Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

• 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.
• 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.
• many of these steel sheets have corrosion resistance
• chromate treatment and phosphate treatment are applied for the purpose of improving paint adhesion.
• 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.
• 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.
• 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. .
• the techniques disclosed in Japanese Patent Application Laid-Open Nos. 3-39485 and 3-28380 generate galling and abrasion during press working described above.
• 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.
• 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.
• 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.
• the gist of the present invention is as follows.
• 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 ⁇ m.
• the surface-treated metal sheet according to (1) which is excellent in press galling resistance and coil deformation resistance.
• a water-based organic-inorganic composite coating comprising: a colloidal silica; and water.
• 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.
• the gist of the present invention is as follows.
• aqueous resin and a silicate compound 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 .
• aqueous resin and the silicate compound composed of a polyolefin wax dispersion having a molecular weight of 600 to 1500, a molecular weight of 100
• 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.
• 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 ⁇ . (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.
• 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.
• the gist of the present invention is as follows.
• 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
• 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.
• 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.
• Surface treated metal sheet with excellent resistance to press galling and coil deformation.
• 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 0.1 ⁇ , lubricant ( ⁇ ) 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 ⁇ . Surface-treated metal sheet with excellent resistance to press galling and coil deformation.
• 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.
• 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 ⁇ 5.0 ⁇ m, characterized by at least one or more lubricants selected from modified polyolefin wax dispersions.
• 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.
• 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 ⁇ , an acid value of 40 to 150, an acid value of 40 or less, and a lubricant ( ⁇ ) 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.
• 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.
• 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.
• 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.
• 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.
• the particles are present in a granular form on the film surface, ⁇ ⁇ 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.
• 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.
• 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.
• a base treatment for the purpose of improving adhesion or corrosion resistance
• 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.
• a cross-linking agent such as various melamine resins and amino resins may be added.
• an acrylic resin such as a copolymer of olefin-acrylic acid.
• 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.
• 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.
• 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.
• 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
• 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.
• 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.
• 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 ⁇ m, more preferably from 1.0 to 4.0 ⁇ . 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. ⁇ , 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.
• Measurement temperature 130 to 140 ° C -Detector: Differential refractometer (RI) or infrared detector
• 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.
• JISK 6 7 6 0 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.
• 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. .
• lubricants (A) and (B) having different molecular weights are used as a lubricant in a predetermined amount in the aqueous organic / inorganic composite paint.
• 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).
• 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 (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a lubricant (A), a
• a polyolefin wax dispersion having a low molecular weight and a polyolefin wax dispersion having a high molecular weight which have been conventionally used, they can be added together.
• 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.
• 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.
• 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.
• water-based resin those described above for the surface-treated metal plate on the first side surface can also be used.
• a cross-linking agent such as various melamine resins and amino resins as necessary. It is.
• an acrylic resin such as an olefin-acrylic acid copolymer.
• a urethane-epoxy resin having both hardness and elongation.
• 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.
• 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 ⁇ m, which does not contain a polar group, and a molecular weight of 600 to 1
• (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.
• 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.
• polyethylene wax, polypropylene wax, or polypropylene wax containing a polar group is emulsifier concentration of 5% or less, preferably water without emulsifier.
• 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.
• an oxidizing agent such as oxygen, ozone, or nitric acid
• a catalyst polyolefin oxide wax
• acrylic acid methacrylic acid
• An ethylene unsaturated monomer such as crotonic acid, maleic acid, fumaric acid, and itaconic acid
• the mass average particle diameter of the polyolefin waxed dispersion and the modified polyolefin waxed purged is preferably from 0.1 to 5.0 ⁇ m, more preferably from 1.0 to 4.0 ⁇ . use Is done. If the mass average particle size is less than 0.1 ⁇ , it is not preferable because the particles are likely to aggregate and have poor stability. Further, when the mass average particle diameter exceeds 5. ⁇ , 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. .
• the mass average molecular weight is less than 60 ° 0, it is too soft, so that continuous sliding wear resistance cannot be improved.
• 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. .
• 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.
• 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.
• 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.
• 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.
• FIG. 3 shows an example of the surface-treated metal plate of the first embodiment according to the third aspect of the present invention
• FIG. 4 shows an example of the surface-treated metal plate of the second embodiment.
