget diameter measurement every 100 strike points
Weld with current value and finish when nugget diameter is less than 4√t
In the end and judgment evaluation, the number of welding points of 500 or more was regarded as acceptable.
The evaluation results are shown in Table 13. Table 13 investigates the influence of the composition of the lubricating film. All of the products of the present invention had good adhesion, workability, post-processing corrosion resistance, and weldability.

(A) is a drawing-substituting photomicrograph (magnification 1000 times) of the plated layer of the plated steel material of the present invention, and (b) is a diagram showing a distribution state of each structure in the photo. (A) is a drawing-substituting photomicrograph (magnification of 3500 times) in which the “Al ″ phase” of FIG. 1 is enlarged, and (b) is a diagram showing the distribution state of each tissue in the photograph.

Claims (25)

On one or both sides of the steel sheet, Al: 4 to 10 mass%, Mg: 1 to 5 mass%, Ti: Na remainder containing 0.1 wt% or less than the zinc and unavoidable impurities is, and [Al / [Zn / Zn ₂ Mg ternary eutectic structure] has a metal structure in which one or more of [Al phase], [Zn ₂ Mg phase], and [Zn phase] are mixed, and A zinc-based plating layer containing a Ti—Al-based intermetallic compound in one or more of the above [Al phase], [Zn ₂ Mg phase] and [Zn phase] is used as a lower layer, and a base is formed thereon. It has a treatment layer, and further, 5 to 50% by mass of silica particles (b) and 1 to 40% by mass of solid lubricant (c) with respect to 100% by mass of the solid content of the aqueous resin (a). applying the aqueous lubricant paint containing, film obtained by drying is formed at a coverage of 0.2-5 g / m ² Non removal membrane lubricating plated steel sheet with excellent workability, characterized in that there. On one or both sides of the steel sheet, Al: 4 to 22% by mass, Mg: 1 to 5% by mass, Ti: 0.1% by mass or less, Si: 0.5% by mass or less, with the balance being zinc and inevitable impurities 1 type of [Mg ₂ Si phase], [Al phase], [Zn ₂ Mg phase], and [Zn phase] in the substrate of [Al / Zn / Zn ₂ Mg ternary eutectic structure] Or, it has a metal structure in which two or more kinds are mixed, and further, Ti—Al-based intermetallic compound is contained in one or more kinds of the above [Al phase], [Zn ₂ Mg phase] and [Zn phase]. The zinc-based plating layer is used as a lower layer, and further, 5 to 50% by mass of silica particles (b) and a solid lubricant (c) with respect to 100% by mass of the solid content of the aqueous resin (a). the aqueous lubricant paint application containing 1 to 40 wt%, the film obtained by drying of 0.2-5 g / m ² Non removal membrane lubricating plated steel sheet with excellent workability, characterized in that it is formed by deposition amount.   The aqueous resin (a) is at least one selected from the group consisting of an aqueous epoxy resin, an aqueous phenol resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous polyolefin resin. 2. A non-delaminating lubricated plated steel sheet excellent in workability described in 2.   4. The non-delaminating lubricated plated steel sheet having excellent processability according to claim 1, wherein the aqueous resin (a) is a polyurethane resin having a polyester skeleton portion and a polyether skeleton.   The non-development excellent in processability according to claim 4, wherein the mass ratio of the polyether skeleton to the polyester skeleton of the polyurethane resin having a polyester skeleton portion and a polyether skeleton is 10:90 to 70:30. Film-type lubricated steel sheet.   6. The non-delaminating lubricated plated steel sheet having excellent workability according to claim 1, wherein the glass transition temperature (Tg) of the aqueous resin (a) is 70 ° C. or higher and 200 ° C. or lower.   The non-delaminating type lubricating plated steel sheet excellent in workability according to any one of claims 1 to 6, wherein the solid lubricant (c) is a polyolefin wax having a particle size of 0.1 to 5 µm.   The water-based lubricating paint further contains at least one crosslinking agent (d) selected from the group consisting of an amino resin, a polyisocyanate compound, its block, an epoxy compound, and a carbodiimide compound, and the solid content of the aqueous resin (a) is 100 mass. The non-delaminating lubricated plated steel sheet having excellent workability according to any one of claims 1 to 7, wherein the content is 1 to 40% by mass relative to%. 