JP2009102549A - Water-based magnetic coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based magnetic coating composition having excellent storage stability, and capable of forming a magnetic pattern having stereoscopic effects according to the magnetic field of a material to be coated. <P>SOLUTION: The water-based magnetic coating composition contains one or more kinds of rust proof pigments (A) selected from a phosphate-based rust proof pigment of a compound of phosphoric acid and one or more kinds of elements (a), a phosphite-based rust proof pigment of a compound of phosphorous acid and one or more kinds of the elements (a), and a condensed phosphate-based rust proof pigment of a compound of condensed phosphoric acid and one or more kinds of the elements (a), a scaly iron pigment and a resin composition. The one or more kinds of the elements (a) are selected from zinc, calcium, aluminum, titanium, silicon, magnesium, manganese, strontium, barium, iron, zirconium and cerium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an aqueous magnetic coating composition that is excellent in storage stability and forms a magnetic pattern that three-dimensionally expresses characters and patterns corresponding to the magnetic field of an object to be coated.

  Traditionally, industrial products such as automobile interior parts and electrical products have been painted for the purpose of protecting the material. In recent years, in addition to protecting products, painting is also performed in various colors in order to further enhance the consumer's impression of the product. In recent years, in various industrial products, in order to increase the product power, there are cases where various patterns are given in addition to simply coloring the surface.

  One of the patterns that can be expressed by painting is a magnetic pattern that expresses characters and patterns in three dimensions. Specifically, magnetic pigments are blended in the paint, a magnetic field is formed around the object to be coated when the coating is formed, and the orientation of the magnetic pigment is controlled according to the formed magnetic field. By doing so, a magnetic pattern can be formed. Among the magnetic pigments, scaly iron pigments can be mentioned as pigments that have a sharp response to a magnetic field and can form a sharp pattern on a coating film obtained by applying a paint blended with a magnetic pigment.

  On the other hand, in recent years, in order to reduce the environmental load, the conversion from organic solvent-based paints to water-based paints is progressing. When scale-like iron pigments are blended into water-based paints, iron and water react to generate hydrogen gas, resulting in a decrease in storability, and the surface of the scale-like iron pigment is modified to reduce the finish. Had a problem to do.

  Patent Document 1 relates to a magnetic pattern forming paint and a method of forming a coating film using the same. Patent Document 1 describes a coating composition mainly composed of a resin component, a magnetic metal-coated pigment, and an organic solvent. However, it is a solvent-type coating using an organic solvent as a solvent. There is no description or suggestion.

Japanese Patent Laid-Open No. 2003-176252

The object of the present invention is to form a sharp magnetic pattern corresponding to the magnetic field formed around the substrate to be coated, and to suppress the generation of hydrogen gas due to the reaction between the scaly iron pigment and water during storage. Another object of the present invention is to provide a water-based magnetic coating composition.

1. Phosphate rust preventive pigment which is a compound of phosphoric acid and one or more elements (a), Phosphate rust preventive pigment which is a compound of phosphorous acid and one or more elements (a), and One or more rust preventive pigments (A) selected from condensed phosphate rust preventive pigments, which are compounds of condensed phosphoric acid and one or more elements (a), scaly iron pigments, and resin compositions The one or more elements (a) are selected from zinc, calcium, aluminum, titanium, silicon, magnesium, manganese, strontium, barium, iron, zirconium, and cerium. 1. a water-based magnetic coating composition that is one or more elements that have been produced; 2. The aqueous magnetic coating composition according to item 1, wherein the antirust pigment (A) is an antirust pigment obtained by treating aluminum dihydrogen phosphate with zinc.

The aqueous magnetic coating composition of the present invention can form a sharp magnetic pattern corresponding to the magnetic field formed around the substrate to be coated, and generates hydrogen gas by the reaction of iron and water during storage. In addition, the coating film obtained by further painting has the effect of being white with highlights and having a shade that does not become cloudy yellow.

The aqueous magnetic coating composition of the present invention contains a rust preventive pigment, a scaly iron pigment, and a resin composition.

  The aqueous magnetic coating composition of the present invention contains a scaly iron pigment as a magnetic pigment that is oriented in accordance with the magnetic field formed around the object to be coated when the coating film is formed.

