WO2002057510A1

WO2002057510A1 - Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same

Info

Publication number: WO2002057510A1
Application number: PCT/JP2002/000359
Authority: WO
Inventors: Kengo Yoshida; Atsushi Morishita; Yujiro Miyauchi; Akira Takahashi
Original assignee: Nippon Steel Corporation
Priority date: 2001-01-19
Filing date: 2002-01-18
Publication date: 2002-07-25
Also published as: KR20030077580A; MY128667A; KR100543157B1; CN1488010A; CN1276995C; TW573062B; KR20050105288A

Abstract

A surface-treated metal sheet having a coating film formed in an amount of 0.3 to 5.0 g/m2 from a water-based organic/inorganic composite coating material which comprises: a lubricant comprising either (1) a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 or (2) a combination of a polyolefin wax dispersion (A) having a molecular weight of 6,000 to 15,000 and a polyolefin wax dispersion (B) having a molecular weight of 1,000 to 5,000; and colloidal silica of 5 to 35 wt.% on a solid basis. Also provided is a surface-treated metal sheet which has a first layer which is a coating film formed in an amount of 0.05 to 0.3 g/m2 on a dry basis from a water-based organic/inorganic composite comprising a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 and a second layer which is a coating film formed in an amount of 0.5 to 5.0 g/m2 on a dry basis from a water-based organic/inorganic composite comprising colloidal silica of 5 to 35 wt.% on a solid basis. The water-based organic/inorganic composite coating material with which these surface-treated metal sheets can be produced is further provided.

Description

Description Surface treated metal sheet excellent in press galling resistance and coil deformation resistance and manufacturing method

The present invention provides a surface-treated metal sheet that is suitably used for automobiles, home appliances, building materials, and the like, and is excellent in various properties such as corrosion resistance, adhesion, and weldability, as well as excellent in press galling resistance and coil deformation resistance. And a method for producing the same, and an aqueous organic-inorganic composite paint capable of obtaining a surface-treated metal plate.

The present invention also provides a surface excellent in various properties such as corrosion resistance, adhesion and weldability, and also excellent in press galling resistance and continuous sliding wear resistance, which is also suitably used for automobiles, home appliances, building materials and the like. The present invention relates to a treated metal sheet, a method for producing the same, and a water-based organic inorganic composite paint capable of producing the surface-treated metal sheet.

The present invention further provides various performances such as corrosion resistance, adhesion, and weldability, which are also suitably used for automobiles, home appliances, building materials, and the like, while maintaining coil press resistance while maintaining press galling resistance. Surface treated metal sheet that has improved the problems such as collapse of the load at the time of cutting and cutting board pilling, and also suppressed the generation of sticky residue caused by the lubricant falling off from the film at the time of pressing, and a method of manufacturing the same. . Background art

To date, surface-treated steel sheets, such as electro-zinc coated steel sheets and hot-dip zinc-coated steel sheets, have been developed and widely used in applications such as home appliances, building materials, and automotive parts. In addition, many of these steel sheets have corrosion resistance In addition, chromate treatment and phosphate treatment are applied for the purpose of improving paint adhesion.

Furthermore, in recent years, in particular, in the home appliance industry, those that are applied unpainted have been increasing from the viewpoint of saving processes and costs. Not only corrosion resistance and paint adhesion, but also galling resistance, fingerprint resistance, and The demand for various performance requirements for the surface appearance quality of steel sheets, such as unevenness of dew condensation, is increasing.In order to respond to such performance demands from customers, special resin is applied on the steel sheet with a chromate treatment. Painted metal sheets with an organic composite film as the base have been developed. For example, Japanese Patent Publication No. 4-141191 discloses the formation of an organic composite film in which a colloid sol of a specific fine particle size is added to a water-based organic resin on a steel plate coated with chromate, and the corrosion resistance is improved. A method of manufacturing a surface-treated steel sheet with improved performance such as fingerprint resistance is disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 3-394855 discloses that after subjecting a zinc-based plated steel sheet to a close mate treatment, the aqueous resin has silica and a glass transition point (T g point) of 40 ° C. A coating material in which the above-mentioned paint is dispersed is coated with 0.3 to 3.0 g Zm ² as a dry mass. Japanese Patent Application Laid-Open No. 3-28380 discloses that after a chromate treatment is applied to a galvanized steel sheet, a carboxylated polyethylene resin and a Teflon (trademark) lubricant are used. A lubricated steel sheet coated with 0.5 to 4.0 g Zm ^{2 of the} paint as a dry mass is disclosed. Furthermore, in order to meet the demands of customers 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. Hei 6-173,037 discloses a steel sheet having a lubricating film in which silica and a polyolefin are added to an ether-ester type urethane resin and an epoxy resin. I have.

The technology disclosed in Japanese Patent Publication No. 41-11991 has excellent performance parameters such as corrosion resistance, paint adhesion, fingerprint resistance, and dew condensation resistance. It is used as one. However, even surface-treated steel sheets coated with such an organic film may have scratches during handling, galling during press working, and abrasion during product transportation. .

On the other hand, the techniques disclosed in Japanese Patent Application Laid-Open Nos. 3-39485 and 3-28380 generate galling and abrasion during press working described above. In particular, the technique disclosed in Japanese Patent Application Laid-Open No. Hei 6-173,037 has excellent press galling resistance even in severe processing such as deep drawing workability. However, it is manufactured by the technology disclosed in JP-A-3-39485, JP-A-3-28380, and JP-A-6-17370. The surface of the steel plate is slippery, causing coil collapse due to loose winding and load collapse during cutting plate cutting. Therefore, measures are currently being taken to avoid these problems, such as increasing the tension during coil winding and increasing the number of bands to prevent coil loosening after packing. .

A first main object of the present invention is to improve the various performances such as corrosion resistance, adhesion, and weldability, and maintain the press galling resistance, while crushing a coil due to loose winding and load during cutting plate cutting. A surface-treated metal plate with a controlled coating composition, a coefficient of kinetic friction and a coefficient of static friction of the coating surface, a method of manufacturing the same, and an aqueous organic-inorganic composite that enables the production of the surface-treated metal plate to improve problems such as collapse To provide a paint.

The second main object of the present invention is to provide a sheet having excellent properties such as corrosion resistance, adhesion, and weldability, and excellent press galling resistance and continuous sliding wear resistance. It is an object of the present invention to provide a surface-treated metal plate, a method for producing the same, and an aqueous organic-inorganic composite paint capable of producing the surface-treated metal plate.

A third main object of the present invention is to improve the various properties such as corrosion resistance, adhesion, weldability, etc., and to maintain the resistance to press galling while crushing a coil due to loose winding and load collapse during cutting of a cut plate. Another object of the present invention is to provide a surface-treated metal sheet which suppresses the generation of sticky scum caused by the lubricant falling off the film during pressing, and a method for producing the same. Disclosure of the invention

The present inventors have conducted various studies to achieve the first object, and as a result, have a polyolefin wax dispersion having a molecular weight of 600 to 1500 and an appropriate amount of colloidal silicide force. Applying the aqueous organic-inorganic composite paint on a plated metal plate and drying it to form an aqueous organic-inorganic composite coating not only excels in various properties such as corrosion resistance, adhesion, and weldability, but also on the surface of the metal plate Has a dynamic friction coefficient of 0.07 to 0.15, and a surface-treated metal sheet with a controlled static friction coefficient of 0.10 or more and excellent in press galling resistance and coil deformation resistance. And completed the present invention.

Therefore, in the first aspect, the gist of the present invention is as follows.

(1) One or both of the water-based resin and the silicate compound, and a polyolefin wax with a molecular weight of 600 to 1500, a spazone and a solid content of 5 to 35 0.3 to 5 the aqueous organic-inorganic composite film containing colloidal silica force mass%. O g / m ² with this and resistant press galling resistance and coil deformation excellent in surface treated metals plate, wherein . (2) The polyolefin wax dispersion contains a polar group-free polyolefin wax particle having a molecular weight of 600 to 1500 and a particle size of 0.1 to 5.0 μm. It is characterized in that it is at least one selected from a modified polyolefin wax dispersion having a size of 600 to 150, an acid value of 40 or less, and a particle size of 0.1 to 5.0 m. The surface-treated metal sheet according to (1), which is excellent in press galling resistance and coil deformation resistance.

(3) The anti-press galling property described in (1) or (2) above, wherein the surface has a dynamic friction coefficient of 0.07 to 0.15 and a static friction coefficient of 0.10 or more. Surface-treated metal sheet with excellent coil deformation resistance.

(4) One or both of the aqueous resin and the silicate salt, and a polyolefin wax dispersion having a molecular weight of 600 to 1500 and a solid content of 5 to 35 mass ⁰ /. A water-based organic-inorganic composite coating, comprising: a colloidal silica; and water.

(5) wherein the poly Orefui Nwa Kkusudei Supajiyo emissions is, molecular weight 6 0 0 0-1 5 0 0 0 containing no polar group, particle size 0.1 to 5. Po Li Orefui Nwa Kkusudei scan Nono ⁰ 0 - di ® At least one selected from modified polyolefin wax dispersions with a molecular weight of 600-150-500, an acid value of 40 or less, and a particle size of 0.1-5.0 μm. The aqueous organic-inorganic composite coating according to the above (4), which is characterized in that:

(6) the (4) was 0. 3~ 5. 0 g / m ² coated with paint drying mass conversion to plated metal plate according to a feature to form an aqueous organic-inorganic composite coating baked A method for producing a surface-treated metal sheet that excels in press galling resistance and coil deformation resistance.

(7) the (5) 0 paints dry weight terms of plated metal plate according to. 3~ 5. 0 g / m ² was coated, the aqueous organic-inorganic composite baked A method for producing a surface-treated metal sheet having excellent press galling resistance and coil deformation resistance characterized by forming a film.

The present inventors also conducted various studies to achieve the second object, and found that a polyolefin wax dispersion having a molecular weight of 600 to 1500 and a molecular weight of 100 A water-based organic-inorganic composite coating containing a polyolefin dispersion of 0 to 500 and an appropriate amount of colloidal sily force is coated on a plated metal plate and dried to form an aqueous organic-inorganic composite coating. It has been found that by forming such a metal sheet, a surface-treated metal sheet having excellent press galling resistance and continuous sliding wear resistance can be obtained, and the present invention has been completed.

Therefore, in the second aspect, the gist of the present invention is as follows.

(1) One or both of an aqueous resin and a silicate compound, and a lubricant (A) composed of a polyolefin wax dispersion having a molecular weight of 600 to 1500, a molecular weight of 100 A lubricant (B) composed of up to 500,000 polyolefin wax dispersion purge ion and an aqueous organic-inorganic composite coating containing 5 to 35% by mass in terms of solids, having a co-idal sily force. A surface-treated metal sheet excellent in press galling resistance and continuous sliding wear resistance, characterized in that said aqueous organic-inorganic composite film has a thickness of 0.3 to 5.0 g Zm ² .

(2) Polyolefin wax dispersion having a molecular weight of 600 to 150,000 and a particle size of 0.1 to 5.O / xm, wherein the lubricant (A) does not contain a polar group and a molecular weight of 600,000 At least one lubricant selected from the group consisting of modified polyolefin wax dispersions with a particle size of 0.1-5.0 j «m. ) Is a polyolefin waxed purge _ion having a molecular weight of 100 to ₅₀₀ and a particle size of 0 to 5.0 _μπ1 containing no polar group. The surface-treated metal sheet excellent in press galling resistance and continuous sliding wear resistance according to the above (1).

(3) One or both of the aqueous resin and the silicate compound, and a lubricant (A) composed of a polyolefin wax dispersion having a molecular weight of 600 to 1500, a molecular weight of 100 Aqueous organic-inorganic composite containing a lubricant (B) composed of 0 to 500 000 polyolefin wax purge and a colloidal sily power of 5 to 35% by mass in terms of solid content and water paint.

