JP2002210866A - Surface-treated metallic sheet with outstanding press scoring resistance and coil deformation resistance and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated metallic sheet with outstanding press scoring resistance and coil deformation resistance and a manufacturing method for obtaining the surface-treated metallic sheet. SOLUTION: The 0.05-0.3 g/m2, in terms of a dry mass, of an aqueous organic and inorganic composite paint (E) constituted of a lubricant (A) 1 which is a polyolefin wax dispersion with a molecular weight of 6,000-15,000 obtained by adding an aqueous resin and/or a chloride silicate and water, and if necessary, a lubricant (B) 5 which is a polyolefin wax dispersion with a molecular weight of 1,000-5,000, are applied to the upper layer of a plated metallic sheet 3. Next, the aqueous organic and inorganic composite paint (E) is baked to form a first layer and 0.5-5.0 g/m2, in terms of a dry mass, of an aqueous organic and inorganic composite paint (F) which is constituted of the aqueous resin and/or the chloride silicate, a colloidal silica and water and contains 5-35 mass% of the colloidal silica in terms of a solid matter are applied and baked to form a second layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION An object of the present invention is to provide a coil which is excellent in various performances such as corrosion resistance, adhesion, weldability, etc., while maintaining press galling resistance, and crushing of a coil due to loose winding and load collapse during cutting of a cut plate. More particularly, the present invention relates to a surface-treated metal plate that suppresses the generation of sticky scum caused by the lubricant falling off from a film during pressing, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Surface-treated steel sheets, such as electro-galvanized steel sheets and hot-dip galvanized steel sheets, have been developed so far.
It is widely used in applications such as building materials and automotive parts. Many of these steel sheets are subjected to a chromate treatment, a phosphate treatment or the like for the purpose of improving corrosion resistance and paint adhesion.

Further, in recent years, in particular, in the home appliance industry, those which are applied without coating are increasing from the viewpoint of saving steps and costs, and not only corrosion resistance and paint adhesion but also galling resistance, fingerprint resistance, and fingerprint resistance are improved. The required level of various performances such as dew condensation unevenness on the surface appearance quality of a steel sheet is increasing. In order to respond to such performance demands from consumers, a coated metal plate in which an organic composite film based on a special resin is formed on a plated steel plate subjected to a chromate treatment has been developed.
For example, Japanese Patent Publication No. 4-14191 discloses that an organic composite film in which a colloid sol having a specific fine particle size is additionally adjusted to an aqueous organic resin is formed on a chromate-coated plated steel sheet to improve performance such as corrosion resistance and fingerprint resistance. A method for producing a surface-treated steel sheet is disclosed.

Japanese Patent Application Laid-Open No. 3-39485 discloses that after a chromate treatment is performed on a zinc-based plated steel sheet, silica and a wax having a glass transition point (Tg point) of 40 ° C. or higher are dispersed in an aqueous resin. 0.3 to 3 as the dry weight of the paint.
A coating with 0 g / m ² is disclosed. Japanese Patent Application Laid-Open No. Hei 3-28380 discloses that a paint composed of a carboxylated polyethylene resin and a Teflon (trademark) lubricant is subjected to a chromate treatment on an electrogalvanized steel sheet in a dry mass of 0.5 to 4%. A lubricated steel sheet coated with 0.0 g / m ² is disclosed. Furthermore, in order to meet the demands of consumers who require severe galling resistance, such as deep drawing workability, a surface treated steel sheet with improved lubricity by adding a solid lubricant to the organic film was developed. . For example, Japanese Patent Application Laid-Open No. 6-1
No. 73037 discloses a steel sheet having a lubricating film in which silica and a polyolefin wax are added to an ether / ester type urethane resin and an epoxy resin.

[0005] The technique disclosed in Japanese Patent Publication No. 4-14191 is excellent in a balance of performance such as corrosion resistance, paint adhesion, fingerprint resistance and dew condensation resistance, and is one of the main products for home appliances at present. Has been used as. However, even with such a surface-treated steel sheet coated with an organic film, scratches may occur during handling, galling during press working, and abrasion (abrasion) during product transportation may occur.

On the other hand, the techniques disclosed in JP-A-3-39485 and JP-A-3-28380 are less likely to cause galling and abrasion at the time of the press working described above. -173037
The technique disclosed in Japanese Patent Laid-Open Publication No. H10-143 has excellent press galling resistance even in severe processing such as deep drawing workability. However, JP-A-3-39485, JP-A-3-28380 and JP-A-6-173037
The surface of a steel plate manufactured by the technique disclosed in Japanese Patent Application Laid-Open Publication No. H11-163,199 is slippery, which causes problems such as coil collapse due to loose winding and load collapse during cutting plate piling. Therefore, in order to avoid these problems, countermeasures such as increasing the tension at the time of winding the coil and increasing the number of bands to prevent the coil from loosening after packing are being taken.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coil crushing due to loose winding and cutting plate piling, while maintaining excellent performance such as corrosion resistance, adhesion and weldability, and maintaining press galling resistance. It is an object of the present invention to provide a surface-treated metal plate that can solve problems such as collapse of a load and that suppresses the generation of sticky residue caused by the lubricant falling off from a film at the time of pressing, and a method of manufacturing the same.