  The flaky iron pigment is generally produced by pulverizing and grinding particulate iron in a ball mill or attritor mill in the presence of a pulverizing medium solution, and usually has an average particle diameter (D50) of 1 to 50 μm for coatings. In particular, those in the range of 5 to 20 μm, and those having a thickness in the range of 0.01 μm to 10 μm, especially 0.1 μm to 5 μm, are stable in the paint and finish of the coating film to be formed. Used from the point of. The average particle diameter means a long diameter. Aliphatic hydrocarbons such as mineral spirits are used as the grinding fluid.

  In the aqueous magnetic coating composition of the present invention, the amount of the scaly iron pigment is 0 with respect to 100 parts by mass of the solid content of the resin composition to be described later, from the viewpoint of the metallic feeling and finished appearance of the obtained coating film. 0.1 to 50 parts by mass is preferable, and 5 to 25 parts by mass is more preferable.

  The antirust pigment is blended for the purpose of suppressing the generation of hydrogen caused by the surface of the scaly iron pigment reacting with the water in the coating composition. One or more rust preventive pigments selected from acid salt rust preventive pigments, phosphite rust preventive pigments and condensed phosphate rust preventive pigments can be used.

  Phosphate-based rust preventive pigments are phosphoric acid and one or more elements selected from zinc, calcium, aluminum, titanium, silicon, magnesium, manganese, strontium, barium, iron, zirconium and cerium. Means a compound of

  The phosphite-based anticorrosive pigment is phosphorous acid and one or more selected from zinc, calcium, aluminum, titanium, silicon, magnesium, manganese, strontium, barium, iron, zirconium and cerium. It means a compound with an element.

  Condensed phosphate rust preventive pigment is a salt of condensed phosphoric acid in which a plurality of phosphoric acids are bonded, and includes zinc, calcium, aluminum, titanium, silicon, magnesium, manganese, strontium, barium, iron, zirconium and cerium. It is a compound with 1 type, or 2 or more types of elements selected from these. A typical example is aluminum dihydrogen tripolyphosphate.

  The rust preventive pigment to be blended in the aqueous magnetic coating composition of the present invention is the above-mentioned phosphate-based rust preventive pigment, phosphite-based rust preventive pigment, and condensed phosphate-based rust preventive pigment subjected to a surface treatment. And those modified with metal oxides or metal salts.

  The water-based magnetic coating composition of the present invention can contain one or more kinds selected from the above rust preventive pigments. The content is 0.1 to 50 parts by mass based on the storage stability of the aqueous magnetic coating composition and the finish of the coating film obtained by coating with respect to 100 parts by mass of the solid content of the scale-like iron pigment. It is preferable to be within the range, more preferably within the range of 5 to 25 parts by mass.

  The aqueous magnetic coating composition of the present invention contains a resin composition as a vehicle-forming component. As the resin composition, a thermosetting resin composition is preferable. Specifically, a base resin such as an acrylic resin, a polyester resin, an alkyd resin, or a urethane resin having a crosslinkable functional group such as a hydroxyl group is used as a melamine resin. , Urea resins, polyisocyanate compounds (including block bodies) and the like are also used in combination, and these can be used by dissolving or dispersing in water. A combination of an acrylic resin, a polyester resin, and a melamine resin as a crosslinking agent is particularly preferred from the viewpoints of finish and coating film performance.

  Moreover, a color pigment can be mix | blended with the water-based magnetic coating composition of this invention as needed. As the color pigment, conventionally known pigments for ink and paint can be used alone or in combination of two or more. Specific examples of color pigments include metal oxide pigments such as titanium oxide and iron oxide, composite metal oxide pigments such as titanium yellow, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, and perinone pigments. Examples thereof include pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrene pigments, dioxazine pigments, and indigo pigments.

  The preferred content of these color pigments in the aqueous magnetic coating composition of the present invention is 50 masses with respect to 100 mass parts of the solid content in the resin composition from the viewpoint of the color tone and finish of the coating film obtained by coating. It is preferably no greater than 1 part, more preferably within the range of 1-30 parts by weight.