(4) The lubricant (A) has a molecular weight of 600 to 1500 without a polar group and a particle size of 0:! To 5. At least one lubricant selected from the group consisting of modified polyolefin wax dispersions with a particle size of 0.1 to 5.0 μιη. (3) wherein (iii) is a polyolefin wax disposable ion having a molecular weight of 100 to 500 and a particle size of 0.1 to 5.0 tm without a polar group. The aqueous organic-inorganic composite paint according to the above.

(5) the (3) was 0. 3~ 5. 0 g Zm ² coating on a dry weight terms of plated metal plate of an aqueous organic-inorganic composite coating according to, baked child form an aqueous organic-inorganic composite coating film A method for producing a surface-treated metal sheet having excellent press galling resistance and continuous sliding wear resistance characterized by the following.

(6) the (4) was 0. 3~ 5. 0 g / m ² coating on a dry weight terms of plated metal plate of an aqueous organic-inorganic composite coating according to, to form an aqueous organic-inorganic composite coating baked A method for producing a surface-treated metal sheet having excellent press galling resistance and continuous sliding wear resistance.

The present inventors further conducted various studies to achieve the third object, and as a result, found that a polyolefin wax dispenser having a molecular weight of 600 to 1500 was added to the upper layer of the plated metal plate. Lubricant (A), If necessary, a water-based organic inorganic composite paint (E) containing a lubricant (B), which is a polyolefin dexpurge ion having a molecular weight of 1000 to 500, is further applied. The first layer is formed by baking, then an aqueous organic-inorganic composite paint (F) containing an appropriate amount of colloidal silicide is applied, and the second layer is formed by baking to obtain the surface of the metal plate. Surface treatment that can control the dynamic friction coefficient to 0.07 to 0.15, the static friction coefficient to 0.10 or more, and suppress the generation of sticky residue caused by the lubricant falling off from the film during pressing. They found that a metal plate could be obtained, and completed the present invention.

Therefore, in the third aspect, the gist of the present invention is as follows.

(1) Lubricant composed of one or both of an aqueous resin and a silicate compound as the first layer, and a polyolefin wax disperse purge having a molecular weight of 600 to 1500 The aqueous organic / inorganic composite film (C) containing (A) has a dry mass of 0.05 to 0.3 g / m ² , and the second layer contains an aqueous resin and a silicate compound. The aqueous organic-inorganic composite film (D) composed of colloidal silica in an amount of 5 to 35% by mass in terms of solids is used as a dry mass in an amount of 0.5 to 5.0 g / m ^2. A surface-treated metal sheet with excellent resistance to press galling and coil deformation.

(2) The lubricant (A) does not contain a polar group and has a molecular weight of 600 to 1500 and a particle size of 0.1 to 5. Om Polyolefin wax dispersion and a molecular weight of 600 to 150, an acid value of 40 or less, and a particle size of 0.1 to 5. At least one kind of lubricant selected from a modified polyolefin wax dispersion having a particle size of ίίΐ η. (1) A surface-treated metal sheet excellent in press galling resistance and coil deformation resistance described in (1). (3) The lubricant (A) in which the aqueous organic-inorganic composite film (C) is an aqueous resin and a polyolefin wax dispersion having a molecular weight of 600 to 1500 and a molecular weight of 100 (1) or (2), which is composed of a composite lubricant mixed with a lubricant (B), which is a polyolefin disperse purge ion of up to 500,000. Surface treated metal sheet with excellent resistance to press galling and coil deformation.

(4) The lubricant (A) does not contain a polar group, and has a molecular weight of 600 to 150, a particle size of 0.1 to 5. and a polyolefin wax dispersion having a particle size of 0.1 to 5. 150 000, acid value 40 or less, particle size 0.1-5. At least one lubricant selected from modified polyolefin wax dispersion with a particle size of 0.1μιη, lubricant (潤滑) polarity The above (3) is characterized in that the polyolefin is a polyolefin wax-based dispersion having a group-free molecular weight of 1,000 to 500,000 and a particle size of 0.1 to 3.0 μιη. Surface-treated metal sheet with excellent resistance to press galling and coil deformation.

(5) The anti-press galling property described in (1) to (4), wherein the coefficient of dynamic friction of the surface is 0.07 to 0.15 and the coefficient of static friction is 0.10 or more. Surface-treated metal sheet with excellent coil deformation resistance.

(6) An aqueous resin and / or a silicate compound, and a lubricant (A), which is a polyolefin wax day dispersion having a molecular weight of 600 to 1500, is formed on the upper layer of the plated metal plate. , and was 0. 0 5~ 0. 3 g / m 2 coating constituted aqueous organic-inorganic composite coating material (E) by dry mass conversion with water to form a first layer and baked, then aqueous resin Aqueous organic-inorganic composite paint (F) composed of one or both of a silicate salt and colloidal silica and water and having a colloidal silica content of 5 to 35% by mass in terms of solid content is a dry mass. after 0. 5~ 5. 0 g / m ² coated at the exchange, forming a second layer by baking A method for producing a surface-treated metal sheet having excellent resistance to press galling and coil deformation.

(7) The lubricant (A) does not contain a polar group and has a molecular weight of 600 to 1500 and a particle size of 0.1 to 5. Polyolefin wax dispersion having a particle size of 0.1 to 5. ~ 1500, acid value of 40 or less, particle size of 0.1 ~ 5.0μm, characterized by at least one or more lubricants selected from modified polyolefin wax dispersions. The method for producing a surface-treated metal sheet having excellent press galling resistance and coil deformation resistance according to the above (6).

(8) The aqueous organic-inorganic composite paint (E) is an aqueous resin, a lubricant (A) having a molecular weight of 600 to 1500 and a molecular weight of 100 to 5 The above (6) or (7), which is composed of a composite lubricant obtained by mixing a lubricant (B), which is a polyolefin disposable purge ion of 0.000, and water. A method for producing a surface-treated metal sheet that excels in press galling resistance and coil deformation resistance.

(9) The lubricant (A) does not contain a polar group and has a molecular weight of 600 to 150, a particle size of 0.1 to 5. and a polyolefin wax dispersion having a particle size of 0.1 to 5. At least one lubricant selected from the group consisting of modified polyolefin waxed dispersions with a particle size of 0.1 to 50,000 μηι, an acid value of 40 to 150, an acid value of 40 or less, and a lubricant (Β) Has a molecular weight of 100 to 500, which does not contain a polar group, and a particle diameter of 0: (6) to (8), wherein the surface-treated metal plate is excellent in press galling resistance and coil deformation resistance. Production method. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a diagram illustrating a surface-treated metal plate according to the first aspect of the present invention.

FIG. 2 is a diagram illustrating a surface-treated metal plate according to the second aspect of the present invention.

FIG. 3 is a diagram illustrating an example of a surface metal plate according to the third aspect of the present invention.

FIG. 4 is a view for explaining another example of the surface metal plate according to the third aspect of the present invention. 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 aqueous organic / inorganic composite coated steel sheets, a method of adding a lubricant such as polyolefin with a low molecular weight to the aqueous organic / inorganic composite coating on the steel sheet is generally used. It has been done. By blending such a low molecular weight polyolefin dispersion having no polar group into the aqueous organic / inorganic film, the particles are present in the form of particles on the film surface and reduce the affinity of the metal plate surface. 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. As a result, an excellent lubrication effect can be obtained, and galling during pressing can be reduced.

On the other hand, in the first aspect of the present invention, a predetermined amount of a polyolefin wax dispersion having a molecular weight of 600 to 1500 is blended into an aqueous organic / inorganic composite paint as a lubricant. Further, the content of colloidal silicide in the aqueous organic / inorganic composite film is adjusted to 5 to 35% by mass in terms of solid content.

FIG. 1 shows an example of the surface-treated metal plate of the present invention. Surface treatment of the present invention Metal plate attached Metal plate 3 with aqueous organic-inorganic composite coating 2 on It has become. The aqueous organic / inorganic composite film 2 is an aqueous organic compound containing one or both of an aqueous resin and a silicate compound, and further containing colloidal silica, water, and a polyolefin phenol dispersion 1 as a lubricant. It is formed by applying an inorganic composite paint on the plated metal plate 3 by an appropriate method. As shown in FIG. 1, the polyolefin wax dispurge ion 1 is granularly exposed from the aqueous organic-inorganic composite film 2.

In this way, by adding a polyolefin wax dispersion to the aqueous organic / inorganic composite film and adjusting the molecular weight of the wax to an appropriate value, the particles are present in a granular form on the film surface,制御 Control the hardness of the tuss and the affinity of the coating surface. Furthermore, the content of silica is adjusted to achieve both film hardness and film performance such as corrosion resistance and adhesion. As described above, not only has good corrosion resistance and adhesion, but also a non-conventional press galling with a dynamic friction coefficient of 0.07 to 0.15 and a static friction coefficient controlled to 0.10 or more. A surface-treated metal plate with excellent heat resistance and coil deformation resistance can be obtained.

Hereinafter, a method for producing a surface-treated metal sheet having excellent press galling resistance and coil deformation resistance according to the first aspect of the present invention will be described.

The surface-treated metal plate according to the first aspect of the present invention is manufactured by applying a predetermined aqueous organic-inorganic composite paint to a metal plate with a base and baking to form an aqueous organic-inorganic composite coating. The base metal plate applicable in the present invention includes a metal plate with zinc plating, a metal plate with zinc-nickel plating, a metal plate with zinc-iron plating, a metal plate with zinc-chromium plating, and a metal plate with zinc-aluminum plating. Sheet, zinc-titanium-plated metal sheet, zinc-magnesium-plated metal sheet, zinc-manganese-plated metal sheet, etc., zinc-based electric plating, hot-dip plating, vapor-deposited steel sheet, aluminum or aluminum alloy Metal plate, metal plate with lead or lead alloy, Tin or tin-alloy-plated metal plates, as well as a small amount of foreign metal elements or impurities such as cobalt, molybdenum, tanda stainless, nickele, titanium, chromium, anoremium, manganese, iron, magnesium, and lead in these plating layers , Antimony, tin, copper, cadmium, arsenic, etc., and / or silica, alumina, titania, etc. dispersed therein. Furthermore, the present invention can be applied to a multi-layer metal plate in which the above-mentioned plating is combined with another type of plating, for example, iron plating or iron-rimp plating.

The plating adhesion amount on each plated metal plate is preferably 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. In addition, it is also possible to form an aqueous organic-inorganic composite film directly on a plated metal plate without performing a base treatment. The undercoating treatment is not particularly limited as long as the above object can be achieved, but in general, a chromate treatment capable of improving corrosion resistance and adhesion is preferable.

Means for forming a chromate film include, for example, immersion in an aqueous solution mainly containing chromic anhydride, chromate, or dichromate (reactive type) chromate treatment, electrolytic chromate treatment Further, there is a coating type mouth mate treatment method in which a treatment liquid obtained by mixing a colloidal sily force or the like with the aqueous solution is applied and dried without washing with water.

Chromate coating weight is preferably between 5~ 1 0 O mg Z m ² approximately by C r terms. If the adhered amount is less than 5 mg / m ^{2 in} terms of Cr, sufficient corrosion resistance cannot be obtained, and if it exceeds 10 O mg / m ² , the chromate film itself will undergo cohesive failure and the paint adhesion will be reduced.