[0008]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventors have found that a lubricant, which is a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000, is formed on an upper layer of a plated metal plate. (A) If necessary, an aqueous organic-inorganic composite paint (E) containing a lubricant (B), which is a polyolefin wax dispersion having a molecular weight of 1,000 to 5,000, is applied and baked to form a first layer. Then, after applying an aqueous organic-inorganic composite coating material (F) containing an appropriate amount of colloidal silica, the coating is baked to form a second layer, so that the dynamic friction coefficient of the metal plate surface is 0.07 to 0.1. 15, the static friction coefficient is set to 0.
The present inventors have found that a surface-treated metal plate that can be controlled to 10 or more and that can suppress the generation of sticky residue caused by the lubricant falling off from the film during pressing can be obtained, and have completed the present invention. That is, the gist of the present invention is as follows. (1) As the first layer, one or both of an aqueous resin and a silicate compound, and further, a molecular weight of 6000 to 15
Aqueous organic-inorganic composite film (C) containing a lubricant (A) composed of a polyolefin wax dispersion having a dry weight of 0.05 to 0.3 g / m ^2, and an aqueous resin as a second layer And an aqueous organic-inorganic composite film (D) composed of one or both of a silicate compound and a colloidal silica of 5 to 35% by mass in terms of a solid content as a dry mass of 0.5 to 5.0 g / m ^2. A surface-treated metal plate excellent in press galling resistance and coil deformation resistance characterized by having: (2) the lubricant (A) having a molecular weight of 6,000 to 15,000 containing no polar group and a particle size of 0.1.
A polyolefin wax dispersion having a molecular weight of 6,000 to 15,000, an acid value of 40 or less, and a particle size of 0.1 to 5.0 μm. A surface-treated metal sheet excellent in press galling resistance and coil deformation resistance according to the above (1);
(3) a lubricant (A) in which the aqueous organic-inorganic composite coating (C) is an aqueous resin and a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000;
(1) or (2), which is composed of a composite lubricant mixed with a lubricant (B) that is a polyolefin wax dispersion of up to 5000. (4) a polyolefin wax dispersion in which the lubricant (A) does not contain a polar group and has a molecular weight of 6,000 to 15,000 and a particle size of 0.1 to 5.0 μm, and a molecular weight of 60
00-15000, acid value 40 or less, particle size 0.1-5.0
at least one lubricant selected from modified polyolefin wax dispersions having a molecular weight of 1,000 to 5,000, wherein the lubricant (B) does not contain a polar group;
(5) a surface-treated metal sheet excellent in press galling resistance and coil deformation resistance according to (3), which is a polyolefin wax dispersion having a particle size of 0.1 to 3.0 μm; Dynamic friction coefficient is 0.07 to 0.1
5. The surface-treated metal sheet excellent in press galling resistance and coil deformation resistance according to the above (1) to (4), wherein the static friction coefficient is 0.10 or more; (6) a plated metal sheet An aqueous organic and inorganic composite paint (E) composed of one or both of an aqueous resin and a silicate compound, a lubricant (A) which is a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000, and water is provided on the upper layer. After applying 0.05 to 0.3 g / m ^{2 in} terms of dry mass, it is baked to form a first layer, and then is composed of one or both of an aqueous resin and a silicate compound, colloidal silica and water. and after the aqueous organic-inorganic composite coating material (F) was 0.5 to 5.0 g / m ² coating on a dry mass conversion is 5 to 35 mass% content of colloidal silica in terms of solid content, baked and second layer Shape eyes A method of producing a surface-treated metal sheet having excellent resistance to press galling and coil deformation, characterized in that (7) the lubricant (A) has a polar group-free molecular weight of 6,000 to 15,000 and a particle size of 0. 0.1 to 5.0 μm polyolefin wax dispersion and molecular weight 600
0-15000, acid value 40 or less, particle size 0.1-5.0μ
m, wherein at least one kind of lubricant selected from modified polyolefin wax dispersions is used. (8) the aqueous organic-inorganic composite coating material (E) is an aqueous resin having a molecular weight of 60;
Lubricant (A) which is a polyolefin wax dispersion having a molecular weight of 1,000 to 5,000
The above-mentioned (6) or (7), which comprises a composite lubricant obtained by mixing a lubricant (B), which is a polyolefin wax dispersion, and water. A method for producing a surface-treated metal sheet having excellent deformability, (9) the lubricant (A) has a molecular weight of 6,000 to 15000 containing no polar group, and a particle size of 0.1 to 5.
0 μm polyolefin wax dispersion, molecular weight 6,000-15,000, acid value 40 or less, particle size 0.1
At least one lubricant selected from modified polyolefin wax dispersions of up to 5.0 μm,
Lubricant (B) having a molecular weight of 1000 to 50 containing no polar group
(6) characterized in that it is a polyolefin wax dispersion having a particle size of 0.1 to 3.0 μm.
(8) A method for producing a surface-treated metal sheet excellent in press galling resistance and coil deformation resistance according to (8).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Conventionally, in order to improve the press galling resistance of an aqueous organic-inorganic composite coated steel sheet, a method of adding a lubricant such as a polyolefin wax having a low molecular weight to an aqueous organic-inorganic composite coating on the steel sheet is generally used. I have. By blending such a low molecular weight polyolefin wax dispersion having no polar group into the aqueous organic / inorganic film, the wax is present in a granular form on the film surface, and the affinity of the metal plate surface can be reduced. At the same time, the wax is crushed during the press working, and a lubricating layer is formed between the steel plate and the mold. Therefore, an excellent lubricating effect can be obtained, and galling at the time of pressing can be reduced.