  The water-based magnetic coating composition of the present invention can contain a bright pigment in addition to the scale-like iron pigment. Examples of the bright pigment include scaly metal pigments such as aluminum and copper (other than magnetic metals such as nickel and stainless steel), scaly metal pigments whose surfaces are coated with metal oxides, and chemical adsorption of colored pigments on the surface. Scale-like metal pigments, scale-like metal pigments having a metal oxide layer formed by causing a redox reaction on the surface, glass flake pigments, glass flake pigments whose surfaces are coated with metal oxides, and color pigments on the surface Chemically adsorbed glass flake pigment, interference mica pigment coated with titanium dioxide on the surface, reduced mica pigment reduced from interference mica pigment, colored mica pigment chemically adsorbed on the surface or coated with iron oxide on the surface, Graphite pigments coated with titanium dioxide on the surface, silica flakes and alumina flake pigments coated with titanium dioxide on the surface, Grams pigment, synthetic mica pigments, cholesteric liquid crystal polymer pigments having a helical structure, and the like oxy bismuth pigments chloride. Various glitter pigments can be appropriately used depending on the glitter feeling for which one or more of these are desired.

  When the above-mentioned glitter pigment is used, its blending amount is the glitter of the coating film obtained by coating with respect to 100 parts by mass of the resin solid content in the aqueous magnetic coating composition as the total amount with the scaly iron pigment. From the viewpoint of feeling and finish, 50 parts by mass or less is preferable, and more preferably in the range of 1 to 30 parts by mass.

  In the aqueous magnetic coating composition of the present invention, water or an organic solvent, a rheology control agent, a pigment dispersant, an anti-settling agent, a curing catalyst, an antifoaming agent, an antioxidant, an ultraviolet absorber, etc., as necessary. Various additives, extender pigments and the like can be appropriately blended.

  The aqueous magnetic coating composition of the present invention can be prepared by mixing and dispersing the aforementioned components. In addition, the rust preventive pigment (A) is previously mixed with the resin composition and water to prepare a rust preventive pigment dispersion, and the rust preventive pigment dispersion is mixed with the above-described components to form an aqueous magnetic coating composition. Can be blended.

  The pigment dispersion will be described. When a pigment is blended in the coating composition, it is necessary to stably exist in a good dispersion state in the coating composition. Therefore, the pigment may be blended into the coating composition as a powder and then dispersed, but a pigment dispersion containing a high concentration of the pigment and maintaining a good dispersion state is prepared in advance. And can be blended into the coating composition as a pigment dispersion.

When preparing the pigment dispersion of the anticorrosive pigment (A) for blending in the aqueous magnetic coating composition of the present invention, for example, it can be carried out as follows. The resin composition, which is a vehicle forming component of the aqueous magnetic coating composition of the present invention, and the rust preventive pigment (A) are mixed. The blending ratio at this time is preferably from the viewpoint of the dispersion state in the pigment dispersion so that the rust preventive pigment is in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the solid content of the resin composition. . Furthermore, water is added and it adjusts so that solid content may be in the range of 30-80 mass%.
The mixture of the obtained antirust pigment (A), resin and water is used in combination with a grinding medium such as glass beads or ceramic beads, and dispersed using a disperser such as a bead mill or paint conditioner. Can be prepared in a high concentration. Further, the pigment dispersion may contain a commercially available pigment dispersant for the purpose of maintaining a good dispersion state of the pigment.

  The aqueous magnetic coating composition of the present invention is prepared by mixing a rust preventive pigment (A), the aforementioned scaly iron pigment, a resin composition, and, if necessary, a coloring pigment or a bright pigment, and then a basic neutralizing agent. It is preferable to adjust the pH within the range of 6 to 10 by adding the composition in order to enhance the effect of suppressing gas generation during storage.

  Examples of the basic neutralizer composition include aliphatic tertiary amines, and specifically include triethylamine, N, N-dimethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine, triethanolamine, and the like. Ethanolamine or the like can be used.