Aqueous resin includes acrylic ester-acrylic acid copolymer, POXY-acrylic acid copolymer, styrene-acrylic acid copolymer, olefin ionomer, styrene-at-alinoleic acid copolymer, urethane-acrylic acid copolymer, urethane-epoxy resin, ethylene-imine- An acrylic resin or the like can be used. In order to obtain a paint using such an aqueous resin, it is preferable to disperse the resin in an aqueous solvent to form an emulsion. If necessary, a cross-linking agent such as various melamine resins and amino resins may be added. Among these, when considering both performance and cost, it is preferable to use an acrylic resin such as a copolymer of olefin-acrylic acid. When severe deep drawing is required, 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 ₂₀ · n SiO ₂ (where M is an alkali metal such as sodium, potassium and lithium, and n is an arbitrary number). , Sodium silicate, calcium silicate, and lithium silicate. Aru in the M ₂ 0 and S 1 0 ₂ molar ratio! 1 is preferably in the range of 1 to 10. If the value of n is less than 1, the obtained film is likely 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 of a spherical, linear, or branched colloidal sily with a branched spherical colloidal sily may be used. Spherical silica has a particle diameter of 5 to 50 nm, linear silica has a diameter of 5 to 50 nm and a length-to-thickness ratio of 1 to 5 chemically bonded, and has branches. In the case of beaded silica, those having a ratio of [length of the conjugate / average particle diameter of the spherical silica] of 4 or more and having one or more branches are preferable. Colloidal silica is incorporated into the aqueous organic / inorganic composite coating material of the present invention in an amount of 5 to 35% by mass in terms of solid content. If the amount is less than 5% by mass, sufficient corrosion resistance and press galling resistance cannot be obtained, and if the amount exceeds 35% by mass, coating adhesion and press galling resistance deteriorate.

The aqueous organic-inorganic composite paint used in the first aspect of the present invention may contain one or both of the above-mentioned water-based resin and silicate compound, colloidal silicide, and water, and have a molecular weight of 600 to 1500. It is prepared by blending Polyolefin Inks Dispurgeon. More preferably, a polyolefin wax dispenser having a molecular weight of 600 to 1500, substantially free from polar groups, and a particle size of 0.1 to 5.0 zm, and a molecular weight of 600 Aqueous organic-inorganic composite paint with at least one selected from a modified polyolefin wax purge purge with a particle size of 0.1 to 5.0 μm, a particle size of 0.1 to 5.0 μm Used by mixing in. As the polyolefin wax dispersion, an emulsifier having a concentration of 5% or less, preferably an emulsifier, is used. A substance dispersed in water or an aqueous solution without using it is used.

As the modified polyolefin wax dispersion, a polyethylene wax, a polypropylene wax or a polybutylene wax containing a polar group was emulsifier concentration of 5% or less, preferably dispersed in water or an aqueous solution without using an emulsifier. Use something. The polar group can be introduced by oxidizing the polyolefin wax with an oxidizing agent such as oxygen, ozone or nitric acid in the presence of a catalyst (oxidized polyolefin wax), or acrylic acid or methacrylic acid. An ethylenically unsaturated carboxylic acid monomer such as lylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and a polyolefin wax are dissolved with benzol or the like, and a polymerization initiator (peroxide, redox) is dissolved. , Heavy metal catalysts, etc.) and heated in a nitrogen stream to make a graph.

The mass average particle diameter of the polyolefin wax dispersion and the modified polyolefin wax dispersion is preferably from 0.1 to 5.0 βm, more preferably from 1.0 to 4.0 βμπι. Things are used. If the mass average particle size is less than 0.1 / zm, it is not preferable because it tends to aggregate and has poor stability. On the other hand, when the mass average particle size exceeds 5.Ομηι, the dispersion stability is poor, which is not preferable. The ratio of the mass average particle diameter to the number average particle diameter is preferably in the range of mass average particle diameter / number average particle diameter <3.

The range of the weight average molecular weight of the polyolefin wax dispersion and the modified polyolefin wax dispersion is preferably from 600 to 1500. If the weight average molecular weight is less than 600, the coil deformation resistance is undesirably deteriorated. On the other hand, if the mass average molecular weight exceeds about 500, press galling resistance is undesirably deteriorated.

The method and conditions for analyzing the mass 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.

• Analysis method: GPC for high temperature (gel pe rmeat ion chromatography)

• Column: Mixed type of PS (polystyrene) gel (2 to 4 in series)

• Solvents: 0—dichlorobenzene (ODCB), trichlorobenzene (TCB), etc.

• Measurement temperature: 130 to 140 ° C -Detector: Differential refractometer (RI) or infrared detector

• Preparation of calibration curve: Conversion to each molecular weight using commercially available monodisperse PS

The acid value (KOH-mg / g) defined by JIS 592 of the modified polyolefin wax purge ion is preferably 40 or less. If the acid value exceeds 40, sufficient lubricity cannot be obtained because the lubricant becomes hard.

Moreover, these polyolefins emissions wax disperser job down and modified poly Orefi emissions wax disperser job down, the density defined by JISK 6 7 6 0 is 9 5 0~: L 0 0 0 kg / m 3, JISK

The hardness (penetration) specified by 222 is 0.2 mm or less, the crystallinity determined by X-ray diffraction method is 80% or more, and the melting point is 110 to 150 °. C's are preferred.

At least one selected from these polyolefin wax dispersions and modified polyolefin wax dispersions is contained in the aqueous organic / inorganic composite paint in an amount of 1 to 30% by mass in terms of solid content. It is preferable to mix them. If the amount is less than 1% by mass, sufficient resistance to press galling cannot be obtained, and if it exceeds 30% by mass, paint adhesion deteriorates, which is not preferable.

Adhesion amount range of these aqueous organic-inorganic composite coating film is a dry mass 0. 3 5. and O g Zm ^2. And more preferably 1. 0~ 3. 0 g / m 2. If the amount of adhesion is less than 0.3 g / m ² , the desired resistance to press galling will be poor, and if it exceeds 5.0 g Zm ² , weldability will be difficult, which is not preferable.

Coating methods for forming these aqueous organic / inorganic composite coatings include any of spraying, curtains, flow coaters, lono-recorders, no-coaters, brush coating, dipping, and air knife drawing. Method may be used.

The baking temperature is desirably set to 80 to 250 ° C. More preferably, the temperature is higher than the melting point of the lubricant used. If the temperature is lower than 80 ° C, the water in the coating is hardly volatilized completely, so that the corrosion resistance is lowered. If the temperature is higher than 250 ° C, the film is excessively hardened 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 using a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be adopted.

The surface-treated metal plate of the present invention preferably has a dynamic friction coefficient of 0.07 to 0.15 and a static friction coefficient of 0.10 or more. If the coefficient of kinetic friction is higher than 0.15, the galling resistance of the press deteriorates, and if the coefficient of kinetic friction is 0.07 and the coefficient of static friction is lower than 0.10, the coil is inferior in deformation resistance. .

Next, in the second aspect of the present invention, lubricants (A) and (B) having different molecular weights are used as a lubricant in a predetermined amount in the aqueous organic / inorganic composite paint. Here, a polyolefin wax dispersion having a molecular weight of 600 to 1500 is used as the lubricant (A), and a molecular weight of 100 to 500 is used as the lubricant (B). Use a polyolefin wax dispersion of 00. Furthermore, by adjusting the content of silicide force in the aqueous organic-inorganic composite coating to 5 to 35% by mass in terms of solid content, it is possible to achieve compatibility between film hardness and film performance such as corrosion resistance and adhesion. . FIG. 2 shows an example of the surface-treated metal plate of the present invention. The surface-treated metal plate of the present invention has a configuration in which an aqueous organic / inorganic composite film 13 is provided on a metal plate 14 attached thereto. The aqueous organic-inorganic composite film 13 may be made of one or both of an aqueous resin and a silicate compound, and a lubricant (A), a lubricant ( An aqueous organic / inorganic composite paint obtained by mixing B) with 5 to 35% by mass of colloidal silica and water in terms of solid content is applied on a plated metal plate 14 by an appropriate method to form the coating. As shown in FIG. 2, the lubricant (A) 11 and the lubricant (B) 12 are exposed in a granular form from the aqueous organic-inorganic composite film 13.

In this way, by adding a polyolefin wax dispersion having a low molecular weight and a polyolefin wax dispersion having a high molecular weight, which have been conventionally used, to an aqueous organic / inorganic composite film, they can be added together. In addition, the wax is present in a granular form on the surface of the film, and at the same time, suppresses the crushing of the wax during press molding and continuous sliding. Furthermore, the content of silica is adjusted to achieve compatibility between film hardness and film performance such as corrosion resistance and adhesion. As described above, it is possible to not only have good corrosion resistance and adhesion, but also to increase the resistance to press galling and the durability of the lubricating effect during continuous sliding.

Hereinafter, a method for producing a surface-treated metal sheet having excellent press galling resistance and continuous sliding wear resistance according to the second aspect of the present invention will be described. This manufacturing method is basically the same as the method for manufacturing a surface-treated metal plate according to the first aspect of the present invention, except that the aqueous organic / inorganic composite paint used is different.

The surface-treated metal plate according to the second aspect of the present invention is also produced by applying a predetermined aqueous organic-inorganic composite coating to a metal plate with a base and baking to form an aqueous organic-inorganic composite coating.

Applicable metal plates with a base are as described above for the surface-treated metal plate on the first side surface. The plating adhesion amount on each plated metal plate is preferably at least Ig Zm ^{2 on} one side, and if it is less than this, the corrosion resistance is reduced. An aqueous organic-inorganic composite film can be formed on the plated metal plate after applying a base treatment for the purpose of improving adhesion or corrosion resistance, etc. It is also possible to form an inorganic composite film. The undercoating is not particularly limited as long as the above object can be achieved. Generally, a chromate treatment capable of improving corrosion resistance and adhesion is preferable. The means for forming the chromate film and the amount of chromate adhering are as described above for the surface-treated metal plate on the first side surface.

As the water-based resin, those described above for the surface-treated metal plate on the first side surface can also be used. In order to form a paint, it is preferable to disperse the resin in an aqueous solvent to form an emulsion, and it is also possible to add a cross-linking agent such as various melamine resins and amino resins as necessary. It is. In particular, when both performance and cost are considered, it is preferable to use an acrylic resin such as an olefin-acrylic acid copolymer. When severe deep drawing is required, and when continuous sliding wear resistance is required, it is preferable to use a urethane-epoxy resin having both hardness and elongation.

As the silicate compound and colloidal silicic acid according to the second aspect of the present invention, those described above for the surface-treated metal plate of the first aspect can be used. '

The colloidal silicide force is incorporated in the water-based organic-inorganic composite paint 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, adhesion and press galling resistance deteriorate. '

The aqueous organic-inorganic composite paint used in the second aspect of the present invention is a lubricant (A) having a different molecular weight from one or both of the above-mentioned water-based resin and the silicate compound, and having different molecular weights. B) is prepared by blending in a predetermined amount. Here, a polyolefin wax dispersion having a molecular weight of 600 to 1500 is used as the lubricant (A), and a molecular weight of 1000 to 500 is used as the lubricant (B). Polyolefin of 0 Use wax dispensing. More preferably, a lubricant

(A) is a polyolefin wax-based purge gas having a molecular weight of 600 to 150 and a particle size of 0.1 to 5.0 μm, which does not contain a polar group, and a molecular weight of 600 to 1 Use at least one lubricant selected from the group consisting of modified polyolefin wax particles with a particle size of 0.1 to 5.0 μιη As (B), use a polyolefin waxed purge ion having a molecular weight of 100 to 50,000 and a particle size of 0.1 to 5.0 im, which does not contain a polar group.

As a polyolefin wax dispersion, polyethylene wax, polypropylene wax, or polybutylene wax, which does not substantially contain a polar group, is emulsifier concentration of 5% or less, preferably water or emulsifier without using an emulsifier. Use those dispersed in an aqueous solution.

As the modified polyolefin wax dispersion, polyethylene wax, polypropylene wax, or polypropylene wax containing a polar group is emulsifier concentration of 5% or less, preferably water without emulsifier. Alternatively, a material dispersed in an aqueous solution is used. The polar group can be introduced by oxidizing polyolefin wax with an oxidizing agent such as oxygen, ozone, or nitric acid in the presence of a catalyst (polyolefin oxide wax), or acrylic acid, methacrylic acid, An ethylene unsaturated monomer such as crotonic acid, maleic acid, fumaric acid, and itaconic acid, and a monomer of olevonic acid and a polyolefin wax are dissolved with benzene or the like, and a polymerization initiator (peroxide, redox) is dissolved. , Heavy metal catalyst, etc.) and heated in a nitrogen stream to make a graph.