On the other hand, in the present invention,
First, as a first layer, an aqueous organic-inorganic composite film (C) composed of one or both of an aqueous resin and a silicate compound and a lubricant (A) which is a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 is defined as a dry mass. 0.05 to 0.3 g / m ² has one or both of the aqueous resin and silicate compounds, the content of which is composed of colloidal silica and colloidal silica in terms of solid content 5 to 35 as a second layer Mass% organic composite film (D)
Of 0.5 to 5.0 g / m ² as a dry mass.

FIG. 1 shows an example of a surface-treated metal plate according to the first embodiment of the present invention, and FIG. 2 shows an example of a surface-treated metal plate according to the second embodiment of the present invention. In FIG. 1, a surface-treated metal sheet according to a first embodiment of the present invention comprises a first aqueous-organic composite coating (C) 2 and a second aqueous-organic composite coating (D) on a plated metal plate 3. ) 4. The first layer of the aqueous organic / inorganic composite film (C) 2 is prepared by coating one or both of an aqueous resin and a silicate compound, and a coating material (E) composed of a lubricant (A) and water by an appropriate method. And then baking to form an aqueous organic-inorganic composite paint (F) composed of one or both of an aqueous resin and a silicate compound, and further composed of colloidal silica and water, as a second layer. After coating by a method, it is formed by baking.

In FIG. 2, a surface-treated metal plate according to a second embodiment of the present invention has a first-layer aqueous organic-inorganic composite film (C ′) 2 and a second-layer aqueous The structure has an organic-inorganic composite film (D) 4. The first layer of the aqueous organic / inorganic composite film (C ′) 2 is a coating material composed of one or both of an aqueous resin and a silicate compound, a lubricant (A), a lubricant (B), and water ( E) is applied by an appropriate method and then baked to form an aqueous organic / inorganic composite coating composed of one or both of an aqueous resin and a silicate compound, furthermore, colloidal silica and water as a second layer. After applying (F) by an appropriate method,
It is formed by baking.

As described above, the aqueous organic-inorganic composite coating (C) or (C ') is formed by adding the polyolefin wax dispersion whose molecular weight is adjusted to an appropriate value, and the aqueous organic-inorganic composite coating is formed on the aqueous organic-inorganic composite coating. By forming (D), the wax is made to protrude from the bottom of the aqueous organic / inorganic composite coating (D) to the coating surface in a granular manner, and at the same time, the hardness of the wax and the affinity of the coating surface are controlled. Further, the content of silica in the aqueous organic / inorganic composite film (D) is adjusted to achieve compatibility between film hardness and film performance such as corrosion resistance and adhesion.
As described above, not only has good corrosion resistance and adhesion, but also has a dynamic friction coefficient of 0.07 to 0.15, and has a static friction coefficient of 0.10 or more, and is excellent in press galling resistance and coil deformation resistance, Furthermore, a surface-treated metal plate that can suppress the generation of sticky residue caused by the lubricant falling off from the film during pressing can be obtained.

Hereinafter, a method for producing a surface-treated metal sheet excellent in press galling resistance and coil deformation resistance according to the present invention will be described. As a base plating metal plate applicable in the present invention, a zinc plating metal plate, a zinc-nickel plating metal plate,
Zinc-based electroplating and melting of zinc-iron plated metal plate, zinc-chrome plated metal plate, zinc-aluminum plated metal plate, zinc-titanium plated metal plate, zinc-magnesium plated metal plate, zinc-manganese plated metal plate Plating,
Evaporated plated steel sheet, aluminum or aluminum alloy plated metal sheet, lead or lead alloy plated metal sheet, tin or tin alloy plated metal sheet, and a small amount of different metal elements or impurities such as cobalt, molybdenum, tungsten, nickel , Titanium, chromium, aluminum, manganese, iron, magnesium, lead, antimony, tin, copper, cadmium, arsenic and the like, and / or those in which inorganic substances such as silica, alumina and titania are dispersed. Further, the present invention is also applicable to a multi-layer plating in which the above plating is combined with another type of plating, for example, iron plating, iron-phosphorus plating, or the like.

