JP5172526B2 - Rust-proof metal parts and coat paint - Google Patents

Description

  The present invention relates to a rust-proof metal member in which a zinc composite film and a coat layer are formed on the surface of a metal member, and a coating material used for this type of metal member.

  2. Description of the Related Art Conventionally, a technique for rust-proofing a metal member by forming a zinc composite film on the surface of the metal member has been known. Due to the rust prevention effect (sacrificial anticorrosive action) of zinc contained in the zinc composite film, rust is unlikely to occur in this type of rust-proof metal member. Moreover, the technique which maintains the rust prevention effect | action of a zinc composite film over a long period of time by forming a coating layer in the upper layer of a zinc composite film is proposed (for example, refer patent document 1).

  In Patent Document 1, a metal composite-chromium oxide treatment (so-called dacrotized (registered trademark) treatment) is applied to the surface of a metal member to form a zinc composite coating, and an aqueous resin and silica are further formed on the upper layer of the zinc composite coating. A technique for forming a coat layer using an aqueous processing solution containing a material as a material is disclosed. According to the technique disclosed in Patent Document 1, since the zinc composite coating and the metal member can be isolated from the outside by the coat layer, the rust preventive action of the zinc composite coating can be maintained for a relatively long period of time. Further, since the coating layer includes a resin material, there is a possibility that the coating layer can be deformed following the elastic deformation of the metal member. Therefore, for example, when a hose clip or a spring is used as the metal member, the metal member and the zinc composite film may be isolated from the outside world.

  By the way, the material of the coat layer (hereinafter referred to as coat paint) disclosed in Patent Document 1 is obtained by dispersing a water-based resin and a silica material in water. The water-based resin in this type of coating paint does not dissolve in water, and thus is dispersed as emulsion particles in water. In other words, the water-based resin exists as particles having a relatively large molecular weight in the coat paint. Therefore, with the technique disclosed in Patent Document 1, it is difficult to control the viscosity of the coating material, and it is difficult to make the coating layer thin.

Furthermore, when forming a coating layer of this type of coating material (especially during baking), the coating material forms a network while curing a water-based resin composed of polymer emulsion particles. Therefore, with the technique disclosed in Patent Document 1, it is difficult to sufficiently soften the coat layer, and it is difficult to obtain a coat layer that is difficult to peel (not easily cracked). When the coat layer is peeled off, it becomes difficult to maintain the rust preventive action of the composite zinc film for a long time. For this reason, in the conventional technique, it was difficult to impart excellent rust prevention performance to the metal member subjected to rust prevention treatment.
JP-A-6-146005

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a rust-prevented metal member that can reduce the thickness of the coat layer, suppress the peeling of the coat layer, and is excellent in rust prevention performance. And

The metal member subjected to rust prevention treatment of the present invention that solves the above-mentioned problems comprises a metal member having a predetermined shape, a zinc composite film formed by bonding zinc powder with a binder, and formed on the upper layer of the metal member, and a coat A coating layer formed by applying and drying a coating on the upper layer of the zinc composite film, the coating coating comprising a coating substrate containing an organic solvent and a resin material dissolved in the organic solvent, and the coating base An extender pigment and a rust preventive pigment dispersed and held in the material, the rust preventive pigment comprising zinc phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphite, calcium phosphite, phosphorous acid Magnesium, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, aluminum polyphosphate, sodium silicate, potassium silicate, lithium silicate Are at least one selected from um, bodily quality pigments, talc, magnesium silicate, aluminum sulfate, are at least one selected from barium sulfate, it contained 42 to 50 wt% relative to the coating layer 100 wt% It is characterized by.

The metal member subjected to rust prevention treatment according to the present invention preferably includes at least one of the following (1) to ( 6 ).

( 1 ) The rust preventive pigment is contained in an amount of 9 to 13% by mass with respect to 100% by mass of the coat layer.
( 2 ) The mass cumulative particle diameter D90 of the extender pigment by a laser diffraction / scattering particle size distribution measurement method is 18 μm or more.
(3) The organic solvent is an aromatic solvent composed of at least one selected from toluene, xylene, and ethylbenzene, an alcohol solvent composed of at least one selected from ethylene glycol monobutyl ether, butanol, methanol, and phenol, methyl ethyl ketone, And at least one selected from a ketone solvent consisting of at least one selected from methyl butyl ketone.
(4) The resin material is at least one selected from an epoxy resin, a phenol resin, and an acrylic resin.
(5) The coating paint comprises 10 to 15 parts by mass of a resin material, 4 to 6 parts by mass of the rust preventive pigment, 17 to 24 parts by mass of the extender pigment, and 50 to 59 parts by mass of the organic solvent. And including.
( 6 ) The pencil hardness of the coating layer is F to B.

The coating composition of the present invention that solves the above problems is a coating composition that becomes a material of a coating layer formed on the upper layer of a zinc composite film formed by binding zinc powder with a binder, and is dissolved in an organic solvent and the organic solvent. A coating base material containing a resin material, and an extender pigment and an antirust pigment dispersed and held in the coating base material, the antirust pigment comprising zinc phosphate, calcium phosphate, magnesium phosphate , From aluminum phosphate, zinc phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, aluminum polyphosphate, sodium silicate, potassium silicate, lithium silicate are at least one selected, bodily quality pigments, talc, magnesium silicate, aluminum sulfate, sulfuric Are at least one selected from barium, characterized in that it contains 42 to 50 parts by mass with respect to 100 parts by weight of component other than the organic solvent in the coating composition.

Another coating composition of the present invention that solves the above problems is a coating composition that is used as a material for a coating layer formed on an upper layer of a zinc composite film formed by binding zinc powder with a binder, and includes an organic solvent and the organic solvent. A coating base material containing a resin material dissolved in the coating base material, and an extender pigment and an antirust pigment dispersed and held in the coating base material, the antirust pigment comprising zinc phosphate, calcium phosphate, phosphorus Magnesium phosphate, aluminum phosphate, zinc phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, aluminum polyphosphate, sodium silicate, potassium silicate, silicic acid are at least one selected from lithium, bodily quality pigments, talc, magnesium silicate, aluminum sulfate Are at least one selected from barium sulfate, characterized in that it contains 17 to 24 parts by weight with respect to the coating composition is 100% by mass.