The mass average particle diameter of the polyolefin waxed dispersion and the modified polyolefin waxed purged is preferably from 0.1 to 5.0 μm, more preferably from 1.0 to 4.0 μπι. use Is done. If the mass average particle size is less than 0.1 μπΐ, it is not preferable because the particles are likely to aggregate and have poor stability. Further, when the mass average particle diameter exceeds 5.Ομπΐ, the dispersion stability is poor, so that it is not preferable. Further, the ratio of the mass average particle diameter to the number average particle diameter is preferably in the range of mass average particle diameter / number average particle diameter <3.

The range of the weight average molecular weight of the polyolefin wax dispersion ion and the modified polyolefin wax dispersion in the lubricant (A) is preferably from 600 to 1500. . When the mass average molecular weight is less than 60 ° 0, it is too soft, so that continuous sliding wear resistance cannot be improved. On the other hand, when the weight average molecular weight exceeds 150,000, press galling resistance is deteriorated, which is not preferable.

The weight average molecular weight of the polyolefin wax purge ion in the lubricant (B) is preferably in the range of 100 to 500,000. If the weight average molecular weight is less than 1000, thermal decomposition is liable to occur, and a direct-fired drying furnace whose surface is exposed to a high temperature of around 1000 ° C. is not preferable because sufficient lubricating properties may not be obtained in some cases. On the other hand, when the average molecular weight exceeds 50,000, continuous sliding wear resistance is deteriorated, which is not preferable. The method and conditions for analyzing the mass average molecular weight of these polyolefin wax dispersions and modified polyolefin wax dispersions are as already described in the description of the surface-treated metal plate according to the first aspect of the present invention. .

As the range of the acid value (KOH-mg / g) specified by JIS 592 of the modified polyolefin wax purge ion in the lubricant (A), a value of 40 or less is preferable. If the acid value exceeds 40, the lubricating agent will be too hard to obtain sufficient lubricity.

Furthermore, the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (A) are: JISK 6 7 6 0 density 9 5 0-1 0 0 defined by ^{0 kg / m 3, JISK 2} 2 0 7 in defined by the hardness (penetration) of 0. 2 mm or less, X-rays diffractometry It is preferable that the crystallinity determined by the method described above is 80% or more and the melting point is 110 to 150 ° C.

The total content of these lubricants (A) and (B) is preferably 1 to 30% by mass in terms of solid content in the aqueous organic / inorganic composite paint. 1 mass. /. If it is less than 30%, sufficient continuous sliding wear resistance cannot be obtained, and if it exceeds 30% by mass, paint adhesion deteriorates, which is not preferable.

The content of the lubricant A with respect to the total content of the lubricants (A) and (B) is preferably in the range of 10 to 90%. If it is less than 10%, the sliding wear property cannot be increased. On the other hand, if it is more than 90%, press galling resistance is deteriorated as compared with the lubricant B alone, which is not preferable.

The coating amount range of the aqueous organic-inorganic composite film is 0.3 to 5 g Zm ² as a dry mass. Preferably the is found is ^{1. 0~ 3. O g Zm 2} . If the adhesion amount is less than 0.3 g Zm ² , the desired resistance to press galling is inferior, and if it exceeds 5.0 g Zm ² , the weldability becomes difficult, which is not preferable.

The coating method, baking temperature, and drying equipment for forming the aqueous organic-inorganic composite coating according to the second aspect of the present invention are as described above for the formation of the aqueous-organic composite coating in the first aspect. Next, according to a third aspect of the present invention, the molecular weight of the aqueous resin and / or the silicate compound is set to 600,000 to 1,500,000 on the upper layer of the plated metal plate. 0 poly Orefui emissions wax disperser di yo down a is a lubricant (a) consists of aqueous organic-inorganic composite coating film (C) is in a dry mass 0. 0 5~ 0. 3 g / m 2 was formed, As the second layer, one or both of the aqueous resin and the silicate compound, colloidal The organic composite coating film (D), which is composed of resiliency and has a content of co-idal-sili force of 5 to 35% by mass in terms of solids, is 0.5 to 5.0 g / m ² as a dry mass. Form.

FIG. 3 shows an example of the surface-treated metal plate of the first embodiment according to the third aspect of the present invention, and FIG. 4 shows an example of the surface-treated metal plate of the second embodiment.

In FIG. 3, the surface-treated metal plate of the first embodiment according to the third aspect of the present invention comprises a first-layer aqueous organic-inorganic composite film (C) 22 and a second The structure has a layer of aqueous organic / inorganic composite film (D) 24. The first layer of the aqueous organic-inorganic composite film (C) 22 is coated with one or both of an aqueous resin and a silicate compound, and furthermore, a paint (E) composed of a lubricant (A) and water as appropriate. The second layer of the aqueous organic-inorganic composite film (D) 24 is formed by applying one or both of the aqueous resin and the silicate compound, and furthermore, by using the colloidal sily force and water. The aqueous-organic composite paint (F) thus formed was applied by an appropriate method and then baked.

In FIG. 4, the surface-treated metal plate of the second embodiment according to the third aspect of the present invention comprises a first layer of an aqueous organic-inorganic composite film (C 22 and a second layer) on a plated metal plate 23. The first aqueous-organic composite coating (C ′) 22 has a structure having an aqueous organic-inorganic composite coating (D) 24. One or both of the aqueous resin and the silicate compound Further, a paint (E) composed of a lubricant (A), a lubricant (B) and water is applied by an appropriate method, and then baked to form a second layer of the aqueous organic-inorganic composite film ( D) 24 is an aqueous resin and / or a silicate compound, or an aqueous organic / inorganic composite paint (F) composed of colloidal silica and water, applied by an appropriate method, and baked. It was formed. In this way, a polyolefin wax having a molecular weight adjusted to an appropriate value is added, and an aqueous organic-inorganic composite film (C) or

(C ') is formed, and the aqueous organic-inorganic composite film (D) is formed on the upper layer, so that the wax is projected from the lower surface of the aqueous organic-inorganic composite film (D) to the film surface in a granular manner. Controls wax hardness and film surface affinity. Furthermore, by adjusting the content of silicide force in the aqueous organic / inorganic composite coating (D), the compatibility of the coating hardness and the coating performance such as corrosion resistance and adhesion will be achieved. In this way, not only good corrosion resistance and adhesion, but also a galling resistance and coil resistance with a dynamic friction coefficient of 0.07 to 0.15 and a static friction coefficient controlled to 0.10 or more are obtained. A surface-treated metal plate having excellent deformability and capable of suppressing the generation of sticky scum caused by the lubricant falling off from the film during pressing can be obtained.

Hereinafter, a method for producing a surface-treated metal plate having excellent press galling resistance and coil deformation resistance according to the third aspect of the present invention will be described. This production method is also basically the same as the production method of the surface-treated metal plate on the first side, except that the aqueous organic / inorganic composite paint used is different and that two aqueous / organic composite coatings are formed. is there.

Applicable metal plates with a base are as described above for the surface-treated metal plate on the first side surface. The plating adhesion amount on each plated metal plate is preferably 1 g / m ² or more on one side, and if it is less than this, the corrosion resistance decreases. An aqueous organic-inorganic composite film can be formed on the plated metal plate after applying an undercoat treatment for the purpose of improving adhesion or corrosion resistance, etc., or directly to the aqueous organic-inorganic composite coat without applying the undercoat treatment. It is also possible to form The undercoating is not particularly limited as long as the above object can be achieved. Generally, a chromate treatment capable of improving corrosion resistance and adhesion is preferable. The method of forming the chromate film and the amount of chromate The surface-treated metal plate on the side surface is as described above.

As the water-based resin, those described above for the surface-treated metal plate on the first side surface can also be used. In order to form a paint, it is preferable to disperse the resin in an aqueous solvent to form an emulsion, and it is also possible to add a cross-linking agent such as various melamine resins and amino resins as necessary. It is. In the third aspect of the present invention, it is more preferable to select a highly hydrophilic resin as the aqueous resin used in the first layer. Also, as the resin used for the second layer, it is preferable to use an acryl-based resin such as a copolymer of mono-acrylic acid, especially when considering both performance and cost. When severe deep drawing is required, it is preferable to use a urethane-epoxy resin having both hardness and elongation.

As the silicate compound and colloidal silicity used in the third aspect of the present invention, those described above for the surface-treated metal plate of the first aspect can be used.

Colloidal silica is incorporated in the aqueous organic / inorganic composite paint (F) in a solid content of 5 to 35% by mass. 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.

According to a third aspect of the present invention, a lubricant (A) or a lubricant (A) and (B) are combined with an aqueous organic-inorganic composite together with one or both of the aqueous resin and the silicate compound, colloidal silica, and water. The paint (E) is used in a prescribed amount. Here, a polyolefin wax disposable with a molecular weight of 600 to 1500 is used as the lubricant (A), and a molecular weight of 1000 to 5 is used as the lubricant (B). Use a polio reflex dispersion of 0.000. More preferably, the lubricant (A) has a molecular weight of 600 to 15 without a polar group. 0.000 and particle size 0.1 to 5.Polyolefin Wax Dispurge Yone with Ομπι, molecular weight 600 000 to 150 000, acid value 40 or less, particle size 0.1 to 5.変性 Use at least one or more lubricants selected from modified polyolefin wax dispersions of μππι, and use a lubricant (Β) with a polar group-free molecular weight of 100 to 5 Use a polyolefin wax dispenser with a particle size of 0.1 to 3. Ομπι.

As the polyolefin wax dispersion, polyethylene wax, polypropylene wax or polyethylene wax having substantially no polar groups can be prepared by emulsifier concentration of 5% or less, preferably in water or aqueous solution without using emulsifier. Is used.

In addition, as the modified polyolefin wax dispersion, a polyethylene or wax containing a polar group, a polypropylene wax or a polypropylene wax is used in an emulsifier concentration of 5% or less, preferably in an aqueous or aqueous solution without using an emulsifier. Is used. The polar group can be introduced by oxidizing the polyolefin wax with an oxidizing agent such as oxygen, ozone or nitric acid in the presence of a catalyst (polyolefin wax), or acrylic acid. Dissolves ethylene-unsaturated olevonic acid monomer such as methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and polyolefin resin with benzene, etc. However, it can be heated and graphitized in a nitrogen stream together with a polymerization initiator (peroxide, redox, heavy metal catalyst, etc.) and introduced.

The weight average particle diameter of the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (Α) is preferably from 0 :! to 5. 5.μΟη, more preferably from 1.0 to 4 4. 0 μηι is used. In addition, the particle size of the lubricant (Α) Use a film larger than the thickness of the formed aqueous organic-inorganic composite film (D). If the mass average particle diameter of the lubricant (A) is less than 0.1 μππι, it is not preferable because it tends to aggregate and has poor stability. If the weight average particle diameter of the lubricant (Α) is smaller than that of the aqueous organic / inorganic composite film (D) formed on the upper layer, press galling resistance deteriorates, which is not preferable. On the other hand, when the mass average particle diameter exceeds 5.Ομπι, the dispersion stability is poor, which is not preferable. Further, the ratio between the mass average particle diameter and the number average particle diameter is preferably within the range of mass average particle diameter and number average particle diameter, in particular. The mass average particle diameter of the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (Β) is preferably from 0.1 to 3.Ομπι. The lubricant (粒径) should be smaller in particle size than the aqueous organic / inorganic composite film (D) formed on the upper layer. When the mass average particle diameter is less than ◦ .1 / m, it is not preferable because it easily aggregates and the stability is poor. In addition, when the mass average particle size exceeds 3.0 μπι, or when a lubricant (Β) having a particle size larger than the thickness of the aqueous organic / inorganic composite film (D) is used, the coil deformation resistance is reduced. Inferior because it is inferior.

The weight average molecular weight of the polyolefin wax dispersion and the modified polyolefin wax dispersion in the lubricant (A) is preferably in the range of 600 to 1500. If the weight average molecular weight is less than 600, the coil deformation resistance is inferior. On the other hand, when the weight average molecular weight exceeds 150,000, press galling resistance is poor, which is not preferable.