It is preferable that the coating weight of each plated metal plate is 1 g / m ² or more on one side, and if it is less than this, the corrosion resistance decreases. The surface-treated metal plate of the present invention can be obtained by subjecting a plated metal plate to a base treatment for the purpose of improving adhesion or corrosion resistance, and then forming an aqueous organic-inorganic composite film. It is also possible to obtain by directly forming an aqueous organic / inorganic composite coating without applying the coating.
The undercoating treatment is not particularly limited as long as the above object can be achieved, but generally, a chromate treatment capable of improving corrosion resistance and adhesion is preferable.

Means for forming a chromate film include, for example, immersion (reaction type) chromate treatment in an aqueous solution mainly containing chromic anhydride, chromate, and dichromate, electrolytic chromate treatment, and the above-mentioned aqueous solution. And a coating solution in which colloidal silica or the like is mixed and dried without washing with water.

The amount of chromate adhered is 5 to 100 in terms of Cr.
It is preferably about mg / m ² . If the adhesion amount is less than 5 mg / m ^{2 in} terms of Cr, sufficient corrosion resistance cannot be obtained, and
If it exceeds 0 mg / m ² , cohesive failure of the chromate film itself will occur, and paint adhesion will decrease. As the aqueous resin used in the present invention, acrylic ester / acrylic acid copolymer, epoxy / acrylic acid, olefin acrylic acid copolymer,
An olefin ionomer, a styrene acrylic acid copolymer, a urethane acrylic acid copolymer, a urethane epoxy resin, an ethylene imine acrylic resin, or the like can be used. As the coating, it is preferable to use an emulsion dispersed in an aqueous solvent. If necessary, a crosslinking agent such as various melamine resins and amino resins may be added. In addition, it is more preferable to select a highly hydrophilic resin as the aqueous resin used for the first layer. In addition, as the resin used for the second layer, it is preferable to use an acrylic resin such as an olefin acrylic acid copolymer, particularly when both performance and cost are taken into consideration. In this case, it is preferable to use a urethane epoxy resin having both hardness and elongation.

The silicate compound used in the present invention is generally represented by M ₂ O.nSiO ₂ (M is an alkali metal such as sodium, potassium and lithium, and n is an arbitrary value), and includes sodium silicate, potassium silicate, It is a mixture of at least one kind selected from lithium silicate. N, which is the molar ratio of M ₂ O to SiO ₂
Is preferably in the range of 1 to 10. If the value of n is less than 1, the resulting film tends to absorb moisture and the adhesion of the film becomes insufficient. On the other hand, if it exceeds 10, the obtained film becomes brittle and the workability deteriorates, which is not preferable.

As the colloidal silica used in the present invention, any one of spherical, linear, and beaded silica having branched spherical colloidal silica bonded thereto may be used. In the case of spherical silica, the particle diameter is 5 to 50 nm, and in the case of linear silica, the diameter is 5 to 50 nm and the length / thickness ratio is 1
In the case of a beaded silica having a branch chemically bonded to -5 or [branched silica] [Length of bonded body / average particle diameter of spherical silica]
Are preferably 4 or more and have one or more branches.

These colloidal silicas are blended in the aqueous organic / inorganic composite coating material (F) of the present invention in an amount of 5 to 35% by mass in terms of solid content. If it is less than 5% by mass, sufficient corrosion resistance and press galling resistance cannot be obtained, and if it exceeds 35% by mass, paint adhesion and press galling resistance deteriorate. In the present invention, a predetermined amount of the lubricant (A) or the lubricants (A) and (B) is blended with the aqueous resin, colloidal silica, and water in the aqueous organic-inorganic composite paint (E). Here, a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 is used as the lubricant (A), and a polyolefin wax dispersion having a molecular weight of 1,000 to 5,000 is used as the lubricant (B). More preferably, as the lubricant (A), a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 and a particle size of 0.1 to 5.0 μm containing no polar group, and a molecular weight of 6,000
１５15000, acid value 40 or less, particle size 0.1０．１5.0 μm
At least one lubricant selected from the group consisting of modified polyolefin wax dispersions having a molecular weight of 1000 to 50 containing no polar group as the lubricant (B).
A polyolefin wax dispersion having a particle size of 0.1 to 3.0 μm is used.

As the polyolefin wax dispersion, those obtained by dispersing polyethylene wax, polypropylene wax, or polybutylene wax in an emulsifier concentration of 5% or less, preferably in water or an aqueous solution without using an emulsifier, are used. Further, as the modified polyolefin wax dispersion, a dispersion obtained by dispersing polyethylene wax, polypropylene wax, and polybutylene wax in an emulsifier concentration of 5% or less, preferably in water or an aqueous solution without using an emulsifier, is used. Polar groups, in the presence of a catalyst, oxygen, polyolefin wax obtained by oxidizing polyolefin wax with an oxidizing agent such as ozone or nitric acid, or acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, It is obtained by dissolving an ethylenically unsaturated carboxylic acid monomer such as itaconic acid and a polyolefin wax with benzol or the like, and heating and grafting with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.) in a nitrogen stream.