The coat paint of the present invention preferably comprises at least one of the following ( 7 ) to ( 9 ).

(7) The rust preventive pigment is included in an amount of 9 to 13 parts by mass with respect to 100 parts by mass of the components other than the organic solvent in the coat paint.
(8) 4 to 6 parts by mass of the rust preventive pigment is included with respect to 100 parts by mass of the coating material.
( 9 ) The mass cumulative particle diameter D90 of the extender pigment by a laser diffraction / scattering particle size distribution measurement method is 18 μm or more.

  The metal member subjected to rust prevention treatment of the present invention uses a coating material containing an organic solvent, a resin material, an extender pigment, and a rust prevention pigment (that is, a lacquer material). The organic solvent functions as a medium (that is, a solvent) for melting the resin material. By using an organic solvent as the solvent, the resin material in the coating material can be dispersed in a molecular state in the organic solvent. In other words, the resin material in the coating paint exists in a state where low molecular weight molecules are dissolved in an organic solvent. Therefore, according to the metal member subjected to rust prevention treatment of the present invention, the viscosity of the coating material can be easily controlled, so that the coating layer can be thinned.

  In addition, by using an organic solvent as a solvent for the coating material, the resin material in the coating material exists in a stable low molecular weight molecular state. For this reason, when the coat layer is formed (particularly during the baking treatment), the molecules (low molecular weight molecules) of the resin material are three-dimensionally crosslinked. For this reason, the resin material in the coat layer forms a high-density network. Therefore, according to the metal member subjected to the rust prevention treatment of the present invention, the coat layer can be sufficiently softened and peeling of the coat layer can be suppressed.

  Furthermore, in the metal member subjected to the rust prevention treatment of the present invention, the coating layer contains an extender pigment, so that the coating layer is further softened.

  Furthermore, in the metal member subjected to rust prevention treatment according to the present invention, the coating material contains a rust-preventive pigment, so that the occurrence of rust on the metal member can also be suppressed by the coating layer.

  Since the coating layer in the metal member (hereinafter abbreviated as a rust-preventing metal member) of the present invention is soft and easily deformed, the metal member that elastically deforms during use (for example, a hose clip or a spring) Exhibits excellent rust prevention performance when using. However, as the metal member in the rust-proof metal member of the present invention, a metal member (for example, a bolt) that does not elastically deform during use may be used. In the rust-proof metal member of the present invention, the metal member has a predetermined shape. The predetermined shape of the metal member here is a concept encompassing various shapes typified by a clip shape, a spring shape, a plate shape, and the like, and does not indicate a specific shape.

  As the zinc composite film, a general film containing zinc can be used. For example, a zinc composite film processed by dacrotized (registered trademark) or a zinc composite film processed by geomet (registered trademark) as a general film in which flaky or granular zinc powder is bonded with an organic or inorganic binder. Is mentioned. Since these zinc composite films are excellent in rust prevention performance, they can be preferably used.

  The coating paint contains a rust preventive pigment, an extender pigment, a resin material, and an organic solvent. As the rust preventive pigment, it is preferable to use a pigment having a small particle diameter.

  By the way, an oxide film (a so-called passive film) may be formed on the surface of zinc contained in the zinc composite film. When a passive film is formed, the zinc covered with the passive film becomes difficult to corrode (over-corrosion protection). Phosphate stabilizes this passive film over a long period of time because the zinc composite film is maintained alkaline by releasing phosphate ions slowly. For this reason, by using a phosphate as a rust preventive pigment for a coating paint, it is possible to suppress zinc anticorrosion over a long period of time and maintain the rust preventive action of zinc for a long period of time. In addition, silicate stabilizes the passive film over a long period of time because the zinc composite film is maintained alkaline by releasing silicate ions gradually. Therefore, by using a silicate as a rust preventive pigment for a coating material, it is possible to suppress zinc anticorrosion over a long period of time and maintain the rust preventive action of zinc for a long period of time.

  For this reason, since at least one of phosphate and silicate can be used as a rust-preventive pigment for coating paints, it is possible to suppress the elution of zinc in the zinc composite film. Can be maintained for a long time. Therefore, when at least one of phosphate and silicate is used as the rust preventive pigment of the coating paint, the rust preventive metal member of the present invention exhibits very excellent rust preventive performance. Furthermore, when at least one of phosphate and silicate is used as a rust preventive pigment for a coating material, rust preventive performance and insulating performance can be imparted to the coat layer. Therefore, in this case, the rust-proof metal member of the present invention is hardly rusted even when it comes into contact with a different metal.

  Examples of phosphates include zinc phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, polyphosphorus It is preferable to use at least one selected from aluminum oxide. This is because these phosphates are dissolved little by little (gradually) to release phosphate ions over a long period of time. As the silicate, it is preferable to use at least one selected from sodium silicate, potassium silicate, and lithium silicate. This is because these silicates are also gradually dissolved to release silicate ions over a long period of time.

  It is preferable that 4-6 mass parts of phosphate is contained with respect to 100 mass parts of coating materials. In addition, the compounding quantity of the phosphate in this case is 9-13 mass% with respect to 100 mass% of coating layers. When the blending ratio of the phosphate with respect to 100 parts by mass of the coating material is 4 parts by mass or more, excellent rust prevention performance can be imparted to the coating layer. Moreover, if the blending ratio of the phosphate with respect to 100 parts by mass of the coating material is 6 parts by mass or less, the coating layer can be sufficiently softened.

  It is preferable that 4-6 mass parts of silicate is contained with respect to 100 mass parts of coating materials. In addition, the compounding quantity of the silicate in this case is 9-13 mass% with respect to 100 mass% of coating layers. If the compounding ratio of the silicate with respect to 100 parts by mass of the coating material is 4 parts by mass or more, an excellent rust prevention performance can be imparted to the coating layer. Moreover, if the compounding ratio of the silicate with respect to 100 parts by mass of the coating material is 6 parts by mass or less, the coating layer can be sufficiently softened.