  The method for producing the aqueous magnetic coating composition of the present invention will be described. As a first aspect, a high concentration scaly iron pigment liquid containing a scaly iron pigment and an organic solvent is prepared in advance. Next, the high-concentration scaly iron pigment liquid is added to the mixture of the resin composition, which is a vehicle-forming component in the aqueous magnetic coating composition, and mixed with stirring. Further, when a bright pigment is blended, a high-concentration bright pigment liquid containing the bright pigment and, for example, ethylene glycol monobutyl ether is previously prepared and added. When a coloring pigment is blended, a coloring pigment dispersion can be prepared and added in the same manner as the preparation of the antirust pigment dispersion described above. Next, the aforementioned rust preventive pigment dispersion is added and further stirred and mixed, and then the basic neutralizing agent composition is added to adjust the pH of the aqueous magnetic coating composition. Thereafter, if necessary, an additive or water can be added to produce an aqueous magnetic coating composition having a viscosity suitable for coating.

  As a 2nd aspect, the high concentration scaly iron pigment liquid containing a scaly iron pigment, an organic solvent, and a rust preventive pigment is prepared beforehand. Next, the high-concentration scaly iron pigment liquid is added to a mixture of resin compositions that are vehicle-forming components in the aqueous coating composition and mixed with stirring. Thereafter, an aqueous magnetic coating composition having a viscosity suitable for coating can be produced in the same manner as in the first embodiment.

  The organic solvent used for the high-concentration scaly iron pigment liquid is not particularly limited. For example, glycol ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, hexyl cellosolve, Ethylene glycol monomethyl ether, methyl methoxybutanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl and propylene glycol monobutyl ether, ether ester solvent methoxybutyl, alcohol solvent methyl alcohol, ethyl Alcohol, isopropyl alcohol, 2-ethylhexyl alcohol and n-butyl alcohol, n It can be used methylpyrrolidone or mixtures thereof.

  Next, an Example is given and this invention is demonstrated more concretely.

Production Example 1
(Manufacture of acrylic resin emulsion)
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, 130 parts by mass of deionized water, Aqualon KH-10 (trade name, surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.52 mass The components were charged, stirred and mixed in a nitrogen stream, and heated to 80 ° C. Next, 1% of the total amount of the following monomer emulsion (1) and 5.3 parts by mass of 6% ammonium persulfate aqueous solution were introduced into the reaction vessel and maintained at 80 ° C. for 15 minutes. Then, the remaining monomer emulsion (1) was dripped in the reaction container hold | maintained at the same temperature over 3 hours, and it age | cure | ripened for 1 hour after completion | finish of dripping. Thereafter, the following monomer emulsion (2) was added dropwise over 1 hour, and after aging for 1 hour, the mixture was cooled to 30 ° C while gradually adding 40 parts by mass of a 5% dimethylethanolamine aqueous solution to the reaction vessel, It was discharged while being filtered through a nylon cloth, and the average particle size was 100 nm (submicron particle size distribution measuring device “COULTER N4 type” (manufactured by Beckman Coulter, Inc.), diluted with deionized water and measured at 20 ° C.). An acrylic resin emulsion having a solid content concentration of 30% was obtained. The obtained acrylic resin had an acid value of 33 mgKOH / g and a hydroxyl value of 25 mgKOH / g.

  Monomer emulsion (1): 42 parts by weight of deionized water, 0.72 parts by weight of Aqualon KH-10, 2.1 parts by weight of methylenebisacrylamide, 2.8 parts by weight of styrene, 16.1 parts by weight of methyl methacrylate, ethyl acrylate Monomer emulsion (1) obtained by mixing and stirring 28 parts by mass and 21 parts by mass of n-butyl acrylate.

  Monomer emulsion (2): 18 parts by weight of deionized water, 0.31 part by weight of Aqualon KH-10, 0.03 part by weight of ammonium persulfate, 5.1 parts by weight of methacrylic acid, 5.1 parts by weight of 2-hydroxyethyl acrylate Monomer emulsion (2) obtained by mixing and stirring 3 parts by weight of styrene, 6 parts by weight of methyl methacrylate, 1.8 parts by weight of ethyl acrylate, and 9 parts by weight of n-butyl acrylate.