The mass average particle diameter of the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (A) is 0.1 to 5.0 μm.
m is preferable, and more preferably 1.0 to 4.0 μm is used. Further, the lubricant (A) having a particle size larger than the thickness of the aqueous organic / inorganic composite film (D) formed on the upper layer is used. When the mass average particle diameter of the lubricant (A) is less than 0.1 μm, it is not preferable because it tends to aggregate and has poor stability. When the mass average particle diameter of the lubricant (A) is smaller than that of the aqueous organic-inorganic composite film (D) formed on the upper layer, the press galling resistance deteriorates, which is not preferable. On the other hand, when the mass average particle size exceeds 5.0 μm, the dispersion stability is poor, so that it is not preferable. The ratio of the mass average particle diameter to the number average particle diameter is as follows: mass average particle diameter / number average particle diameter <
It is preferably within the range of 3.

The weight average particle diameter of the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (B) is 0.1 to 3.0 μm.
m is preferred. Further, the lubricant (B) having a particle size smaller than the thickness of the aqueous organic-inorganic composite film (D) formed on the upper layer is used. If the mass average particle size is less than 0.1 μm, it is not preferable because it tends to aggregate and has poor stability. Further, when the thickness exceeds 3.0 μm or when a lubricant (B) having a particle diameter larger than the thickness of the aqueous organic / inorganic composite coating (D) is used, the coil deformation resistance is poor, which is not preferable.

The range of the mass average molecular weight of the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (A) is as follows.
Those having 6000 to 15000 are preferred. If the weight average molecular weight is less than 6000, the coil deformation resistance is poor, so that it is not preferable. Further, when the weight average molecular weight exceeds 15,000, press galling resistance is inferior, so that it is not preferable.

The weight average molecular weight of the polyolefin wax dispersion in the lubricant (B) is preferably from 1,000 to 5,000. When the mass average molecular weight is less than 1,000, thermal decomposition easily occurs, and
A direct-fired drying furnace exposed to a high temperature close to ° C is not preferable because sufficient lubrication characteristics may not be obtained. On the other hand, if the average molecular weight exceeds 5,000, the effect of adding the lubricant B is not preferable because the effect of further improving the anti-seizing property cannot be obtained.

The method and conditions for analyzing the weight average molecular weight of these polyolefin wax dispersions and modified polyolefin wax dispersions are shown below, but the molecular weight analysis is not limited to this method alone.・ Analytical method: GPC for high temperature (gel permeation chromatography) ・ Column: Mixed type of PS (polystyrene) gel (2-4 connected in series) ・ Solvent: o-dichlorobenzene (ODCB), trichlorobenzene (TCB), etc.-Measurement temperature: 130 to 140 ° C-Detector: Differential refractometer (RI) or infrared detector-Preparation of calibration curve: Converted to each molecular weight using commercially available monodispersed PS.

Further, JIS K 5902 of the modified polyolefin wax dispersion in the lubricant (A)
Is preferably 40 or less. If the acid value exceeds 40, the lubricant becomes too hard, so that sufficient lubricity cannot be obtained. further,
The density specified by JIS K 6760 for the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (A) is 950.
１０００1000 kg / m ³ , and the hardness (penetration) specified by JIS K 2207 is 0.2 mm or less,
The degree of crystallinity determined by the X-ray diffraction method is preferably 80% or more and the melting point is preferably 110 to 150 ° C.

The lubricant (A) or the total content of the lubricants (A) and (B) is preferably 2 to 60% by mass in terms of solid content in the aqueous organic / inorganic composite paint. If the amount is less than 2% by mass, sufficient resistance to press galling cannot be obtained, and if it exceeds 60% by mass, the paint adhesion deteriorates, which is not preferable. The amount of these aqueous organic-inorganic composite coatings (C) to be applied is 0.05 to 0.3 as a dry mass.
g / m ² . More preferably 0.05 to 0.2 g
/ M ² . Is not preferable because the amount adhering is difficult to withstand press-galling properties of interest is poor, also the wettability exceeds 0.3 g / m ² to form an upper layer film decreases is less than 0.05 g / m ² . Aqueous organic-inorganic composite coating (D)
Ranges from 0.5 to 5.0 g / m ² as a dry mass.
And More preferably, it is 1.0 to 3.0 g / m ² . If the amount is less than 0.5 g / m ² , the desired resistance to press galling will be poor, and if it exceeds 5.0 g / m ² , the weldability will be difficult, which is not preferable.

As a coating method for forming these aqueous organic / inorganic composite films, any method such as spraying, curtain, flow coater, roll coater, bar coater, brush coating, dipping, and air knife drawing may be used. . Further, the baking temperature is desirably set to 80 to 250 ° C. More preferably, the temperature is preferably higher than the melting point of the lubricant used. If the temperature is lower than 80 ° C., the water in the paint is difficult to completely volatilize, so that the corrosion resistance is lowered, and
If the temperature exceeds 0 ° C., the curing of the film is excessively advanced, and the workability is deteriorated.