  In addition, also when using rust preventive pigments other than a phosphate and a silicate, a rust preventive pigment is 4-6 mass parts with respect to 100 mass parts of coating materials (9-13 with respect to 100 mass% of coating layers). Mass%) is preferably included.

  As the extender pigment, it is preferable to use a soft one. Talc, magnesium silicate, aluminum sulfate, barium sulfate and the like are soft and can be used particularly preferably.

  The extender is preferably contained in an amount of 17 to 24 parts by mass with respect to 100 parts by mass of the coating material. In addition, the compounding quantity of the extender in this case is 42-50 mass% with respect to 100 mass% of coating layers, when using a talc, magnesium silicate, aluminum sulfate, barium sulfate etc. as an extender. When the blending ratio of the extender pigment to 100 parts by mass of the coat paint is 17 parts by mass or more, the coat layer is softened. Further, when the blending ratio of the extender pigment to 100 parts by mass of the coat paint is 24 parts by mass or less, the extender pigment is uniformly dispersed in the coat paint.

  As the resin material, it is preferable to use a resin material that is excellent in adhesion to metal and water resistance and has a low viscosity in a molten state. Examples of such resin materials include epoxy resins and phenol resins. It is preferable that 10-15 mass parts of resin materials are contained with respect to 100 mass parts of coating materials. In addition, the compounding quantity of the resin material in this case is 24-31 mass% with respect to 100 mass% of coating layers. When the blending ratio of the resin material with respect to 100 parts by mass of the coating material is 10 parts by mass or more, the coating layer can be softened. Moreover, if the mixture ratio of the resin material with respect to 100 mass parts of coating materials is 15 mass parts or less, compounding quantities, such as a rust preventive pigment and an organic solvent, can be increased.

  As the organic solvent, it is preferable to use a solvent having a high boiling point and a high solubility of the resin material, such as an aromatic solvent, an alcohol solvent, and a ketone solvent. Examples of the aromatic solvent include toluene, xylene, ethylbenzene and the like. Examples of the alcohol solvent include ethylene glycol monobutyl ether, butanol, methanol, phenol and the like. Examples of the ketone solvent include methyl ethyl ketone and methyl butyl ketone. These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably contained in an amount of 50 to 59 parts by mass with respect to 100 parts by mass of the coating material. When the blending ratio of the organic solvent with respect to 100 parts by mass of the coating material is 50 parts by mass or more, the resin material, the rust preventive pigment, and the like are more uniformly dispersed in the organic solvent. Moreover, if the compounding ratio of the organic solvent with respect to 100 parts by mass of the coating material is 59 parts by mass or less, the compounding amount of the resin material, the rust preventive pigment and the like can be increased.

  The pencil hardness of the coating layer in the rust-proof metal member of the present invention is preferably F to B. If the pencil hardness of the coat layer is within this range, the coat layer can be softened and the strength of the coat layer can be sufficiently secured. In addition, the pencil hardness said by this specification points out the pencil hardness by JISK5400.8.4.2.

  In addition to the rust preventive pigment, extender pigment, resin material, and organic solvent, the coating paint of the present invention may further contain a coloring pigment. As the coloring pigment, a general pigment can be used. For example, at least one selected from carbon black, iron trioxide, titanium oxide, and zinc oxide can be preferably used as the color pigment.

  Hereinafter, the rust-proof metal member and the coating material of the present invention will be specifically described.

( Test Example 1)
A perspective view schematically showing the rust-proof metal member of Test Example 1 is shown in FIG. A cross-sectional view schematically showing the rust-proof metal member of Test Example 1 is shown in FIG.

As shown in FIG. 1, the rust preventive metal member 1 of Test Example 1 is a hose clip. As shown in FIG. 2, the rust-proof metal member 1 of Test Example 1 is formed on the metal member 2, the zinc composite coating 3 formed on the upper layer of the metal member 2, and the zinc composite coating 3. And coat layer 4.

The metal member 2 is made of steel and has substantially the same shape as the hose clip shown in FIG. As a material of the zinc composite film (hereinafter referred to as a film material), Geomet 720 (manufactured by Nippon Dacro Shamrock) was used. As a material of the coat layer (coat paint), 14 parts by mass of an epoxy resin (resin material), 21 parts by mass of magnesium silicate (extreme pigment), 5 parts by mass of zinc phosphate (rust preventive pigment), A mixture of 5 parts by mass of titanium oxide (color pigment) and 55 parts by mass of methyl ethyl ketone (organic solvent) was used. The rust-proof metal member of Test Example 1 was produced as follows.

First, shot peening treatment was performed on a metal member prepared in advance to roughen the oxide film on the surface of the metal member. The metal member after the treatment was immersed in a Geomet 720 treatment solution at 20 to 25 ° C. for 2 to 6 minutes. After immersion, the Geomet 720 treatment liquid was attached to the metal member using a dip spin apparatus, and heated at 320 to 360 ° C. for 30 to 45 minutes in an electrically heated hot air circulating furnace. After heating, the mixture was allowed to cool at room temperature. By repeating the above treatment twice, an intermediate of a rust-proof metal member was obtained in which a zinc composite film was formed on the upper layer of the metal member at a coating amount of 220 mg / dm ² .