Production Example 2
(Manufacture of polyester resin)
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and water separator, 109 parts by weight of trimethylolpropane, 141 parts by weight of 1,6-hexanediol, 126 parts by weight of hexahydrophthalic anhydride and 120 parts of adipic acid A mass part was charged, and the temperature until reaching 160 ° C. to 160 ° C. was increased to 3 hours, and then a condensation reaction was performed at 230 ° C. for 4 hours. Subsequently, in order to add a carboxyl group to the obtained condensation reaction product, 38.3 parts by mass of trimellitic anhydride was further added and reacted at 170 ° C. for 30 minutes, and then 2-ethyl-1-hexanol (20 The polyester resin solution having a solid content concentration of 70% was obtained by diluting with a mass dissolved in 100 g of water at 0.1 ° C. (0.1 g). The obtained polyester resin had an acid value of 46 mgKOH / g, a hydroxyl value of 150 mgKOH / g, and a weight average molecular weight of 6,400. Here, the weight average molecular weight means that measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

Example 1
In a stainless steel beaker, STAPA FERRICON (trade name, scaly iron pigment, solid content 70% by mass, D50 = 18 μm, manufactured by Ecart Co., Ltd.) 100 parts by mass, ethylene glycol monobutyl ether 140 parts by mass and K-WHITE 140W (trade name, 4.7 parts by mass of an anticorrosive pigment obtained by treating aluminum dihydrogen trihydrogenphosphate with zinc (manufactured by Teika) was stirred and mixed to obtain a high-concentration scaly iron pigment liquid (1).

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 52.4 parts by mass of the above high-concentration scaly iron pigment liquid (1) and Cymel 325 (trade name) 37.5 parts by mass of Nippon Cytec Industries, Inc., melamine resin, solid content 80%), and further mixed with Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener) , 2- (dimethylamino) ethanol and deionized water were added, pH 8.0, paint solids 25%, Ford Cup No. 20 at 20 ° C. An aqueous magnetic coating composition (1) having a viscosity of 40 seconds according to 4 was prepared.

Example 2
The aqueous magnetic coating composition (2) was the same as in Example 1 except that K-WHITE 105 (trade name, a rust preventing pigment obtained by treating aluminum dihydrogen trihydrogenphosphate with zinc, manufactured by Teika) was used as the rust preventing pigment. Was prepared.

Example 3
An aqueous magnetic coating composition (3) was prepared in the same manner as in Example 1 except that EXPERT NP-530 (trade name, zinc phosphate, manufactured by Toho Pigment Industries Co., Ltd.) was used as the rust preventive pigment.

Example 4
An aqueous magnetic coating composition (4) was prepared in the same manner as in Example 1 except that EXPERT NP-1007 (trade name, zinc phosphate / calcium phosphite, manufactured by Toho Pigment Industries Co., Ltd.) was used as a rust preventive pigment.

Example 5
In a stainless steel beaker, STAPA FERRICON (trade name, scaly iron pigment, solid content 70% by mass, D50 = 18 μm, manufactured by Ecart Co., Ltd.) 100 parts by mass, ethylene glycol monobutyl ether 140 parts by mass and K-WHITE 140W (trade name, 14 parts by mass of an anticorrosive pigment obtained by treating aluminum dihydrogen trihydrogenphosphate with zinc (manufactured by Teika) was stirred and mixed to obtain a high-concentration scaly iron pigment liquid (2).

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 54.4 parts by mass of the above high-concentration scaly iron pigment liquid (2) and Cymel 325 (trade name) 37.5 parts by mass of Nippon Cytec Industries, Inc., melamine resin, solid content 80%), and further mixed with Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener) , 2- (dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. 25 at 20 ° C. An aqueous magnetic coating composition (5) having a viscosity of 40 seconds according to 4 was prepared.

Example 6
The aqueous magnetic coating composition (6) was the same as in Example 5 except that K-WHITE 105 (trade name, a rust preventing pigment obtained by treating aluminum dihydrogen phosphate with zinc, manufactured by Teika) was used as the rust preventing pigment. Was prepared.

Example 7
An aqueous magnetic coating composition (7) was prepared in the same manner as in Example 5 except that EXPERT NP-530 (trade name, zinc phosphate, manufactured by Toho Pigment Industries Co., Ltd.) was used as the rust preventive pigment.