Although there is no particular limitation on the drying equipment, a method using hot air blowing, a method using indirect heating with a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted. The coefficient of kinetic friction of the surface-treated metal plate surface of the present invention is 0.07 to 0.5.
15. It is preferable that the coefficient of static friction is 0.10 or more. When the dynamic friction coefficient is higher than 0.15, the resistance to press galling is poor, and when the dynamic friction coefficient is 0.07 and the static friction coefficient is lower than 0.10.

[0031]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. (1) Kinds of drugs Table 1 shows a list of drugs used in the examples. Here, as the lubricant A excluding D7, the density specified by JIS K 6760 is 950 to 1000 kg / m ³ ,
The hardness (penetration) specified by K 2207 is 0.2 mm
Below, the crystallinity determined by the X-ray diffraction method was 80% or more and the melting point was 110 to 150 ° C.

[0032]

[Table 1]

(2) Kinds of Metal Plate The metal plates shown in Table 2 were used.

[0034]

[Table 2]

(3) Chromate treatment EG and ZN shown in Table 2 were converted to an electrolytic type by passing a predetermined amount of electricity at a current density of 10 A / dm ² in a bath of chromic acid 50 g / l and sulfuric acid 0.3 g / l. After a chromate treatment and washing with water, the plate was dried at a reaching plate temperature of 80 ° C. using a hot air drying furnace.
GI shown in Table 2 was coated with a chromate treatment solution in which reduced chromic acid and silica having a reduction ratio of 40% were mixed at a ratio of SiO ₂ / CrO ₃ of 3 and then dried without washing with water. The amount of the chromate film deposited was quantified in terms of Cr by fluorescent X-ray analysis. (4) Adjustment of aqueous-organic composite paint One or both of the aqueous resin and the silicate compound shown in Table 1, colloidal silica, and a lubricant are blended in the ratios shown in Tables 4 to 6 to prepare the aqueous-organic composite paint. did. (5) Coating and drying method of aqueous organic-inorganic composite paint The plated metal plate subjected to the chromate treatment shown in (3)
The aqueous organic-inorganic composite paint prepared in (4) was applied so as to have a dry mass having a value shown in Tables 4 to 6, and the ultimate plate temperature was 14
The sample for evaluation was prepared by baking and drying at 0 ° C. The amount of the organic composite film deposited was calculated by measuring the amount of the liquid film at the time of coating by a mass method. (6) Performance evaluation items a: Flat plate corrosion resistance The evaluation sample prepared in (5) was tested in accordance with the salt spray test method described in JIS Z 2371. Was sprayed on a coated steel sheet sample, and the white rust occurrence rate after 72 hours was measured. In the following evaluations, ◎ and ○ were judged to be good.

◎: No white rust generated ○: White rust generation rate less than 10% △: White rust generation rate 10% or more and less than 50% ×: White rust generation rate 50% or more b: Corrosion resistance at the processed part (5) A 6 mm Erichsen process was performed on the test sample for evaluation, and a 5% NaCl aqueous solution was sprayed on the coated steel plate sample at an ambient temperature of 35 ° C. according to the salt spray test method described in JIS Z 2371 for 48 hours. The white rust occurrence rate in the later processed part was measured. In the following evaluations, ◎ and ○ were judged to be good.

◎: No white rust generated ○: White rust generation rate of less than 5% △: White rust generation rate of 5% or more and less than 20% ×: White rust generation rate of 20% or more c: Paint adhesion (5) Using a bar coater, a melamine alkyd resin paint (manufactured by Kansai Paint Co., Ltd., Amirac # 1000) was further applied to the evaluation sample thus obtained, to a dry film thickness of 25 μm.
m and baked at a furnace temperature of 130 ° C. for 20 minutes.
Next, after being left overnight, those immersed in boiling water for 30 minutes and those not immersed were subjected to 7 mm Erichsen processing, and an adhesive tape (Nichiban Co., Ltd .: Scotch tape)
Was adhered to the Erichsen-processed portion of the test piece. The adhesive tape was quickly pulled obliquely at an angle of 45 °, and the appearance of the Erichsen processed portion was visually evaluated. In the following evaluations, ◎ and ○ were judged to be good.

◎: No peeling ○: Peeling area ratio less than 5% △: Peeling area ratio 5% or more and less than 50% ×: Peeling area ratio 50% or more d: Continuous weldability Table 3 shows the samples prepared in (5). A continuous spot welding test was performed under the conditions shown in (1), and the number of spots at which a nugget diameter of 3 mmφ or more could be formed stably was determined.

[0039]

[Table 3]

In the following evaluations, ◎ and ○ were judged to be good. ◎: The number of spots is 5,000 or more ○: The number of spots is 2,500 or more and less than 5,000 Δ: The number of spots is 1000 or more and less than 2500 ×: The number of hits is less than 1000 e: Press galling resistance The sample prepared in (5) was subjected to a square cylinder crank press test. . The conditions of the rectangular cylinder crank press test were as follows: a sample (0.8 × 220 × 180 mm) was molded to a size of 65 × 115 mm and a height of 50 mm with a wrinkle holding pressure of 6 tons, and the sliding surface after the molding was visually evaluated. . In the following evaluations, ◎ and ○ were judged to be good.