Next, a mixture of resin material, rust preventive pigment, extender pigment and colored pigment (hereinafter referred to as coated powder material) was stirred for 180 minutes by a ball mill. The coated powder material after stirring was mixed with an organic solvent to prepare a coated paint. At this time, the resin material was dissolved in an organic solvent. The rust preventive pigment, extender pigment, and colored pigment were dispersed in a coated substrate containing an organic solvent and a resin material. The intermediate of the rust-proof metal member described above was immersed in this coat paint (at room temperature) for 2 to 6 minutes. After the immersion, the coat paint was attached to the intermediate using a dip spin apparatus and heated at 160 ° C. to 220 ° C. for 15 to 45 minutes in an electric heating hot air circulating furnace. After heating, it was allowed to cool at room temperature. By repeating the above treatment twice, a coating layer was formed in the upper layer of the intermediate. The coating amount of the coat layer at this time was 150 mg / dm ² . The coating layer 4 in the rust-proof metal member 1 of Test Example 1 is about 31% by mass of resin material, about 47% by mass extender pigment, and about 11% by mass of anti-corrosion with respect to 100% by mass of the coating layer. Rust pigment and about 11% by weight color pigment.

Through the above steps, the rust-proof metal member 1 (FIG. 2) of Test Example 1 is manufactured, in which the zinc composite film 3 is formed on the upper layer of the metal member 2 and the coat layer 4 is formed on the upper layer of the zinc composite film 3. did.

( Test Example 2)
The rustproof metal member of Test Example 2 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 2, as a coating material, 14 parts by mass of a phenol resin (resin material), 21 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, and 5 parts by mass of titanium oxide And a mixture of 55 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 2 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 2 was 180 minutes.

( Test Example 3)
The rustproof metal member of Test Example 3 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 3, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, and 5 parts by mass A mixture of parts of titanium oxide and 55 parts by weight of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 3 is about 31% by weight resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Moreover, the stirring time of the coated powder material in Test Example 3 was 180 minutes.

( Test Example 4)
The rustproof metal member of Test Example 4 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 4, as a coating material, 5 parts by mass of an epoxy resin, 5 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, and 5 parts by mass. A mixture of parts of titanium oxide and 59 parts by weight of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 4 is about 24% by weight resin material, about 51% by weight extender pigment, about 12% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 12% by weight of a coloring pigment. Moreover, the stirring time of the coated powder material in Test Example 4 was 180 minutes.

( Test Example 5)
The rustproof metal member of Test Example 5 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 5, as a coating material, 7.5 parts by mass of an epoxy resin, 7.5 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of zinc phosphate And a mixture of 5 parts by mass of titanium oxide and 54 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 5 is about 33% by weight resin material, about 46% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Moreover, the stirring time of the coated powder material in Test Example 5 was 180 minutes.

( Test Example 6)
The rustproof metal member of Test Example 6 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 6, as a coating material, 20 parts by mass of an epoxy resin, 21 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, 5 parts by mass of titanium oxide, and 49 parts by mass A mixture of parts of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 6 is about 39% by weight resin material, about 41% by weight extender pigment, about 10% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 10% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 6 was 180 minutes.

( Test Example 7)
The rustproof metal member of Test Example 7 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 7, as a coating material, 5 parts by mass of an epoxy resin, 21 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, 5 parts by mass of titanium oxide, and 64 parts by mass A mixture of parts of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 7 is about 14% by weight resin material, about 58% by weight extender pigment, about 14% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 14% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 7 was 180 minutes.

( Test Example 8)
The rustproof metal member of Test Example 8 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 8, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 17 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, and 5 parts by mass A mixture of parts of titanium oxide and 59 parts by weight of methyl ethyl ketone was used. The coating layer in the rustproof metal member of Test Example 8 is about 34% by weight of resin material, about 42% by weight of extender pigment, about 12% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 12% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 8 was 180 minutes.

( Test Example 9)
The rustproof metal member of Test Example 9 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rustproof metal member of Test Example 9, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenolic resin, 24 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, and 5 parts by mass as a coating material. A mixture of parts of titanium oxide and 52 parts by weight of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 9 is about 29% by weight resin material, about 50% by weight extender pigment, about 10% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 10% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 9 was 180 minutes.

( Test Example 10)
The rustproof metal member of Test Example 10 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 10, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of talc (extreme pigment), 5 parts by mass of zinc phosphate, A mixture of 5 parts by mass of titanium oxide and 55 parts by mass of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 10 is about 31% by weight resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment, with respect to 100% by weight of the coating layer. About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 10 was 180 minutes.

( Test Example 11)
The rustproof metal member of Test Example 11 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 11, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of aluminum sulfate (extreme pigment), and 5 parts by mass of zinc phosphate A mixture of 5 parts by mass of titanium oxide and 55 parts by mass of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 11 is about 31% by weight of resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Moreover, the stirring time of the coated powder material in Test Example 11 was 180 minutes.

( Test Example 12)
The rustproof metal member of Test Example 12 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 12, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of barium sulfate (extreme pigment), and 5 parts by mass of zinc phosphate A mixture of 5 parts by mass of titanium oxide and 55 parts by mass of methyl ethyl ketone was used. The coating layer in the rustproof metal member of Test Example 12 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 12 was 180 minutes.

( Test Example 13)
The rustproof metal member of Test Example 13 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 13, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 15 parts by mass of magnesium silicate, and 5 parts by mass of zinc phosphate are used as the coating material. And a mixture of 5 parts by mass of titanium oxide and 61 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 13 is about 36% by weight resin material, about 39% by weight extender pigment, and about 13% by weight rust-proof pigment with respect to 100% by weight of the coating layer. About 13% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 13 was 180 minutes.

( Test Example 14)
The rustproof metal member of Test Example 14 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 14, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 27 parts by mass of magnesium silicate, 5 parts by mass of zinc phosphate, and 5 parts by mass A mixture of parts of titanium oxide and 49 parts by weight of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 14 is about 27% by weight resin material, about 53% by weight extender pigment, about 10% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 10% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 14 was 180 minutes.

( Test Example 15)
The rustproof metal member of Test Example 15 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 15, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 4 parts by mass of zinc phosphate, and 5 parts by mass A mixture of parts of titanium oxide and 56 parts by weight of methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 15 is about 32% by weight resin material, about 48% by weight extender pigment, about 9% by weight rust-proof pigment, with respect to 100% by weight of the coating layer. About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 15 was 180 minutes.