Example 8
An aqueous magnetic coating composition (8) was prepared in the same manner as in Example 5 except that EXPERT NP-1007 (trade name, zinc phosphate / calcium phosphite, manufactured by Toho Pigment Industries Co., Ltd.) was used as a rust preventive pigment.

Example 9
In a stainless steel beaker, 100 parts by mass of STAPA FERRICON (trade name, scaly iron pigment, solid content 70% by mass, D50 = 18 μm, manufactured by Ecart Co., Ltd.) and 140 parts by mass of ethylene glycol monobutyl ether were mixed with high concentration. A scaly iron pigment liquid (3) was obtained.

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 51.4 parts by mass of the above high-concentration scaly iron pigment liquid (3) and Cymel 325 (trade name) 37.5 parts by mass of Nippon Cytec Industries, Inc., melamine resin, solid content 80%). Next, 3 parts by mass of K-WHITE 140W (trade name, antirust pigment obtained by treating aluminum dihydrogenaluminum tripolyphosphate with zinc, manufactured by Teica) was mixed by stirring, and further, Primal ASE-60 (trade name, manufactured by Rohm and Haas) , Polyacrylic acid thickener), 2- (dimethylamino) ethanol and deionized water, pH 8.0, paint solids 25%, Ford Cup No. A water-based magnetic coating composition (9) having a viscosity of 40 seconds according to 4 was prepared.

Example 10
225 ml of mayonnaise bottle is mixed with 50 parts by weight of K-WHITE 140W, 14.3 parts by weight of the polyester resin solution obtained in Production Example 2 and 45 parts by weight of deionized water, and further 130 parts by weight of 1.5 mm diameter glass beads. The part was introduced and sealed, and dispersed for 120 minutes using a shake type paint conditioner. After the dispersion, 100-mesh wire mesh filtration was performed to remove the glass beads to obtain an antirust pigment dispersion (1). The obtained antirust pigment dispersion (1) was analyzed using deionized water as a medium by a Microtrac MT3000 particle size analyzer (manufactured by MICROTRAC), and D50 = 0.6 μm. Since D50 = 2.7 μm of the pigment solid of K-WHITE140W, it was confirmed that it was certainly atomized.

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 55.9 parts by mass of the polyester resin solution obtained in Production Example 2, 51.4 parts by mass of the above high-concentration scaly iron pigment liquid (3), and Cymel 325 ( 37.5 parts by mass of a product name, manufactured by Nippon Cytec Industries, Ltd., melamine resin, solid content 80%) was mixed. Next, 6.6 parts by mass of the above rust preventive pigment dispersion (1) was stirred and mixed, and further, Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener), 2- ( Dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. A water-based magnetic coating composition (10) having a viscosity of 40 seconds according to 4 was prepared.

Example 11
225 ml of mayonnaise bottle is mixed with 50 parts by mass of K-WHITE 140W, 14.3 parts by mass of the polyester resin solution obtained in Production Example 2 and 45 parts by mass of deionized water, and further 130 parts of zirconia beads having a diameter of 1.5 mm. The part was introduced and sealed, and dispersed for 60 minutes using a shake type paint conditioner. After the dispersion, 100-mesh wire mesh filtration was performed to remove the zirconia beads to obtain a rust preventive pigment dispersion (2). The obtained anti-rust pigment dispersion (2) was analyzed using deionized water as a medium by a Microtrac MT3000 particle size analyzer (manufactured by MICROTRAC). D50 = 0.5 μm. Since D50 = 2.7 μm of the pigment solid of K-WHITE140W, it was confirmed that it was certainly atomized.

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 55.9 parts by mass of the polyester resin solution obtained in Production Example 2, 51.4 parts by mass of the above high-concentration scaly iron pigment liquid (3), and Cymel 325 ( 37.5 parts by mass of a product name, manufactured by Nippon Cytec Industries, Ltd., melamine resin, solid content 80%) was mixed. Next, 6.6 parts by mass of the rust preventive pigment dispersion (2) was stirred and mixed, and further, Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener), 2- ( Dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. A water-based magnetic coating composition (11) having a viscosity of 40 according to 4 was prepared.