The weight average molecular weight of the polyolefin wax purge ion in the lubricant (B) is preferably in the range of 100 to 500,000. If the weight average molecular weight is less than 1000, it is easy to thermally decompose, and sufficient lubrication properties can be obtained in a direct-fired drying furnace whose surface is exposed to a high temperature near 100 ° C. It is not preferable because there is no case. On the other hand, if the average molecular weight exceeds 50,000, the effect of adding the lubricant B is not preferable because the effect of further improving the galling resistance cannot be obtained.

The method and conditions for analyzing the mass average molecular weight of these polyrefin wax dispersions and modified polyolefin wax dispersions are described earlier in the description of the surface-treated metal plate according to the first aspect of the present invention. The acid value (K0H-mg / _g ) specified in JISK592 for the modified polyolefin wax purge ion in the lubricant (A) as described in the above is 40 or less. I like it. If the acid value exceeds 40, the lubricating agent will be too hard, and sufficient lubricity cannot be obtained.

Furthermore, Poriorefui emissions wax disper one job down and modified polyolefin Nwa Kkusudisupa one job down in the lubricant (A) is, JISK 6 7 6 0 Density defined by the 9 5 0~ 1 0 0 0 kg Zm 3, JISK 2 The hardness (penetration) specified by 2007 is 0.2 mm or less, the crystallinity determined by X-ray diffraction method is 80% or more, and the melting point is 110 to 150 ° C. Are preferred.

The content of 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, paint adhesion deteriorates, which is not preferable.

The coating amount range of the aqueous organic / inorganic composite film (C) is 0.05 to 0.3 g / m ² as a dry mass. More preferably, it is 0.05 to 0.2 g / m ² . It is difficult to poor resistance to press galling resistance of interest, also wettability to exceed 0. 3 g Zm ² to form an upper layer film defeating low at a coverage of less than 0. 0 5 g / m ² Therefore, it is not preferable. water Adhesion amount of sex organic-inorganic composite coating film (D) range, as a dry mass is 0. 5 ~ 5. O g / m 2. Preferably 1. 0~ 3. O g / m ² to al of. The amount of adhered 0.5 In gZni less than ² poor resistance to press the steering-resistant for the purpose, also 5. 0 gZm ² to exceed the weldability because undesirable that difficult.

The coating method, baking temperature, and drying equipment for forming the aqueous organic-inorganic composite film in the third aspect of the present invention are as described above for the formation of the aqueous-organic composite film in the first aspect. The surface-treated metal plate according to the third aspect of the present invention preferably has a surface having a dynamic friction coefficient of 0.07 to 0.15 and a static friction coefficient of 0.10 or more. When the coefficient of kinetic friction is higher than 0.15, the resistance to press galling is poor, and when the coefficient of kinetic friction is lower than 0.07 and when the coefficient of static friction is lower than 0.10, the coil deformation resistance It is not preferable because it is inferior. Example

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.

First, an example according to the first aspect of the present invention will be described.

(1) Type of drug

Table 1 shows a list of the drugs used. Polyolefins Nwa Tsu Kusudei sparge Yo down except D 1 and D 8, the hardness of the density defined by JISK 6 7 6 0 is defined by 9 5 0~ 1 0 0 0 kg Zm 3, JISK 2 2 0 7 ( The penetration was 0.2 mm or less, the crystallinity determined by X-ray diffraction method was 80% or more, and the melting point was 110 to 150 ° C. Table 1 List of drugs

(2) Kind of metal plate

The metal plates shown in Table 2 were used. Table 2 Types of metal plates and coating weight (plate thickness: 0.8 mm)

(3) Chromate treatment

The EG and ZN shown in Table 2, chromic acid 5 0 g Z l and sulfuric acid 0. 3 g / 1 of a current density of 1 0 A / dm ² is energized a predetermined quantity of electricity electrolytic click port formate in a bath After being treated and washed with water, it was dried using a hot-air drying oven at an ultimate plate temperature of 80 ° C.

The GI shown in Table 2, after the reduction rate 4 0% reduction chromic acid and silica force was applied to _{S i O 2 / C r O} 3 become so compounded chromate treatment solution ₃ ratio, washing Dried without.

The amount of chromate film adhered was quantified in terms of Cr by X-ray fluorescence analysis.

(4) Preparation of aqueous organic-inorganic composite paint

One or both of the aqueous resin and the silicate compound shown in Table 1, colloidal silica and polyolefin wax dispersion were blended in the ratios shown in Tables 4 to 6 to prepare an aqueous organic-inorganic composite paint.

(5) Application and drying method of aqueous organic-inorganic composite paint

The aqueous organic-inorganic composite paint prepared in (4) was applied to the plated metal sheet subjected to the chromate treatment shown in (3) so as to have the dry weight values shown in Tables 4 to 6 and the ultimate plate temperature was 140. The sample for evaluation was prepared by baking and drying at ° 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 sample for evaluation prepared in (5) was tested according to the salt water fog test method described in JIS Z 2371.At an ambient temperature of 35 ° C, a 5% NaC 1 aqueous solution was sprayed on the coated steel sheet sample. Seventy-two hours later, the whitening rate was measured. In the following evaluations, ◎ and Δ were determined to be good.

◎: No white

〇: Whiteness occurrence rate <10%

△: White △ Occurrence rate of 10% or more and less than 50%

X: White 鲭 incidence rate 50% or more

b. Corrosion resistance of processed part

The test sample for evaluation prepared in (5) was subjected to an Erichsen addition of 6 mm, and was subjected to 5% NaCl at an ambient temperature of 35 ° C in accordance with the salt water fog test method described in JIS Z 2371. The aqueous solution was sprayed on the coated steel sheet sample, and the occurrence of white spots in the processed portion after 48 hours was measured. In the following evaluations, ◎ and Δ were judged to be good.

◎: White 鲭 No occurrence

〇: Whiteness occurrence rate less than 5%

△: White △ Occurrence rate 5% or more, less than 20%

X: Whitening rate 20% or more

c. Paint adhesion

In addition to the evaluation sample prepared in (5), a permeator was used to add a melanin-alkyd resin paint (Amilac # 1000, manufactured by Kansai Paint) to a dry film thickness of 25 μιη. It was baked at a furnace temperature of 130 ° C for 20 minutes. Next, after leaving for 1 晚, those immersed in boiling water for 30 minutes and those not so treated were subjected to 7 mm Erichsen processing, and an adhesive tape (Nichipan Co., Ltd .: Cellotape) was used for the test piece. It was attached to the oxen processed part. Adhesive tape quickly diagonally 45 ° The external appearance of the Eriksen processed part was visually evaluated. In the following evaluations, ◎ and Δ were judged to be good.

◎: No peeling

〇 Peeling area ratio less than 5%

Δ Peeling area ratio5. /. Not less than 50%

X Peeling area ratio 50% or more

d. Continuous weldability

The sample prepared in (5) was subjected to a continuous spot welding test under the conditions shown in Table 3, and the number of spots at which a nugget diameter of 3 mmφ or more could be formed stably was obtained.

Table 3 Welding conditions

In the following evaluations, ◎ and Δ were determined to be good.

◎: Number of hit points 5 0 0 0 or more

〇: Number of hit points 25 0 0 or more and less than 5 0 0 0

△: Number of hits 1 0 0 0 or more and less than 2 500

X: Number of hits less than 100

e. Press galling resistance

A rectangular cylinder crank press test was performed on the sample prepared in (5). The conditions of the square cylinder crank press test were as follows: a sample (0.8 x 220 x 180 mm) was molded to 65 x 115 mm and a height of 50 mm at a wrinkle pressure of 6 tons. The sliding surface after molding was visually evaluated. below ◎ and Δ were determined to be good in the evaluation.

◎: No blackening

〇: Less than 50% of the sliding area is blackened, with sliding flaws

△: 50% or more of the sliding area is blackened, with sliding flaws

X: Base metal is exposed and galling

f. Abrasion resistance test

The sample prepared in (5) was subjected to an elliptical vibration of 360 g / min with a load of 10 g Z cm ² through a vinyl resin film to generate abrasion on the sliding part. The sample surface after one minute test was visually evaluated. In the following evaluations, ◎ and Δ were determined to be good.

◎: No blackening

〇: Area less than 50% of the moving part is blackened

△: 50% or more of the sliding area is blackened

: Base metal is exposed

g. Static friction coefficient

Shinto Kagaku 10 Type HEID ON Static friction coefficient measuring device, 0.5 ° Z sec, a sample with an area of 25 cm ² excluding the paris prepared in (5) was attached to a flat indenter and weighed 2 Under the condition of 00 g, the coefficient of static friction between the samples prepared in (5) was measured.

h. Dynamic friction coefficient

Shinto Kagaku's 14S HEID ON dynamic friction coefficient measuring device, manufactured with (5) under conditions of 10 mm diameter stainless steel ball sliding, load of 100 g, sliding speed of 15 O mm / min The dynamic friction coefficient of the sample was measured.

i. Coil deformation resistance

After manufacturing several types of 10-t coils with an inner diameter of 508 mm and a thickness of 1 mm and different friction coefficients, these coils were moved up and down three times in the crane, The deviation (distance) of the coil winding direction (longitudinal direction) at the end caused by the loosening of the outer winding was measured, and the relationship between the dynamic friction coefficient and the static friction coefficient was investigated. As a result, the dynamic friction coefficient, the static friction coefficient, and the deviation (distance) at the end of the coil winding direction (longitudinal direction) caused by loosening correspond well, and the dynamic friction coefficient is less than 0.07 and the static friction coefficient When the value is less than 0.10, the displacement of the coil end due to loosening was 50 mm or more, but the dynamic friction coefficient was 0.07 or more and the static friction coefficient was 0.10 or more. However, the displacement of the coil end due to loose winding could be suppressed to 30 mm or less. Therefore, in the laboratory tests, the static friction coefficient and the dynamic friction coefficient measured by g and h above were used as indices of coil deformation resistance. 〇 was determined to be good in the following evaluations.

〇: Dynamic friction coefficient 0.07 or more, static friction coefficient 0.1 or more

X: Dynamic friction coefficient less than 0.07, static friction coefficient less than 0.1. As is clear from these results, the technology of the present invention is excellent in various performances such as corrosion resistance, adhesion, and weldability, and has a dynamic friction coefficient of 0.07 to 0.15 and a static friction coefficient of 0.1 or more. It is possible to obtain a surface-treated metal sheet excellent in press galling resistance and coil deformation resistance controlled in a controlled manner.

And ratio of each aqueous resin

Types and ratios

Table 5

Cr inorganic composite coating

1) The type and ratio of each aqueous resin to be added when the total amount of the aqueous resin or pho and silicate compounds is 100 in terms of solid mass.

2) The type and ratio of silica compounded when the entire organic-inorganic composite film is 100 in terms of solid mass.

3) The types and ratios of the spherical wax dispersons mixed when the entire organic-inorganic composite coating is 100 in terms of solid mass.

Table 6

O

2) The type and ratio of silica compounded when the entire organic-inorganic composite film is 100 in terms of solid content mass

3) The types and ratios of the spherical wax dispersions to be blended when the whole organic-inorganic composite film is 100 in terms of solid mass.