( Test Example 16)
The rustproof metal member of Test Example 16 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 16, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 6 parts by mass of zinc phosphate, and 5 parts by mass A mixture of parts of titanium oxide and 54 parts by weight of methyl ethyl ketone was used. The coating layer in the rustproof metal member of Test Example 16 is about 30% by weight of resin material, about 46% by weight of extender pigment, about 13% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 16 was 180 minutes.

( Test Example 17)
The rustproof metal member of Test Example 17 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 17, as a coating material, 7 parts by weight of an epoxy resin, 7 parts by weight of a phenol resin, 21 parts by weight of magnesium silicate, and 5 parts by weight of calcium phosphate (rust preventive pigment) A mixture of 5 parts by mass of titanium oxide and 55 parts by mass of methyl ethyl ketone was used. The coating layer in the rustproof metal member of Test Example 17 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 17 was 180 minutes.

( Test Example 18)
The rustproof metal member of Test Example 18 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 18, 7 parts by weight of an epoxy resin, 7 parts by weight of a phenol resin, 21 parts by weight of magnesium silicate, and 5 parts by weight of magnesium phosphate (rust-proof pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 18 is about 31% by weight resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 18 was 180 minutes.

( Test Example 19)
The rustproof metal member of Test Example 19 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 19, 7 parts by weight of an epoxy resin, 7 parts by weight of a phenol resin, 21 parts by weight of magnesium silicate, and 5 parts by weight of aluminum phosphate (rust-proof pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 19 is about 31% by weight of resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 19 was 180 minutes.

( Test Example 20)
The rustproof metal member of Test Example 20 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 20, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of zinc phosphite (rust prevention) Pigment), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 20 is about 31% by weight resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Moreover, the stirring time of the coated powder material in Test Example 20 was 180 minutes.

( Test Example 21)
The rustproof metal member of Test Example 21 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 21, 7 parts by weight of an epoxy resin, 7 parts by weight of a phenol resin, 21 parts by weight of magnesium silicate, and 5 parts by weight of calcium phosphite (rust preventive pigment) are used as the coating material. And a mixture of 5 parts by mass of titanium oxide and 55 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 21 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 21 was 180 minutes.

( Test Example 22)
The rustproof metal member of Test Example 22 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 22, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of magnesium phosphite (rust prevention) Pigment), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 22 is about 31% by weight resin material, about 47% by weight extender pigment, and about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer. About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 22 was 180 minutes.

( Test Example 23)
The rustproof metal member of Test Example 23 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 23, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of aluminum phosphite (corrosion proof) Pigment), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 23 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment, with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 23 was 180 minutes.

( Test Example 24)
The rustproof metal member of Test Example 24 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust preventive metal member of Test Example 24, 7 parts by mass of epoxy resin, 7 parts by mass of phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of zinc polyphosphate (rust preventive pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 24 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 24 was 180 minutes.

( Test Example 25)
The rustproof metal member of Test Example 25 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 25, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of calcium polyphosphate (rust preventive pigment) are used as the coating material. And a mixture of 5 parts by mass of titanium oxide and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 25 is about 31% by weight resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment, with respect to 100% by weight of the coating layer. About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 25 was 180 minutes.

( Test Example 26)
The rustproof metal member of Test Example 26 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 26, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of magnesium polyphosphate (rust preventive pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 26 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 26 was 180 minutes.

( Test Example 27)
The rustproof metal member of Test Example 27 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 27, 14 parts by weight of phenol resin, 21 parts by weight of magnesium silicate, 5 parts by weight of aluminum polyphosphate (rust-proof pigment), and 5 parts by weight of oxidation were used as the coating paint. A mixture of titanium and 55 parts by mass of methyl ethyl ketone was used. The coating layer in the rustproof metal member of Test Example 27 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 27 was 180 minutes.

( Test Example 28)
The rustproof metal member of Test Example 28 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust preventive metal member of Test Example 28, 7 parts by mass of epoxy resin, 7 parts by mass of phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of sodium silicate (rust preventive pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 28 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rust-proof pigment, with respect to 100% by weight of the coating layer. About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 28 was 180 minutes.

( Test Example 29)
The rustproof metal member of Test Example 29 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 29, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of potassium silicate (rust preventive pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 29 is about 31% by weight of resin material, about 47% by weight of extender pigment, about 11% by weight of rustproofing pigment, with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 29 was 180 minutes.

( Test Example 30)
The rustproof metal member of Test Example 30 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust-proof metal member of Test Example 30, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of lithium silicate (anti-rust pigment) ), 5 parts by mass of titanium oxide, and 55 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 30 is about 31% by weight resin material, about 47% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 30 was 180 minutes.

( Test Example 31)
The rustproof metal member of Test Example 31 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rust-proof metal member of Test Example 31, as a coating material, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 2 parts by mass of zinc phosphate, and 5 parts by mass A mixture of parts titanium oxide and 58 parts by weight methyl ethyl ketone was used. The coating layer in the rust-proof metal member of Test Example 31 is about 33% by weight resin material, about 50% by weight extender pigment, about 5% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 12% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 31 was 180 minutes.

( Test Example 32)
The rustproof metal member of Test Example 32 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating material. In the rustproof metal member of Test Example 32, 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 8 parts by mass of zinc phosphate, and 5 masses as a coating material. A mixture of parts of titanium oxide and 52 parts by weight of methyl ethyl ketone was used. The coating layer in the rustproof metal member of Test Example 32 is about 29% by weight of resin material, about 44% by weight of extender pigment, about 17% by weight of rustproofing pigment with respect to 100% by weight of the coating layer, About 10% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 32 was 180 minutes.

( Test Example 33)
The rustproof metal member of Test Example 33 is the same as the rustproof metal member of Test Example 5 except for the stirring time of the coated powder material (that is, the particle size of the extender pigment in the coated paint). In the rust-proof metal member of Test Example 33, 7.5 parts by mass of an epoxy resin, 7.5 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of zinc phosphate were used as the coating paint. And a mixture of 5 parts by mass of titanium oxide and 54 parts by mass of methyl ethyl ketone. The coating layer in the rustproof metal member of Test Example 33 is about 33% by weight of resin material, about 46% by weight of extender pigment, about 11% by weight of rustproofing pigment, with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 33 was 20 minutes.