• 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.
• 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.
• 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
• 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.
• water-based resin those described above for the surface-treated metal plate on the first side surface can also be used.
• a cross-linking agent such as various melamine resins and amino resins as necessary. It is.
• 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.
• 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.
• 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.
• 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).
• the lubricant (A) has a molecular weight of 600 to 15 without a polar group.
• 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.
• 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.
• 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.
• ethylene-unsaturated olevonic acid monomer such as methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and polyolefin resin with benzene, etc.
• olevonic acid monomer such as methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and polyolefin resin with benzene, etc.
• 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 ( ⁇ ) is preferably from 0 :! to 5. 5. ⁇ , more preferably from 1.0 to 4 4. 0 ⁇ is used.
• the particle size of the lubricant ( ⁇ ) 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 ⁇ , it is not preferable because it tends to aggregate and has poor stability.
• the weight average particle diameter of the lubricant ( ⁇ ) 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. ⁇ , 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 ( ⁇ ) is preferably from 0.1 to 3. ⁇ .
• the lubricant ( ⁇ ) should be smaller in particle size than the aqueous organic / inorganic composite film (D) formed on the upper layer.
• the mass average particle diameter is less than ⁇ .1 / m, it is not preferable because it easily aggregates and the stability is poor.
• the mass average particle size exceeds 3.0 ⁇ , or when a lubricant ( ⁇ ) 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.
• 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
• the melting point is 110 to 150 ° C.
• 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.
• 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
• Table 2 The metal plates shown in Table 2 were used. Table 2 Types of metal plates and coating weight (plate thickness: 0.8 mm)
• 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 amount of chromate film adhered was quantified in terms of Cr by X-ray fluorescence analysis.
• 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.
• 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.
• 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 ⁇ were determined to be good.
• 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 ⁇ were judged to be good.
• a permeator was used to add a melanin-alkyd resin paint (Amilac # 1000, manufactured by Kansai Paint) to a dry film thickness of 25 ⁇ . It was baked at a furnace temperature of 130 ° C for 20 minutes. Next, after leaving for 1 ⁇ , 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 ⁇ were judged to be good.
• 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 mm ⁇ or more could be formed stably was obtained.
• 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 ⁇ were determined to be good in the evaluation.
• 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 ⁇ were determined to be good.
• 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
• 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.
• 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. ⁇ was determined to be good in the following evaluations.
• X Dynamic friction coefficient less than 0.07, static friction coefficient less than 0.1.
• 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.
• 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.
• a 1 Acrylic resin (Toa Gosei Co., Ltd., AP-1508 (1 2)) Organic tree
• a 2 Polyolefin aqueous resin (Toho Chemical Industry, AR-2300)
• Colloids I Aqueous colloidal silica (Nissan Chemical, trade name: Snowtex N) Dulsik aqueous colloidal silica (Nissan Chemical, trade name: Snowtex UP) supra
• D3 polyethylene (molecular weight: 15000, acid value: 0, particle size: 3.0; um,)
• a D 6 polyethylene (Molecular weight:, Acid value: 0, Particle size: 5.0jum,)
• D13 modified polyethylene (Molecular weight 6000, Acid value: 20, Particle size: 5.0 / zm,)
• E20 polyethylene (Molecular weight 1000, Acid value: 0, Particle size: 0.1 jLi m,)
• aqueous resin and the silicate compound shown in Table 10 were blended in the ratios shown in Tables 11 to 13 to prepare an 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.
• the example according to the first aspect is as described above.
• the example according to the first aspect is as described above.
• 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.
• the example according to the first aspect is as described above.
• 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 ( ⁇ ).
• Tables 14 to 16 show the above evaluation 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.
• 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.
• 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)
• 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,)
• D14 modified polyethylene (Molecular weight 6000, Acid value: 40, Particle size: 3,0 ⁇ 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,)
• the example according to the first aspect is as described above.
• 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.
• 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.
• the example according to the first aspect is as described above.
• the example according to the first aspect is as described above.
• the example according to the first aspect is as described above.
• the example according to the first aspect is as described above.
• the example according to the first aspect is as described above.
• Tables 21 to 23 show the above evaluation 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.
• 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.
• 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.

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