Table 8

Performance

Flat plate processing part Paint adhesion Weldability Press resistance Abrasion resistance Coil resistance Dynamic friction Static friction Remarks

;

Corrosion resistance Corrosion resistance J $ No workability Cement resistance Deformation coefficient Coefficient

26 ◎ © ◎ © ◎ ◎ ◎ 〇 0.07 0.15 The present invention

27 ◎ ◎ ◎ ◎ ◎ ◎ 〇 7 0.07 0.18 The present invention

28 X X △ Δ ◎ X X 〇 0.25 0.40 Comparative example

29 〇〇 o ο ◎ ο 〇 Ο 0.15 0.30 The present invention

30 ◎ ◎ © ◎ 〇 © ◎ Ο 0.10 0.20 The present invention

31 ◎ ◎ ο 〇 ◎ ◎ Ο 0.10 0.20 The present invention

32 © ◎ ◎ 〇 X ◎ ◎ Ο 0.10 0.20 Comparative example

33 X X Δ Δ ◎ X X 〇 0.25 0.45 Comparative example

34 〇 O 〇 ο © 〇〇〇 0.15 0.35 The present invention

35 © ◎ ◎ ® 〇 ◎ ◎ Ο 0.15 0.25 The present invention

36 ◎ ◎ ◎ 〇〇 ◎ ◎ 〇 0.10 0.20 The present invention

37 © ◎ ◎ 〇 X © ◎ 〇 0.10 0.20 Comparative example

38 X X △ Room © X X 〇 0.25 0.45 Comparative Example

39 o o 〇〇〇〇〇 0.15 0.35 The present invention

40 ◎ © ◎ ◎ 〇 © ◎ Ο 0.09 0.20 The present invention

41 ◎ @ ◎ 〇〇 ◎ ◎ 〇 0.09 0.20 The present invention

42 ◎ ◎ ◎ ο X ◎ ◎ 〇 0.09 0.20 Comparative example

43 mm Δ ◎ ο ◎ △ 〇〇 0.10 0.20 Comparative example

44 〇〇 ◎ ◎ 〇〇 ο 0.10 0.20 The present invention

45 ◎ ◎ © ◎ ◎ © 〇 0.10 0.20 The present invention

46 ◎ © ◎ 〇 ◎ ◎ © 〇 0.10 0.20 Invention

47 〇 o 〇 Δ 〇 Δ 〇〇 0.10 0.20 Comparative example

48 Δ ◎ ◎ ◎ Δ 〇〇 0.15 0.25 Comparative Example

49 〇〇 ◎ ◎ ◎ 〇〇 ο 0.15 0.25 Invention

50 ◎ ◎ ◎ ◎ ◎ ◎ 〇 5 0.15 0.25 The present invention

Table 9

Performance

¾ · Plate processing part Paint adhesion Weldability Press resistance Anti-ablation-Coil resistance Dynamic friction Static friction Remarks Corrosion resistance Corrosion resistance

¾ tott Workability Chilling property Deformation coefficient Coefficient

51 ◎ ◎ π ◎ © ◎ 〇 0.15 0.25 The present invention

52 〇 O 〇 A 〇 △ 〇〇 0.15 0.25 Comparative example

53 ◎ ◎ ◎ ◎ ◎ ◎ 〇 0.10 0.15 The present invention

54 ◎ ◎ ◎ ◎ 〇 ◎ 〇 0.15 0.20 The present invention

55 ◎ ◎ ◎ ◎ ◎ ◎ 〇 0.09 0.15 The present invention

56 ◎ ◎ ® ◎ ◎ 〇 0.10 0.20 The present invention

57 ◎ ◎ ◎ ◎ 〇 ◎ 〇 0.15 0-25 The present invention C 58 ◎ ◎ ◎ ◎ ◎ ◎ 〇 0.09 0.20 The present invention

59 ◎ 〇〇 m Δ ◎ ◎ 〇 0.10 0.25 The present invention

60 ◎ 〇〇 Δ ◎ ◎ ◎ 〇 0.10 0.25 The present invention

61 ◎ 〇〇 △ ◎ ◎ ◎ Ο 0.10 0.25 The present invention

62 ◎ 〇 ◎ ◎ 〇 0.10 0.25 The present invention

63 ◎ ◎ ◎ ◎ ◎ 〇 0.10 0.25 The present invention

64 Δ Δ 〇 ◎ ◎ ◎ 〇 0.10 0.20 The present invention

65 △ △ 〇 ◎ 〇 ◎ 〇 0.15 0.25 The present invention

66 mm △ 〇 ◎ ◎ ◎ 〇 0.09 0.20 The present invention

67 ◎ ◎ ◎ ◎ ◎ ◎ 〇 0.10 0.20 The present invention

68 ◎ ◎ ◎ 〇〇 0.10 0.20 The present invention

Next, an example according to the second aspect of the present invention will be described.

(1) Type of drug

Table 10 shows a list of the drugs used. Lubricants except D 7 (A), the hardness of the density defined by JISK 6 7 6 0 is defined by 9 5 0~ 1 0 0 0 kg / m 3, JISK 2 2 0 7 ( penetration) Was 0.2 mm or less, the crystallinity determined by X-ray diffraction method was 80% or more, and the melting point was 110 to 150 ° C.

Table 10 List of drugs

Drug type No.

A 1 Acrylic resin (Toa Gosei Co., Ltd., AP-1508 (1 2)) Organic tree A 2 Polyolefin aqueous resin (Toho Chemical Industry, AR-2300)

Fatty A 3 Polyurethane-based aqueous resin (Nippon—NSC, RA-85)

A 4 Epoxy-based water-based resin (Dainippon Ink, Dick Fine EM-60) Gay acid B 1 Lithium silicate

Chloride

B 2

Thing sodium silicate

B 3 Lithium silicate

Colloids I Aqueous colloidal silica (Nissan Chemical, trade name: Snowtex N) Dulsik aqueous colloidal silica (Nissan Chemical, trade name: Snowtex UP) Rica

D 1 polyethylene (molecular weight: 6000, acid value: 0, particle size: 3.0jum)

D 2 polyethylene (Molecular weight: 8000, Acid value: 0, Particle size: 3.0jum)

D3 polyethylene (molecular weight: 15000, acid value: 0, particle size: 3.0; um,)

D4 polyethylene (Molecular weight: 20000, Acid value: 0, Particle size: 3,0jiim,)

D 5 polyethylene (Molecular weight: 6000, Acid value: 0, Particle size: 0.1; um,) Lubricant 6000

A D 6 polyethylene (Molecular weight:, Acid value: 0, Particle size: 5.0jum,)

+ Comparison D 7 Modified polyethylene (Molecular weight 1000, Acid value: 20, Particle size: 1.0jum)

D 8 modified polyethylene (molecular weight 6000, acid value: 20, particle size: 1.0jum)

D 9 modified polyethylene (molecular weight 8000, acid value: 20, particle size: 1.0jum)

D10 modified polyethylene (Molecular weight 15000, Acid value: 20, Particle size: 1.0jum)

D11 Modified polyethylene (Molecular weight 20000, Acid value: 20, Particle size: 1.0μm,)

D12 modified polyethylene (molecular weight 6000, acid value: 20, particle size: 0.1jum)

D13 modified polyethylene (Molecular weight 6000, Acid value: 20, Particle size: 5.0 / zm,)

D14 modified polyethylene (molecular weight 6000, acid value: 40, particle size: 1.0jum)

D15 Modified polyethylene (Molecular weight 6000, Acid value: 100, Particle size: 1.0jum)

E16 polyethylene (molecular weight 500, acid value: 0, particle size: 3.0Aim,) Lubricants E17 polyethylene (molecular weight 1000, acid value: 0, particle size: 3.0 // m,)

B E18 polyethylene (molecular weight 5000, acid value: 0, particle size: 3.0; m,)

+ Comparative E19 polyethylene (molecular weight 1000, acid value: 0, particle size: 5.0 m,)

E20 polyethylene (Molecular weight 1000, Acid value: 0, Particle size: 0.1 jLi m,)

E21 polyethylene (Molecular weight 5500, Acid value: 0, Particle size: m,) (2) Kind of metal plate

The metal plates shown in Table 2 above were used.

(3) Chromate treatment

The example according to the first aspect is described above.

(4) Preparation of aqueous organic-inorganic composite paint

One or both of the aqueous resin and the silicate compound shown in Table 10, a colloidal silicide force, and a lubricant were blended in the ratios shown in Tables 11 to 13 to prepare an aqueous organic-inorganic composite paint.

(5) Application and drying method of aqueous organic-inorganic composite paint

The aqueous organic-inorganic composite paint prepared in (4) was applied to the plated metal plate subjected to the chromate treatment in (3) so as to have a dry weight of the values shown in Tables 11 to 13, and the ambient temperature was 50 ° C. A sample for evaluation was prepared by baking and drying in a hot air circulating drying oven at 0 ° C at an ultimate plate temperature of 140 ° 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 example according to the first aspect is described above.

b. Corrosion resistance of processed part

The example according to the first aspect is described above.

c. Paint adhesion

The example according to the first aspect is as described above.

d. Continuous weldability

The example according to the first aspect is as described above.

e. Press galling resistance

The example according to the first aspect is described above.

f. Abrasion resistance test The example according to the first aspect is as described above.

g. Continuous sliding wear resistance

A plastic (videotape case) punched out to 10 mm is attached to a terminal with a load of 500 g using a rotary sliding abrasion tester, and placed on the surface of a sample applied to a disk. The sample surface was observed every 50 rotations at 60 rotations per minute, and evaluated by the number of rotations at which plating was damaged.

h. Dynamic friction coefficient

The example according to the first aspect is as described above.

i. Thermal decomposition stability

(5) The prepared sample was heat-treated in a direct-fired drying furnace with an ambient temperature of 900 ° C and an air ratio of 1.0 to 1.5 at an ultimate plate temperature of 140 ° C, increasing the dynamic friction coefficient. The case where the resistance to press galling and the resistance to continuous sliding wear deteriorated was judged as poor (X), and the case where they were equal was judged as good (〇).

〇: After heat treatment, dynamic friction coefficient, press galling resistance, continuous sliding wear resistance are equivalent

X: High coefficient of kinetic friction after heat treatment, deteriorates press galling resistance and continuous sliding wear resistance

Tables 14 to 16 show the above evaluation results. As is clear from these results, the surface of the present invention is excellent in various performances such as corrosion resistance, adhesion and weldability, and is also excellent in press galling resistance and continuous sliding wear resistance. A treated metal plate can be obtained.

Table 11

Table 1 2

1) Type and ratio of each aqueous resin to be blended when the total amount of the aqueous resin and / or the gayate compound is set to “100” in terms of solid content mass

3) Type and ratio of each spherical wax dispersion to be blended when the whole organic-inorganic composite film is 100 in terms of solid content mass

Table 13

Table 14

Table 15

Performance

Flat plate processing Paint adhesion Welding Press resistance Affle resistance-Continuous sliding Dynamic friction Pyrolysis Remarks Corrosion resistance Corrosion resistance Deterioration Workability Number of times coefficient Stability

31 ◎ ◎ ◎ o ◎ 800 0.05 0 The present invention

32 ◎ ◎ ^ ΰ) ◎ ◎ ◎ 1000 0.06 o The present invention

33 ◎ ◎ ◎ o ◎ 900 0.05 o The present invention

34 ◎ ◎ © ◎ 1200 0.06 o The present invention

35 ◎ ® © © 1000 0.05 〇 The present invention

36 ◎ ◎ ^ Q) ◎ © 1200 0.06 o The present invention

37 © ◎ ◎ o o 800 0.06 o The present invention

38 ◎ ® © o ◎ 1100 0.05 o The present invention

39 ο o S 'Re ◎ © ◎ 1500 0.05 o The present invention

40 ◎ ◎ o o 800 0.06 o The present invention

41 ◎ ◎ (Q) © o ◎ 1100 0.05 o The present invention

42 ο o (J © ◎ © 1500 0.05 o The present invention

43 X X Δ Δ ◎ X X 100 0.08 o Comparative example

44 ο U u o o 500 0.06 o The present invention

45 (S) is ◎ © 1000 0.05 o The present invention

46 © ◎ U o © ◎

47 o X ◎ ◎ 1800 0.06 0 Comparative example

48 X X Δ △ ◎ X X 100 0.08 比較 Comparative example

49 O o 〇 o ◎ o 〇 500 0.06 o The present invention

50 © ◎ ◎ © ◎ ◎ ◎ 1000 0.05 〇 The present invention

51 ◎ ◎ ◎ o o ◎ 1500 0.05 発明 The present invention

52 ◎ ◎ © o X ◎ ◎ 1800 0.06 o Comparative example

53 X X △ Δ ◎ X X 100 0.08 o Comparative example

54 O o 〇〇 ◎ o 〇 500 0.06 o The present invention

55 © ◎ ◎ ◎ ◎ ◎ 1000 0.05 o The present invention

56 ◎ ® ◎ o o ◎ ◎ 1500 0.05 o The present invention

57 © ◎ o X ◎ ◎ 1800 0.06 〇 Comparative example

58 mm Δ ◎ ◎ ◎ mm o 800 0.10 o Comparative example

59 o O ◎ ◎ ◎ 〇 o 1000 0.10 〇 The present invention

60 ◎ ◎ ◎ ©-◎ © 1000 0.10 o The present invention

Table 16

Performance

Plate processing part Paint adhesion Weldability Press resistance Anti-abrasion resistance -Continuous sliding Dynamic friction Pyrolysis Remarks Jip chapter corrosion resistance Nil `` Recruitment right Workability 14 times coefficient Stability