Example 12
In a stainless steel beaker, STAPA FERRICON (trade name, scaly iron pigment, solid content 70% by mass, D50 = 18 μm, manufactured by Ecart Co., Ltd.) 100 parts by mass, ethylene glycol monobutyl ether 140 parts by mass and K-WHITE 140W (trade name, 0.7 parts by mass of an anticorrosive pigment obtained by treating aluminum dihydrogen trihydrogenphosphate with zinc (manufactured by Teika) was mixed by stirring to obtain a high-concentration scaly iron pigment liquid (4).

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 51.6 parts by mass of the above high-concentration scaly iron pigment liquid (4) and Cymel 325 (trade name) 37.5 parts by mass of Nippon Cytec Industries, Inc., melamine resin, solid content 80%), and further mixed with Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener) , 2- (dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. 25 at 20 ° C. A water-based magnetic coating composition (12) having a viscosity of 40 according to 4 was prepared.

Example 13
In a stainless steel beaker, STAPA FERRICON (trade name, scaly iron pigment, solid content 70% by mass, D50 = 18 μm, manufactured by Ecart Co., Ltd.) 100 parts by mass, ethylene glycol monobutyl ether 140 parts by mass and K-WHITE 140W (trade name, 28 parts by mass of an anticorrosive pigment obtained by treating aluminum dihydrogen trihydrogenphosphate with zinc (manufactured by Teika) was stirred and mixed to obtain a high-concentration scaly iron pigment liquid (5).

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 57.4 parts by mass of the above high-concentration scaly iron pigment liquid (5) and Cymel 325 (trade name) 37.5 parts by mass of Nippon Cytec Industries, Inc., melamine resin, solid content 80%), and further mixed with Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener) , 2- (dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. 25 at 20 ° C. A water-based magnetic coating composition (13) having a viscosity of 40 seconds according to 4 was prepared.

Example 14
100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 55.3 parts by mass of the polyester resin solution obtained in Production Example 2, 51.4 parts by mass of the above high-concentration scaly iron pigment liquid (3) and Cymel 325 ( 37.5 parts by mass of a product name, manufactured by Nippon Cytec Industries, Ltd., melamine resin, solid content 80%) was mixed. Next, 13.1 parts by mass of the above rust preventive pigment dispersion (2) was stirred and mixed, and further, Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener), 2- ( Dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. An aqueous magnetic coating composition (14) having a viscosity of 40 seconds according to 4 was prepared.

Comparative Example 1
100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 51.4 parts by mass of the above high-concentration scaly iron pigment liquid (3) and Cymel 325 (trade name) 37.5 parts by mass of Nippon Cytec Industries, Inc., melamine resin, solid content 80%), and further mixed with Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener) , 2- (dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. 25 at 20 ° C. An aqueous magnetic coating composition (15) having a viscosity of 40 seconds according to 4 was prepared.

Comparative Example 2
100 parts by mass of granular metallic nickel and 50 parts by mass of mineral spirit were placed in a pot mill having a diameter of 10 cm and an internal volume of 500 ml into which 1 kg of a steel ball having a diameter of 3 mm was inserted, and dispersed in a ball mill for 24 hours. The resulting slurry was washed out with 700 g of mineral spirits to separate from the steel balls. This was subjected to suction filtration with a magnetic funnel to obtain a scaly nickel pigment dispersion (D50 = 18 μm: measured by Microtrac) having a solid content of 85% by mass.

  In a stainless steel beaker, 100 parts by mass of the flaky nickel pigment dispersion and 170 parts by mass of ethylene glycol monobutyl ether were stirred and mixed to obtain a high-concentration flaky nickel pigment liquid.

  100 parts by mass of the acrylic resin emulsion obtained in Production Example 1, 57 parts by mass of the polyester resin solution obtained in Production Example 2, 47.6 parts by mass of the above high-concentration scaly nickel pigment solution, and Cymel 325 (trade name, Nippon Cytec 37.5 parts by mass of Industries, Inc., melamine resin, solid content 80%) were mixed uniformly. Further, Primal ASE-60 (trade name, manufactured by Rohm and Haas, polyacrylic acid thickener), 2- (Dimethylamino) ethanol and deionized water were added to adjust the pH of Ford Cup No. An aqueous magnetic coating composition (16) having a viscosity of 40 according to 4 was prepared.