9. The non-delaminating type lubricated plated steel sheet having excellent workability according to claim 1, comprising a chromate film having a Cr adhesion amount of 5 to 100 mg / m ² as a base treatment layer. 9. A non-de-film having excellent workability according to claim 1, wherein the base treatment layer has a chemical conversion film of a phosphate film having an adhesion amount of 0.2 to 5.0 g / m ^2. Lubricating plated steel sheet. It has a film layer formed by applying and drying a surface treatment liquid containing an aqueous resin (e) as a surface treatment layer, and the coating amount of the film layer after drying is 10 to 3000 mg / m ^2. A non-delaminating lubricated plated steel sheet excellent in workability according to any one of claims 1 to 8.   The aqueous resin (e) is at least one selected from the group consisting of an aqueous epoxy resin, an aqueous phenol resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylic resin, and an aqueous polyolefin resin. Non-delaminating lubricated steel plate with excellent workability as described.   The base treatment layer further contains 1 to 300% by mass of the silane coupling agent (f) with respect to 100% by mass of the aqueous resin (e). Non-delaminating lubricated steel sheet.   The silane coupling agent (f) contains at least one selected from the group consisting of an epoxy group and an amino group as a reactive functional group. Film-type lubricated steel sheet.   The processing according to any one of claims 11 to 14, wherein the base treatment layer further contains 1 to 300% by mass of the polyphenol compound (g) with respect to 100% by mass of the solid content of the aqueous resin (e). Non-delaminating lubricated steel sheet with excellent properties.   The base treatment layer further contains at least one type (h) selected from the group consisting of phosphoric acid and hexafluorometal acid in an amount of 0.1 to 100% by mass with respect to 100% by mass of the solid content of the aqueous resin (e). The non-delaminating type lubricating plated steel sheet excellent in workability according to any one of claims 11 to 15.   The non-delaminating lubricating plating with excellent workability according to claim 16, wherein the hexafluorometal acid contains at least one element selected from the group consisting of Ti, Si, Zr, and Nb. steel sheet.   The base treatment layer further contains 0.1 to 100% by mass of the phosphate compound (i) with respect to 100% by mass of the solid content of the aqueous resin (e). Non-delaminating lubricated plated steel sheet with excellent workability as described in 1.   The workability according to claim 18, wherein the phosphate compound (i) contains at least one element selected from the group consisting of Mg, Mn, Al, Ca and Ni as a cation component. Excellent non-delaminating lubricated plated steel sheet.   Furthermore, the metal oxide particles (j) comprising at least one metal element selected from the group consisting of Si, Ti, Al, and Zr are added to the base treatment layer with respect to the solid content of 100% by mass of the aqueous resin (e). The non-delaminating lubricated plated steel sheet having excellent workability according to any one of claims 11 to 19, wherein the non-delaminating lubricated plated steel sheet is contained in an amount of 1 to 300% by mass.   21. The non-delaminating lubricated plated steel sheet having excellent workability according to claim 1, wherein the surface has a coefficient of dynamic friction of 0.09 or less. TiAl-based intermetallic compound according to any one of claims 1 to 21, non-film removal type lubricant coated steel sheet with excellent workability, characterized in that the TiAl _3. The Ti-Al-based intermetallic compound according to any one of claims 1 to 21 is Ti (Al _1-X Si _x ) ₃ (where X = 0 to 0.5). Non-delaminating lubricated plated steel sheet with excellent workability. The Ti-Al intermetallic compound contained in the [Al phase] in the plating layer is present in a Zn-Al eutectoid reaction structure in which the Zn phase is concentrated. 23. A non-delaminating lubricated steel sheet excellent in workability according to any one of 23 . 25. The non-delaminating lubricated plated steel sheet excellent in workability according to any one of claims 1 to 24 , wherein the size of the [Al phase] dendrites in the plating layer is 500 μm or less.

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