61 © ◎ π © ◎ ◎ 1000 0.10 o The present invention

62 o ο Λ o Δ ο 1000 0.10 n Comparative example

63 Δ Δ Re ◎ Δ ο 800 0.10 n

64 o ο ◎ ο ο 1000 0.10 o The present invention

65 ◎ (5) @ © 1000 0.10 o The present invention

66 © © ©) 000 0.J0 o The present invention

67 o ο Re A o Δ ο 1000 0.10 o Comparative example

68 ◎ © ◎ ◎ ◎ 1000 0.05 o The present invention

69 β νϋ) * © ο (0) 1000 0.07 n Invention

70 (0) (0)! 000 0.05 n Invention

71 © ◎ ® ◎ ◎ ◎ ◎ 1000 0.05 o The present invention

72 ◎ ◎ © © ◎ ◎ ◎ 1000 0.07 o The present invention

73 ◎ ◎ © ◎ ◎ ◎ ◎ 1000 0.05 〇 The present invention

74 ◎ ο 〇 Δ ◎ ◎ ◎ 2000 0.06 〇 The present invention

75 ◎ 〇〇 Δ © ◎ ◎ 2000 '0.06 〇 The present invention

76 ◎ ο 〇 △ ◎ ◎ ◎ 2000 0.06 〇 The present invention

77 ◎ ◎ ◎ O ◎ ◎ ◎ 1800 0.06 O The present invention

78 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1800 0.06 〇 The present invention

79 Δ Δ © o ◎ ® ◎ 1000 0.05 〇 The present invention

80 Δ △ ◎ o ◎ ◎ ◎ 1000 0.05 〇 The present invention

81 Δ Δ ◎ o ◎ ◎ ◎ 1000 0.05 〇 The present invention

82 ◎ ◎ ◎ ◎ ◎ © ◎ 1500 0.05 発明 The present invention

83 ◎ ◎ ◎ ◎ ◎ ◎ 2000 0.05 〇 The present invention

Subsequently, an example according to the third aspect of the present invention will be described.

(1) Type of drug

A list of the drugs used is shown in Table 17. Lubricant A except D 7 is J

Density 9 defined by ISK 6 7 6 0 5 0~ 1 0 0 0 kg Zm 3

The hardness (penetration) specified by JISK2207 is 0.2 mm or less, the crystallinity determined by X-ray diffraction method is 80% or more, and the melting point is 110 to 150. ° C.

Table 17 List of drugs

Drug type No.Product name

A 1 Acrylic resin (Toa Gosei Co., Ltd., AP-1 508 (1 2)) Organic resin A 2 Polyolefin-based aqueous resin (Toho Chemical Industry, AR-2300)

A 3 Polyurethane-based aqueous resin (Nippon—made by NSC, RA-85)

A 4 Epoxy-based water-based resin (Dainippon Ink, Dick Fine EM-60) Gay acid salt B 1 Lithium silicate

Compound B 2 Sodium silicate

B 3 force silicate

Colloidal C 1 aqueous colloidal silica (Nissan Chemical, trade name: Snowtex N) Luciri force C 2 aqueous colloidal silica (Nissan Chemical, trade name: Snowtex UP)

D 1 polyethylene (molecular weight 6000, acid value: 0, particle size: 3. Ojum,)

D 2 polyethylene (Molecular weight 8000, Acid value: 0, Particle size: 3.0jum)

D3 polyethylene (Molecular weight 15000, Acid value: 0, Particle size: 3.0jum,)

D4 polyethylene (molecular weight 20000, acid value: 0, particle size: 3.0 / im,)

D 5 polyethylene (molecular weight 6000, acid value: 0, particle size: 0.1 m,)

D 6 Polyethylene (Molecular weight 6000, Acid value: 0, Particle size: 5.0〃m,) Lubricant A

D 7 modified polyethylene (Molecular weight 1000, Acid value: 20, Particle size: 3.0 m) + Comparison

D 8 Modified polyethylene (molecular weight 6000, acid value: 20, particle size: 3,0 / m,)

D 9 modified polyethylene (Molecular weight 8000, Acid value: 20, Particle size: 3. Ojum,)

D10 modified polyethylene (Molecular weight 15000, Acid value: 20, Particle size: 3.0jum)

D11 modified polyethylene (Molecular weight 20000, Acid value: 20, Particle size: 3.0 m,)

D12 modified polyethylene (Molecular weight 6000, Acid value: 20, Particle size: 0.1 m,)

D13 Modified polyethylene (molecular weight 6000, acid value: 20, particle size: 5.0jum)

D14 modified polyethylene (Molecular weight 6000, Acid value: 40, Particle size: 3,0〃m,)

D15 Modified polyethylene (molecular weight 6000, acid value: 100, particle size: 3.0jum) Lubricant B E16 polyethylene (molecular weight 1000, acid value: 0, particle size: 0.6 m,)

E17 polyethylene (molecular weight 5000, acid value: 0, particle size: 0.6 A <m,) + comparison E18 polyethylene (molecular weight 1000, acid value: 0, particle size: 3.0jum,)

E19 Polyethylene (Molecular weight 1000, Acid value: 0, Particle size: 0.1 m,) (2) Kind of metal plate

The metal plates shown in Table 2 above were used.

(3) Chromate treatment

The example according to the first aspect is as described above.

(4) Preparation of aqueous organic-inorganic composite paint

One or both of the aqueous resin and the silicate compound shown in Table 17 and the colloidal sily force and the lubricant were blended in the ratios shown in Tables 18 to 20 to prepare an aqueous organic-inorganic composite paint.

(5) Application and drying method of aqueous organic-inorganic composite paint

The aqueous organic / inorganic composite paint prepared in (4) was applied to the plated metal sheet subjected to the chromate treatment in (3) so that the dry mass was as shown in Tables 18 to 20 and the ultimate plate temperature was 1 A sample for evaluation was prepared by baking and drying at 40 ° 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 example according to the first aspect is described above.

b. Corrosion resistance of processed part

The example according to the first aspect is described above.

c. Paint adhesion

The example according to the first aspect is described above.

d. Continuous weldability

The example according to the first aspect is as described above.

e. Press galling resistance

The example according to the first aspect is as described above.

f. Peeling resistance test of surface lubricant

Square cylinder crank press test on the sample prepared in (5) Was repeated 100 times. After the continuous press test, the state of peeling of the surface lubricant attached to the mold was observed and evaluated. In the following evaluation, 〇 was judged to be good.

：: No sticky lubricant accumulated

X: Sticky lubricant is deposited

g. Abrasion resistance test

The example according to the first aspect is as described above.

h. Static friction coefficient

The example according to the first aspect is as described above.

i. Dynamic friction coefficient

The example according to the first aspect is as described above.

j. Coil deformation resistance

'' As described above for the example according to the first aspect.

Tables 21 to 23 show the above evaluation results. As is evident from these results, the technology of the present invention excels in various performances such as corrosion resistance, adhesion, and weldability, and excels 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 the agent falling off is suppressed.

Table 18

Cr Organic film C Skin D

cn

n

) Type and ratio

3) The types and ratios of the spherical wax dispersions to be blended when the entire organic-inorganic composite film is 100 in terms of solid mass.

Table 19

Cr coating D

1) The type and ratio of each aqueous resin to be mixed when the total amount of the aqueous resin and / or the gayate compound is 100 in terms of solid content mass

Table 20

Cn

1) Aqueous resin or Ζ and the type and ratio of each aqueous resin to be added when the entire gaylate compound is 100 in terms of solid content mass

Table 21

Performance

Plate processing part Paint adhesion Weldability Press resistance Abrasion resistance Peeling resistance Coil dynamic friction Static friction Remarks Corrosion resistance Corrosion resistance Penetration Workability

3 ◎ ◎ ◎ ◎ ◎ ο 〇〇〇 0.15 0.25 The present invention

4 ◎ ◎ ◎ ◎ ◎ Δ 〇〇〇 0.20 0.30 Comparative example

6 ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 0.07 0.12

7 ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 X 0.06 0.10 Comparison

8 ◎ ◎ ◎ ◎ ◎ 〇〇 0.09 0.20 The present invention

1 1 ◎ ◎ ◎ ◎ ◎ X Δ O o 0.20 0.35 Comparative example

14 ◎ ◎ ◎ ◎ ◎ ◎ o 0.15 0.30 The present invention

1 5 ◎ ◎ ◎ ◎ ◎ X X oo 0.20 0.35 Comparative example

16 ◎ ◎ ◎ ◎ ◎ ◎ 〇 o 0.10 0.20 The present invention

17 ◎ ◎ ◎ ◎ ◎ ◎ o o 0.10 0.20 The present invention

18 ◎ ◎ ◎ ◎ 〇 ◎ ◎ o o 0.10 0.20 The present invention

1 9 ◎ ◎ ◎ ◎ ◎ ◎ @ 〇 o 0.10 0.20 The present invention

20 ◎ ◎ ◎ ◎ ◎ ◎ 〇 'o' 0.10 0.20 The present invention

23 ® ◎ ◎ ο ◎ oo 0.10 0.25 The present invention

24 ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 0 0.10 0.25 The present invention

25 ◎ ◎ ◎ ◎ ◎ ◎ o o 0.10 0.25 The present invention

26 ◎ ◎ ◎ ◎ ◎ ◎ ◎ o o 0.12 0.25 The present invention

27 ◎ ◎ ◎ ◎ ◎ ◎ ◎ o o 0.10 0.20 The present invention

29 ◎ ◎ ◎ ◎ ◎ ◎ ◎ o o 0.15 0.30 The present invention

30 ◎ ◎ ◎ ◎ ◎ ◎ ◎ oo 0.10 0.20 The present invention

Table 22

Performance

No.Plate processing part Paint adhesion Weldability Press resistance Abrasion resistance Peeling resistance Coil kinetic friction Static friction equipment Corrosion resistance Corrosion resistance 浸漬 nf Immersion Yes

◎ ◎ Coefficient Coefficient

32 ◎ ◎ ◎ ◎ ◎ 〇〇〇〇 0.15 0.30

◎ The present invention

33 ◎ ◎ ◎ ◎ ◎ o 〇 0.12 0.25 The present invention

34 〇 ◎ ◎ 〇 ◎ ◎ 〇〇 0.10 0.20 The present invention

35 Δ Δ 〇 Δ ◎ ◎ 〇〇 0.10 0.20 The present invention

36 ◎ ◎ ◎ ◎ 〇〇〇〇 o 0.20 0.35

◎ ◎ The present invention

38 〇 ◎ ◎ 〇 ◎ ◎ ◎ o 〇 0.15 0.30 Unit 発

39 Δ Δ room ◎ ◎ ◎ 〇〇 0.15 0.30 The present invention

40 X X Δ ◎ XX X 〇 0.08 0.15 Comparative example

41 〇〇 Ο ο 〇〇 o 〇 0.08 0.15 The present invention

◎ The present invention

43 ◎ 〇〇 ◎ ◎ o o 0.10 0.30 The present invention

46 O 〇〇 ο 〇〇 o o 0.08 0.20 The present invention

47 ◎ ◎ ◎ ◎ ◎ ◎ ◎ o o 0.10 0.25 Invention

48 ◎ ◎ ◎ ο 〇 ◎ ◎ o o 0.J0 0.25 Invention

49 ◎ ◎ ◎ ο X ◎ ◎ o o 0.25 0.35 Comparison row

50 ◎ ◎ ◎ ◎ ◎ X X oo 0.2 0.30 Compare 1 row

51 ◎ ◎ ◎ ◎ ◎ 〇 o o o 0.15 0.25 The present invention

52 ◎ ◎ ◎ ◎ ◎ ◎ 〇 0.2 0.1 0.20 The present invention

53 ◎ ◎ ◎ ◎ ◎ X X oo 0.20 0.30 Comparative example

56 Δ ◎ ◎ ◎ △ O 〇 o 0.10 0.20 Comparative example

57 〇 O ◎ ◎ Ο o o o 0.10 0.20

58 ◎ ◎ ◎ ◎ ◎ ◎ ◎ o 〇 0.10 0.20 The present invention

Table 23

Industrial applicability

The surface-treated metal sheet according to the first aspect of the present invention is excellent in various performances such as corrosion resistance, adhesion, weldability, and the like, while maintaining press galling resistance.