( Test Example 34)
The rustproof metal member of Test Example 34 is the same as the rustproof metal member of Test Example 5 except for the stirring time of the coated powder material (that is, the particle size of the extender pigment in the coated paint). In the rust-proof metal member of Test Example 34, 7.5 parts by mass of an epoxy resin, 7.5 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of zinc phosphate were used as the coating paint. And a mixture of 5 parts by mass of titanium oxide and 54 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 34 is about 33% by weight resin material, about 46% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 34 was 320 minutes.

( Test Example 35)
The rustproof metal member of Test Example 35 is the same as the rustproof metal member of Test Example 5 except for the stirring time of the coated powder material (that is, the particle size of the extender pigment in the coated paint). In the rust-proof metal member of Test Example 35, 7.5 parts by mass of an epoxy resin, 7.5 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, and 5 parts by mass of zinc phosphate are used as the coating paint. And a mixture of 5 parts by mass of titanium oxide and 54 parts by mass of methyl ethyl ketone. The coating layer in the rust-proof metal member of Test Example 35 is about 33% by weight resin material, about 46% by weight extender pigment, about 11% by weight rust-proof pigment with respect to 100% by weight of the coating layer, About 11% by weight of a coloring pigment. Further, the stirring time of the coated powder material in Test Example 35 was 5 minutes.

( Test Example 36 )
The rustproof metal member of Test Example 36 is the same as the rustproof metal member of Test Example 1 except that there is no coat layer.

( Test Example 37 )
The rustproof metal member of Test Example 37 is the same as the rustproof metal member of Test Example 1 except for the composition of the coating paint. In the rust preventive metal member of Test Example 37 , 7 parts by mass of an epoxy resin, 7 parts by mass of a phenol resin, 21 parts by mass of magnesium silicate, 5 parts by mass of titanium oxide, and 60 parts by mass as a coating material. A mixture of methyl ethyl ketone was used. Therefore, the coat layer in the rustproof metal member of Test Example 37 does not contain a rustproof pigment. The coating layer in the rust-proof metal member of Test Example 37 includes about 35% by mass of a resin material, about 53% by mass of extender pigment, and about 13% by mass of a coloring pigment with respect to 100% by mass of the coating layer. . Further, the stirring time of the coated powder material in Test Example 37 was 180 minutes.

(Evaluation test)
(1. Antirust performance evaluation test)
About the antirust metal member of Test Examples 1-35 and Test Examples 36 and 37 , the antirust performance evaluation test (salt water spray test based on JIS Z 2371) was done. The antirust performance evaluation test was conducted for each of the five antirust metal members of each test example .

  The results of the rust prevention performance evaluation test are shown in Tables 1 to 4 described later. In addition, even if 2000 hours or more passed after the rust prevention performance evaluation test start, what did not generate | occur | produce red rust was evaluated as AAA. Red rust did not occur in less than 1500 hours after the start of the test, but those in which red rust occurred in 1500 hours to 2000 hours were evaluated as AA. Red rust was not generated in less than 1000 hours after the start of the test, but A was evaluated as A in which one piece out of 5 rust-preventing metal members was generated in 1000 to 1500 hours. Less than 1000 hours after the start of the test, red rust was not generated, but 2 to 5 of 5 rust-proof metal members were evaluated as B in 1000 to 1500 hours. The others were evaluated as C. In addition, the rust prevention metal member whose result of a rust prevention performance evaluation test is the range of AAA-B is excellent in rust prevention performance.

(2. Pencil hardness measurement test)
About the antirust metal member of Test Examples 1-35 and Test Examples 36 and 37 , the pencil hardness of the coat layer was measured. The pencil hardness was measured according to JIS K 54000.8.4.2. The results of the pencil hardness measurement test are shown in Tables 1 to 4 described later. For Test Example 36 , the pencil hardness of only the zinc composite film was measured.

(3. Peeling resistance evaluation test)
About the antirust metal member of Test Examples 1-35 and Test Examples 36 and 37 , the peeling-proof performance evaluation test was done. The peel resistance evaluation test was performed by enlarging 30 rust preventive metal members of each test example to the maximum diameter with pliers and visually observing the presence or absence of peeling of the coating layer. The metal members used in each test example had the same dimensions (plate thickness 0.7 mm, plate width 8 mm, diameter (free diameter) 8.6 mm). The results of the peel resistance evaluation test are shown in Tables 1 to 4 below. Of the 30 anti-corrosive metal members, the ratio (%) of the exfoliated coating layer was 10% or less was evaluated as AA, and the ratio exceeding 10% and 20% or less was A and The evaluation was such that B exceeded 20% and 30% or less was evaluated as B, and C exceeding 30% was evaluated as C. In addition, as for the antirust metal member whose result of a peeling-proof performance evaluation test is the range of AA-B, a coating layer is hard to peel.

(4. Particle size measurement test)
A particle size measurement test was performed on magnesium silicate which is a kind of extender pigment. The particle size was measured based on a laser diffraction / scattering particle size distribution measurement method. As a measuring device, a Shimadzu laser diffraction particle size distribution measuring device SALD-2200 multifunctional sampler manufactured by Shimadzu Corporation was used. Specifically, a bead mill was used to prepare magnesium silicate stirred for 20 minutes under the same conditions as in each test example (hereinafter referred to as sample 1) and 180 minutes stirred (hereinafter referred to as sample 2). And each sample 1-2 was taken in the container, and the whole container was shaken well. Next, a part of each sample was put into the sampler bath of the measuring apparatus until the concentration became appropriate, and each sample was circulated by the sampler for about 30 seconds. The sampler bath was previously filled with a dispersion solvent (ethyl alcohol) and the pump was started. After circulating each sample for about 30 seconds, each sample was laser diffracted by a measuring device. The refractive index at this time was 1.70-0.00i. The results of the particle size measurement test are shown in FIG.