  The outline of the above Examples and Comparative Examples is shown in Table 1.

(Gas generation measurement)
After preparing the aqueous magnetic paint compositions (1) to (16) for one day, 200 g of the paint is put into a dedicated glass container (internal volume 500 ml), and the container is immersed in a constant temperature bath at 40 ° C. without plugging. Then, after standing for 1 hour, the glass apparatus was stoppered to start (0 hour), the amount of accumulated gas generation for 7 days was measured, and the results are shown in Table 2.
(Creation of test plate)
Cationic electrodeposition paint "Electron GT-100" (trade name: manufactured by Kansai Paint Co., Ltd., cured on epoxy resin polyamine-based cationic resin on degreased and zinc phosphate treated steel plate (JISG3141, size 150 x 70 x 0.8 mm) Electrodeposition coating) using a block polyisocyanate compound as an agent) based on the cured coating film so as to have a film thickness of 20 μm, followed by heating at 170 ° C. for 20 minutes for crosslinking and curing. Obtained.

  On the obtained electrodeposition coating film, an intermediate coating "Lugabek intermediate coating N-2" (trade name: manufactured by Kansai Paint Co., Ltd., polyester resin / melamine resin type, organic solvent type) is applied by air spray. Based on the cured coating film, it was applied to a film thickness of 30 μm, heated at 140 ° C. for 30 minutes to be crosslinked and cured, and a coated plate on which an intermediate coating film was formed was used as a substrate.

  A donut-shaped ferrite magnet (outer diameter 60 mm, inner diameter 45 mm) was attached to the upper surface of the back surface of the base material to form a magnetic field on the surface of the base material.

Aqueous magnetic coating compositions (1) to (16) were each applied to the surface of the base material by air spraying to a thickness of 20 μm based on the cured coating film, allowed to stand for 15 minutes, and heated at 80 ° C. for 10 minutes for moisture. Then, the magnet is removed, and a clear paint (Lugabe Kukuriya, manufactured by Kansai Paint, trade name, acrylic resin / amino resin type, organic solvent type) is applied to these uncured coating surfaces. Using an electric coating machine, the coating film was applied to a thickness of 30 μm as a cured coating film under conditions of a boot temperature of 25 ° C. and a humidity of 75%. After coating, the sample was left at room temperature for 15 minutes, and then heated in a hot air circulating drying oven at 140 ° C. for 30 minutes to dry and cure the multilayer coating film at the same time to obtain test plates 1 to 16.
(Evaluation of test plate)
1) The pattern following property to the magnetic field was evaluated by visual observation, and the results are shown in Table 2.
5: The outline of the magnet appears very clearly and there is a feeling of shading.
4: The outline of the magnet is clearly displayed and there is a slight shading.
3: The outline of the magnet appears and there is a little shading.
2: The outline of the magnet is slightly unclear and there is not much shading.
1: The outline of the magnet is unclear and there is no shading.
2) L * value of highlight (irradiated at 45 degrees, received at 15 degrees from regular reflected light) and b * of face (received at 45 degrees) were measured, and the results are shown in Table 2.

The aqueous magnetic coating composition of the present invention can be applied to various industrial products.

Claims (2)

Phosphate rust preventive pigment which is a compound of phosphoric acid and one or more elements (a), Phosphate rust preventive pigment which is a compound of phosphorous acid and one or more elements (a), and Contains one or more rust preventive pigments selected from condensed phosphate rust preventive pigments, which are compounds of condensed phosphoric acid and one or more elements (a), scaly iron pigments, and resin compositions One or more elements (a) selected from zinc, calcium, aluminum, titanium, silicon, magnesium, manganese, strontium, barium, iron, zirconium and cerium Or the aqueous magnetic coating composition which is 2 or more types of elements. The aqueous magnetic coating composition according to claim 1, wherein the rust-preventive pigment (A) is a rust-preventive pigment obtained by treating aluminum dihydrogen phosphate with zinc.