However, since it has improved the problem of coil collapse due to loose winding and load collapse at the time of cutting board cutting, it is suitable as a material for home appliances, building materials and automotive fields. Further, by the aqueous organic-inorganic composite paint and the production method according to the first aspect of the present invention, a surface-treated metal sheet having good press galling resistance and coil deformation resistance can be provided to the market.

The surface-treated metal plate according to the second aspect of the present invention is excellent in various performances such as corrosion resistance, adhesion, weldability, etc., and is also excellent in press galling resistance and continuous sliding wear resistance. It is also suitable as a material for home appliances, building materials and automobiles. Further, the water-based organic-inorganic composite paint and the production method according to the second aspect of the present invention can provide a surface-treated metal sheet having good press galling resistance and continuous sliding wear resistance to the market. .

The surface-treated metal plate according to the third aspect of the present invention is excellent in various performances such as corrosion resistance, adhesion, weldability, and the like. In addition to improving the problem of load collapse during rolling, it also suppresses the generation of sticky residue caused by the lubricant falling off from the film during pressing, so it is also used in the home appliance, building materials and automotive fields. It is suitable as a material. Further, by the production method according to the third aspect of the present invention, a surface-treated metal plate having good press galling resistance and coil deformation resistance can be provided to the market.

Claims

The scope of the claims

1. One or both of the aqueous resin and the silicate compound, and a polyolefin wax dispersion having a molecular weight of 600 to 1500 and a solid content of 5 to 35% by mass. 0. 3 the aqueous organic-inorganic composite film you containing mouth Idarushiri force 5. 0 g Zm ² anti press galling resistance and coil deformation excellent in surface treated metal plate to feature in that it has.

2. The polyolefin wax dispenser is a polyolefin wax dispersant having a molecular weight of 600 to 150 and a particle size of 0.1 to 5. At least one selected from modified polyolefin wax dispersions having a molecular weight of 600-150 and an acid value of 40 or less, and a particle size of 0.1-5.1 μμπι. The surface-treated metal sheet according to claim 1, which is excellent in press galling resistance and coil deformation resistance.

3. The anti-press galling resistance and coil deformation resistance according to claim 1 or 2, wherein the coefficient of dynamic friction of the surface is 0.07 to 0.15 and the coefficient of static friction is 0.10 or more. Excellent surface treated metal plate.

4. One or both of the aqueous resin and Kei salt compounds, further, the molecular weight of 6 0 0 0-1 5 0 0 0 Poly Orefui emissions wax disperser job down and 5-3 5 mass in terms of solid content ⁰ Aqueous organic-inorganic composite paint, characterized by containing / ₀ colloidal silica and water.

5. The polyolefin wax dispenser is a polyolefin wax disperser having a molecular weight of 600 to 150 and a particle size of 0.1 to 5. At least one selected from a modified polyolefin wax dispenser having a molecular weight of 600 to 1500 and an acid value of 40 or less and a particle size of 0.1 to 5.0 μm The aqueous organic-inorganic composite paint according to claim 4, wherein:

6. 4. 0.3 to 5 paint on a dry weight terms of plated metal sheet according. After O gZm ² coating, and forming an aqueous organic-inorganic composite coating baked, galling resistance press For producing surface-treated metal sheets with excellent heat resistance and coil deformation resistance.

7. Claim 5 0.3 to 5 paint on a dry weight terms of plated metal sheet according. After O gZm ² coating, characterized by forming an aqueous organic-inorganic composite coating baked, resistance galling resistance press And a method for producing a surface-treated metal sheet with excellent coil deformation resistance.

8. Lubricant (A) composed of one or both of an aqueous resin and a silicate compound, and a polyolefin wax dispersion having a molecular weight of 600 to 1500, a molecular weight of 1 An aqueous organic-inorganic composite film containing a lubricant (B) composed of a polyolefin wax dispensing iron of 00000 to 50,000 and a colloidal sili force of 5 to 35% by mass in terms of solid content. A surface-treated metal sheet excellent in press galling resistance and continuous sliding wear resistance, comprising 0.3 to 5.0 g / m ^{2 of} the aqueous organic-inorganic composite coating.

9. The lubricant (A) has a molecular weight of 600 to 1500 without polar groups and a particle size of 0.1 to 5.0 m. At least one lubricant selected from the group consisting of modified polyolefin wax disposables having a particle size of 0.1 to 5.0 μm with an acid value of 40 or less, and a lubricant (B) Is a polyolefin wax dispersion having a molecular weight of 100 to 500,000 containing no polar group and a particle size of 0.1 to 5.0 μm. Surface-treated metal sheet with excellent press galling and continuous wear resistance.

10. One or both of the aqueous resin and the silicate compound, and Lubricant (A) composed of a polyolefin wax dispersion with a molecular weight of 600 to 150,000, and a polyolefin wax dispersion with a molecular weight of 100,000 to 500,000 Aqueous organic-inorganic composite paint containing a lubricant (B) composed of water and colloidal silica and water in an amount of 5 to 35% by mass in terms of solid content.

11. The lubricant (A) has a molecular weight of 600 to 1500 without a polar group and a particle size of 0,0 to 5; 0-: 150 000, acid value 40 or less, particle size 0.1-5. It is characterized in that the agent (オレ) is a polyolefin resin dispersion having a molecular weight of 100 to 500 and a particle size of 0.1 to 5.0 μm which does not contain a polar group. The aqueous organic-inorganic composite paint according to claim 10.

12. After 0. 3~ 5. 0 gZm ² coating an aqueous organic-inorganic composite coating according to claim 1 0, wherein the plated metal plate on a dry燥質amount conversion, characterized by forming an aqueous organic-inorganic composite coating baked A method for producing a surface-treated metal sheet having excellent press galling resistance and continuous sliding wear resistance.

13. After 0. 3~ 5. 0 gZm ² coating an aqueous organic-inorganic composite coating of claim 1 1, wherein a dry燥質amount converted into plated metal plate, characterized by forming an aqueous organic-inorganic composite coating baked A method for producing a surface-treated metal sheet that is excellent in press galling resistance and continuous sliding wear resistance.

14. As a first layer, one or both of the aqueous resin and the silicate compound, and a lubricant (A) composed of a polyolefin powder disposable ion having a molecular weight of 600 to 1500. The aqueous organic-inorganic composite film (C) to be dried has a dry mass of 0.05 to 0.3 g / m ^2, and as the second layer, one or both of the aqueous resin and the silicate compound, and Consists of 5 to 35% by mass of colloidal silica in terms of solid content Aqueous organic-inorganic composite coating film (D) the dry mass and to 0. 5~ 5. 0 g / m ² good surface treated metal sheet resistant to press galling resistance and coil deformation properties characterized by having being .

15. The lubricant (A) has a molecular weight of 600 to 150 without a polar group and a particle size of 0.1 to 5. Polyolefin wax particle purge ion with a particle size of 0.1 to 5. ~: 150,000, acid value of 40 or less, particle size of 0.1 to 5.0 μm, characterized in that it is at least one or more lubricants selected from modified polyolefin waxed purge ion. 15. The surface-treated metal sheet according to claim 14, which is excellent in press galling resistance and coil deformation resistance.

16. The aqueous organic-inorganic composite film (C) is an aqueous resin and a polyolefin wax dispersion having a molecular weight of 600 to 1500 Lubricant (A) and a molecular weight of 100 to 500 16. The galling resistance according to claim 14 or 15, wherein the lubricant is composed of a composite lubricant mixed with a lubricant (B), which is a polyolefin-based discharge purge ion of No. 0. Surface treated metal sheet with excellent coil deformation resistance.

17. Polyolefin Wax Discharge Purge Yon with a molecular weight of 600-150,000 and a particle size of 0.1-5.0 μπι, in which the lubricant (A) does not contain a polar group, and a molecular weight of 600,000 At least one lubricant selected from modified polyolefin waxed dispurgeons with a particle size of 0.1 to 5.0 μm, an acid value of 40 or less, and a particle size of 0.1 to 5.0 μm. The lubricant (B) is a polyolefin wax day dispersion having a molecular weight of 100 to 500 and a particle size of 0.1 to 3.0 μm containing no polar group. 16 Surface-treated metal sheet with excellent press galling resistance and coil deformation resistance described in 6.

18.The coefficient of dynamic friction of the surface is 0.07 ~ 0.15, the coefficient of static friction is 0.

10. Any one of claims 14 to 17, characterized in that it is 10 or more. A surface-treated metal plate with excellent press galling resistance and coil deformation resistance described in (2).

19. On top of the plated metal sheet, one or both of an aqueous resin and a silicate compound, and a lubricant (A), which is a polyolefin wax disposable ion having a molecular weight of 600 to 1500, and after the configuration aqueous organic-inorganic composite coating (E) and 0. 0 5~ 0. 3 g / m 2 coating on a dry mass conversion with water to form a first layer and baked, then the aqueous resins Or an aqueous organic-inorganic composite paint (F) comprising a silicate compound, a colloidal silicide and water and having a colloidal silica content of 5 to 35% by mass in terms of solid content, in terms of a dry mass of 0. 5 ~ 5. O g Zm ² was coated, baked and resistance to press galling resistance and method of manufacturing the excellent surface treated metal plate resistance coil deformability, characterized by forming the second layer.

20. The lubricant (A) does not contain a polar group and has a molecular weight of 600 000 to 150 000 and a particle size of 0:! To 5. 0 to 1500, an acid value of 40 or less, and a particle size of 0.1 to 5.0 μιη. It must be at least one lubricant selected from modified polyolefin resin 10. The method for producing a surface-treated metal sheet according to claim 19, which is excellent in press galling resistance and coil deformation resistance.

21. The aqueous organic-inorganic composite coating material (E) is an aqueous resin, a polyolefin wax dispersion having a molecular weight of 600 to 1500 Lubricant (A) and a molecular weight of 100 to 500 21. The press galling resistance and press resistance according to claim 19 or 20, characterized by comprising a composite lubricant mixed with a lubricant (B), which is a polyolefin powder purge ion of No. 0, and water. A method for producing surface-treated metal sheets with excellent coil deformability.

22. The lubricant (A) contains a polar group-free polyolefin wax particle with a molecular weight of 600 to 150 and a particle size of 0.1 to 5. At least one lubricant selected from the group consisting of modified polyolefin wax disposables having a particle size of 0.1 to 5.0 μm, an acid value of 40,000 or less, and a lubricant (B ) Is a polyolefin wax dispersion having a molecular weight of 100 to 500 and a particle size of 0.1 to 3.0 m containing no polar group. 21. A method for producing a surface-treated metal sheet excellent in press galling resistance and coil deformation resistance described in any one of 1.