  As shown in FIG. 3, the value of the cumulative mass particle diameter D90 (hereinafter simply referred to as D90) by the laser diffraction scattering particle size distribution measurement method of Sample 1 stirred for 20 minutes with a bead mill was 18.613 μm. In other words, 10% by mass of Sample 1 (extension pigment stirred for 20 minutes with a bead mill) had a particle diameter of 18.613 μm or more. The D90 value of Sample 2 stirred for 180 minutes with a bead mill was 15.602 μm. In other words, 10% by mass of Sample 2 (extension pigment stirred for 180 minutes with a bead mill) had a particle size of 15.602 μm or more. D90 is a value obtained by accumulating up to 90% by mass of the particle diameter of each sample from the small diameter side, assuming that the total amount of each sample subjected to laser diffraction is 100% by mass.

From these results, in Test Examples 1 to 32 and Test Example 37 in which the coated powder material was stirred for 180 minutes with a bead mill, D90 of the extender pigment contained in the coated paint and the coated layer was a value approximated to 15.602 μm. Guessed. In addition, when the coated powder material is stirred for 20 minutes with a bead mill, D90 of the extender pigment contained in the coated paint and the coated layer is estimated to be a value approximate to 18.613 μm. For reference, in Test Example 33 in which the coated powder material was stirred with a bead mill for 20 minutes, D90 of the extender pigment contained in the coated coating material and the coated layer was a value (18.6 μm) approximated to 18.613 μm (Table 4). ). Furthermore, in Test Example 35 in which the coated powder material was stirred for 5 minutes with a bead mill, D90 of the extender pigment contained in the coat paint and the coat layer was 18.6 μm, which was the same as D90 in Test Example 33. For this reason, if the bead mill time is within 20 minutes, D90 of the extender pigment contained in the coat paint and the coat layer can be kept at 18 μm or more.

Moreover, although not shown in FIG. 3, D90 of the sample which stirred the magnesium silicate for 320 minutes on the same conditions as each test example using the bead mill was 13.2 micrometers. Therefore, when the coated powder material is stirred with a bead mill for 320 minutes, D90 of the extender pigment contained in the coated coating material and the coated layer is estimated to be a value close to 15.602 μm. For reference, Test Example 34 is an example in which the coated powder material was stirred for 320 minutes with a bead mill, and D90 of the extender pigment contained in the coated paint and the coat layer of Test Example 34 was 13.2 μm (Table 4). .

As shown in Tables 1 to 4, the rust prevention performance of the rust prevention metal members of Test Examples 36 and 37 is C, whereas the rust prevention performance of the rust prevention metal members of Test Examples 1 to 35 is AAA to B. is there. That is, the rustproof metal members of Test Examples 1 to 35 are superior in rustproof performance as compared to the rustproof metal members of Test Examples 36 and 37 . This is because the rust preventive metal member of Test Examples 1 to 35 has a coat layer, whereas the rust preventive metal member of Test Example 36 does not have a coat layer, and in the rust preventive metal members of Test Examples 1 to 35 It is thought that the coating layer (coating paint) contains a rust-preventive pigment, whereas the coating layer (coating paint) in the rust-proof metal member of Test Example 37 does not contain a rust-preventing pigment. It is done.

Moreover, as shown to Tables 1-4, the peeling-proof performance of the antirust metal member of Test Examples 1-35 is in the range of AA-B. From this result, it turns out that the coat layer in the antirust metal member of Test Examples 1-35 is hard to peel. This is supported by the fact that the pencil hardness of the rustproof metal member of Test Example 36 is 8H, whereas the pencil hardness of the rustproof metal member of Test Examples 1 to 35 is 2B to 4H. That is, the portion other than the metal member in the rust-proof metal member of Test Examples 1 to 35 (that is, the layer composed of the zinc composite film and the coat layer) is the portion other than the metal member in the rust-proof metal member of Test Example 36 (that is, , Zinc composite film). This is presumably because the coat layer is softer than the zinc composite film. The soft coat layer can be deformed following the deformation of the metal member. Therefore, the coat layer in the antirust metal member of Test Examples 1 to 35 is difficult to peel off.

Note that the rust-proof metal member of Test Example 36 does not have a coat layer. For this reason, peeling of the coating layer was not seen in the rust preventive metal member of Test Example 36 .

Moreover, sedimentation of the pigment was observed in the coating layers in the rust-proof metal members of Test Example 7 and Test Example 14. This is because the coating ratio of the coating material in the rust-proof metal member of Test Example 7 is relatively small, and the coating ratio of the coating material in the rust-proof metal member of Test Example 14 is relatively large. Conceivable. From this result, it is understood that the blending ratio of the resin material with respect to 100 parts by mass of the coating material is preferably more than 5 parts by mass. Further, it can be seen that the proportion of the extender pigment to 100 parts by mass of the coating material is preferably less than 27 parts by mass.

In other test examples ( Test Examples 1 to 6, 8 to 13, and 15 to 35), precipitation of the pigment was not observed. From this result, it can be seen that the blending ratio of the resin material with respect to 100 parts by mass of the coating material is more preferably 10 parts by mass or more. Furthermore, it can be seen that the blending ratio of the extender pigment to 100 parts by mass of the coating material is more preferably less than 24 parts by mass.

Further, the rust-proof metal members of Test Examples 1 to 5, 7 to 12, 14 to 31, and 33 to 35 are superior to the rust-proof metal member of Test Example 6 in the anti-peeling performance of the coat layer. This is presumably because the coating ratio in the rust-proof metal member of Test Example 6 has a relatively large blending ratio of the resin material and a relatively small blending ratio of the organic solvent. From this result, it is understood that the blending ratio of the resin material with respect to 100 parts by mass of the coating material is preferably less than 20 parts by mass, and more preferably 15 parts by mass or less. Furthermore, it is also understood that the blending ratio of the organic solvent with respect to 100 parts by mass of the coating material is preferably more than 49 parts by mass, more preferably 52 parts by mass or more.