◎: no blackening ○: less than 50% of the sliding portion is blackened and has sliding flaws △: 50% or more of the sliding portion is blackened and has sliding flaws ×: base metal F: Explosion resistance test of surface layer lubricant The sample prepared in (5) was subjected to the square cylinder crank press test 100 times continuously. After the continuous press test, the state of peeling of the surface lubricant attached to the mold was observed and evaluated. ○ was determined to be good in the following evaluations.

：: No sticky lubricating substance was deposited. X: Sticky lubricating substance was deposited. G: Abrasion resistance test: 10 g of the sample prepared in (5) via vinyl.
Elliptical vibration was applied 360 times / minute under a load of / cm ² to generate abrasion at the sliding portion. After performing the test for 10 minutes, the sample surface was visually evaluated. In the following evaluations, ◎ and ○ were judged to be good.

◎: no blackening ○: less than 50% of the sliding portion is blackened △: 50% or more of the sliding portion is blackened ×: base metal is exposed h: static friction coefficient Shinto Kagaku Using a 10D HEIDON static friction coefficient measuring device, a sample with an area of 25 cm ² , from which burrs were removed, prepared in (5) was attached to a plane indenter at 0.5 ° / sec, and prepared in (5) under the condition of a weight of 200 g. The coefficient of static friction between the samples thus obtained was measured.

I: Dynamic friction coefficient The dynamic friction coefficient of the sample prepared in (5) was measured using a Shinto Scientific 14S HEIDON dynamic friction coefficient measuring apparatus under the conditions of 10 mmφ stainless steel ball sliding, load of 100 g, and sliding speed of 150 mm / min. It was measured. j: Coil deformation resistance 10 tons with an inner diameter of 508 mm with a plate thickness of 1 mm and different friction coefficients
After manufacturing several types of coils and lifting and lowering the coils three times with a crane, the deviation (distance) of the coil winding direction (longitudinal direction) end caused by loosening of the outermost winding is measured, and the dynamic friction coefficient, The relationship with the coefficient of static friction was investigated.
As a result, the deviation (distance) of the end of the coil winding direction (longitudinal direction) caused by the dynamic friction coefficient, static friction coefficient, and loose winding
When the dynamic friction coefficient is less than 0.07 and the static friction coefficient is less than 0.10, the displacement of the coil end due to loosening is 50 mm or more, but the dynamic friction coefficient is 0.07 or more, By setting the static friction coefficient to 0.10 or more, the displacement of the coil end due to loose winding could be suppressed to 30 mm or less. Therefore, in a laboratory test, the dynamic friction coefficient and the static friction coefficient measured in 7) and 8) were used as indices of coil deformation resistance. ○ was determined to be good in the following evaluations.

: Dynamic friction coefficient: 0.07 or more, static friction coefficient: 0.1 or more ×: Dynamic friction coefficient: less than 0.07, static friction coefficient: 0.
Tables 7 to 9 show the evaluation results of less than 1. As is evident from these results, the technology of the present invention is excellent in various properties such as corrosion resistance, adhesion, weldability, and is excellent in press galling resistance and coil deformation resistance. It is possible to obtain a surface-treated metal plate in which the generation of sticky residue caused by falling off is suppressed.

[0046]

[Table 4]

[0047]

[Table 5]

[0048]

[Table 6]

[0049]

[Table 7]

[0050]

[Table 8]

[0051]

[Table 9]

[0052]

The surface-treated metal sheet of the present invention is excellent in various performances such as corrosion resistance, adhesion, weldability, etc., while maintaining the press galling resistance, while crushing the coil due to loose winding and load during cutting board piling. It is suitable as a material for home electric appliances, building materials and automobile fields, because it has improved the problem of collapse and also suppressed the generation of sticky residue caused by the lubricant falling off from the film during pressing. Further, by the production method according to the present invention, a surface-treated metal plate having good press galling resistance and coil deformation resistance can be provided to the market.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of a surface metal plate of the present invention.

FIG. 2 is a diagram illustrating another example of the surface metal plate of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Lubricant (A) 2 ... Aqueous organic-inorganic composite film (C, C ') 3 ... Plating metal plate 4 ... Aqueous organic-inorganic composite film (D) 5 ... Lubricant (B)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 123/02 C09D 123/02 201/00 201/00 C23C 22/00 C23C 22/00 Z 22/53 22 / 53 28/00 28/00 C (72) Inventor Yujiro Miyauchi 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Corporation Kimitsu Works (72) Inventor Akira Takahashi 1 Kimitsu, Kimitsu-shi, Chiba New Japan F-term in Kimitsu Works (Reference) 4D075 AE03 CA09 DA03 DB01 DC10 EA06 EA37 EB13 EB42 EB52 EB57 EC03 4F100 AA03B AA03C AA20C AB01A AJ11B JAKA BAKB BA07B05 J07 YY00B YY00C 4J038 CB002 CC061 CG021 CG141 CJ011 CJ131 CJ261 CJ271 CJ281 DA132 DB211 DB281 GA16 HA436 HA446 KA06 MA08 MA10 MA14 NA03 NA12 NA23 PB03 PB05 PB07 PB09 PC02 4K026 A A02 AA07 AA12 AA13 AA22 BA01 BA02 BA06 BA12 BB04 BB06 BB08 BB09 BB10 CA19 CA21 CA27 CA39 CA41 DA02 DA11 DA15 DA16 EB08 EB11 4K044 AA02 AB02 BA10 BA14 BA15 BA21 BB04 BC01 BC02 BC04 BC05 CA17 CA17

Claims (9)

[Claims] 1. A first layer comprising one or both of an aqueous resin and a silicate compound, further having a molecular weight of 6,000 to 15,
Aqueous organic-inorganic composite film (C) containing a lubricant (A) composed of a polyolefin wax dispersion having a dry weight of 0.05 to 0.3 g / m ^2, and an aqueous resin as a second layer And an aqueous organic-inorganic composite film (D) composed of one or both of a silicate compound and colloidal silica of 5 to 35% by mass in terms of solid content as a dry mass of 0.5 to 5.0 g / m ^2. A surface-treated metal sheet excellent in press galling resistance and coil deformation resistance characterized by having. 2. A polyolefin wax dispersion wherein the lubricant (A) does not contain a polar group and has a molecular weight of 6,000 to 15,000 and a particle size of 0.1 to 5.0 μm, and a molecular weight of 60.
00-15000, acid value 40 or less, particle size 0.1-5.0
The surface-treated metal sheet having excellent press galling resistance and coil deformation resistance according to claim 1, characterized in that it is at least one kind of lubricant selected from a modified polyolefin wax dispersion of μm. 3. A lubricant (A) wherein the aqueous organic-inorganic composite coating (C) is an aqueous resin and a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000, and a lubricant (B) which is a polyolefin wax dispersion having a molecular weight of 1,000 to 5,000. 3. The surface-treated metal sheet according to claim 1, wherein the surface-treated metal sheet has excellent press galling resistance and coil deformation resistance. 4. A polyolefin wax dispersion in which the lubricant (A) does not contain a polar group and has a molecular weight of 6,000 to 15,000 and a particle size of 0.1 to 5.0 μm, and a molecular weight of 60.
00-15000, acid value 40 or less, particle size 0.1-5.0
at least one kind of lubricant selected from a modified polyolefin wax dispersion of μm, wherein the lubricant (B) has a polar group-free molecular weight of 1,000 to 5,000,
4. The surface-treated metal sheet according to claim 3, which is a polyolefin wax dispersion having a particle size of 0.1 to 3.0 [mu] m. 5. The surface has a dynamic friction coefficient of 0.07 to 0.1.
5. The surface-treated metal sheet excellent in press galling resistance and coil deformation resistance according to any one of claims 1 to 4, wherein the coefficient of static friction is 0.10 or more. 6. An aqueous resin and / or a silicate compound, further having a molecular weight of 600,
A lubricant (A), which is a polyolefin wax dispersion of 0 to 15,000, and an aqueous organic-inorganic composite paint (E) composed of water are used in an amount of 0.05 to 0.3 in terms of dry mass.
g / m ² and then baked to form a first layer, and then composed of an aqueous resin or / and a silicate compound, colloidal silica and water and having a colloidal silica content of 5 in terms of solids. The aqueous organic-inorganic composite paint (F) having a dry mass of 0.5 to 5.0 g /
After m ² coating, baking and anti-press galling resistance and method of manufacturing the excellent surface treated metal plate resistance coil deformability, characterized by forming the second layer. 7. A polyolefin wax dispersion in which the lubricant (A) does not contain a polar group and has a molecular weight of 6,000 to 15,000 and a particle size of 0.1 to 5.0 μm, and a molecular weight of 60.
00-15000, acid value 40 or less, particle size 0.1-5.0
7. The method for producing a surface-treated metal sheet having excellent press galling resistance and coil deformation resistance according to claim 6, wherein the lubricant is at least one or more kinds of lubricants selected from a modified polyolefin wax dispersion of μm. 8. The lubricant (A), wherein the aqueous organic-inorganic composite paint (E) is an aqueous resin, a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000, and a molecular weight of 1
The anti-press galling and coil resistance according to claim 6 or 7, comprising a composite lubricant obtained by mixing a lubricant (B), which is a polyolefin wax dispersion of 000 to 5000, and water. A method for producing a surface-treated metal sheet having excellent deformability. 9. The polyolefin wax dispersion wherein the lubricant (A) does not contain a polar group and has a molecular weight of 6,000 to 15,000 and a particle size of 0.1 to 5.0 μm, and a molecular weight of 60.
00-15000, acid value 40 or less, particle size 0.1-5.0
at least one kind of lubricant selected from a modified polyolefin wax dispersion of μm, wherein the lubricant (B) has a polar group-free molecular weight of 1,000 to 5,000,
The surface-treated metal sheet having excellent press galling resistance and coil deformation resistance according to any one of claims 6 to 8, wherein the polyolefin wax dispersion has a particle size of 0.1 to 3.0 µm. Manufacturing method.