In addition, the antirust metal members of Test Examples 1 to 5, 7 to 12, 14 to 31, and 33 to 35 are superior to the antirust metal member of Test Example 13 in the anti-peeling performance of the coat layer. This is presumably because the coating ratio of the anticorrosive metal member of Test Example 13 is relatively small in the proportion of extender pigment. From this result, it can be seen that the blending ratio of the extender pigment to 100 parts by mass of the coat paint is preferably more than 15 parts by mass, and more preferably 17 parts by mass or more.

Further, the rust-proof metal members of Test Examples 15 to 31 and 33 to 35 are superior to the rust-proof metal member of Test Example 32 in the peel resistance of the coat layer. This is presumably because the coating ratio in the rust-proof metal member of Test Example 32 has a relatively large blending ratio of the rust-preventing pigment and a relatively small blending ratio of the organic solvent. From this result, it is understood that the blending ratio of the rust preventive pigment with respect to 100 parts by mass of the coating paint is preferably less than 8 parts by mass, and more preferably 6 parts by mass or less.

In addition, the rust-proof metal members of Test Examples 1 to 5, 7 to 12, 14 to 30, and 32 to 35 are superior to the rust-proof metal member of Test Example 31 in rust prevention performance. This is presumably because the coating ratio of the rustproof metal member of Test Example 31 is relatively small in the blending ratio of the rustproof pigment. From this result, it can be seen that the blending ratio of the rust preventive pigment to 100 parts by mass of the coating material is preferably more than 2 parts by mass, and more preferably 4 parts by mass or more.

By the way, as shown in Table 4, the particle size of the extender pigment contained in the coat paint (and coat layer) is involved in the rust prevention performance of the rust preventive metal member. Comparing the particle size and rust prevention performance of the extender pigment in the rust preventive metal members of Test Examples 5, 33 to 35, it can be seen that the rust prevention performance can be improved by using the extender pigment having a large particle size. This is considered to be due to the following reasons.

  As shown in FIG. 4, a through-hole-like defect 9 may occur in the coating layer 4 and the zinc composite coating 3 of the rust-proof metal member 1. This defect 9 is a path when the organic solvent in the coating material evaporates. For this reason, the occurrence of the defect 9 is an unavoidable phenomenon. When water 8 penetrates into the defect 9 generated in the coating layer 4 and the zinc composite coating 3, the zinc contained in the zinc composite coating 3 is ionized and sacrificial anticorrosive. According to the rust-proof metal member 1 of the present invention, rust generation of the metal member 2 is suppressed by this rust-proofing action of zinc. By the way, when the water 8 continues to enter the defect 9 for a long period of time, the zinc 30 located in the vicinity of the defect 9 in the zinc composite film 3 is completely ionized. In this case, since the sacrificial anticorrosive action by zinc is lost, the metal member 2 is rusted. On the other hand, at this time, the zinc separated from the defect 9 in the zinc composite film 3 remains without being ionized. For this reason, it is thought that if the water 8 is ionized by supplying water to the zinc, the rust preventive action of zinc can be maintained for a long time.

  In order to supply the water 8 to the zinc separated from the defect 9 in the zinc composite coating 3, a passage for the water 8 may be formed in the coat layer 4. In the coat layer 4, slight gaps are generated at the interface between the extender pigment 40 and the resin material 41, the interface between the rust preventive pigment 42 and the resin material 41, and the interface between the color pigment 43 and the resin material 41. For this reason, it is considered that these interfaces can be used as a passage for water 8. The blending amount and particle size of the rust preventive pigment 42 and the coloring pigment 43 are significantly smaller than the blending amount and particle size of the extender pigment 40. For this reason, it is considered that the passage of water 8 in the coat layer 4 is mainly constituted by an interface between the extender pigment 40 and the resin material 41 (hereinafter referred to as a passage interface).

  When the particle size of the extender pigment 40 is large (FIG. 5), the distance between adjacent extender pigments 40 is likely to be shorter than when the particle size of the extender pigment 40 is small (FIG. 4). If the distance between the adjacent extender pigments 40 is reduced, the possibility that adjacent passage interfaces are connected to each other increases, and the possibility that the passage interface penetrates the coat layer 4 in the thickness direction is increased. Hereinafter, the passage interface penetrating the coat layer 4 in the thickness direction is referred to as a penetrating interface (indicated by an arrow in FIG. 5).

The larger the number of penetration interfaces, the higher the possibility that a sufficient amount of water 8 can be supplied to zinc that is separated from the defect 9 in the zinc composite coating 3. In other words, by using the extender pigment 40 having a large particle size, a large number of through interfaces can be formed, and the zinc in the zinc composite coating 3 can be used without waste, so that the rust prevention performance of the rust prevention metal member 1 is improved. As shown in Table 4, when the mass cumulative particle diameter D90 of the extender pigment 40 is 15 μm or more ( Test Example 5), excellent rust prevention performance can be imparted to the rust prevention metal member 1. If D90 is 18 μm or more ( Test Example 33), particularly excellent rust prevention performance can be imparted to the rust prevention metal member 1. In addition, D90 in Test Examples 33 and 35 is 18 μm or more, and the mass average particle diameter of extender pigment 40 is 8 μm or more. From this result, it can be seen that even when the mass average particle diameter of the extender pigment 40 is 8 μm or more, particularly excellent rust prevention performance can be imparted to the rust prevention metal member 1.

3 is a perspective view schematically showing a rust-proof metal member of Test Example 1. FIG. 3 is a cross-sectional view schematically showing a rust-proof metal member of Test Example 1. FIG. It is a graph showing the result of a particle size measurement test. It is explanatory drawing which represents typically the effect | action of the coat layer in the rustproof metal member of this invention. It is explanatory drawing which represents typically the effect | action of the coat layer in the rustproof metal member of this invention.

1: Rust preventive metal member 2: Metal member 3: Zinc composite film 4: Coat layer 40: extender pigment 41: Resin material 42: Rust preventive pigment 43: Colored pigment

Claims (12)

A metal member of a predetermined shape;
A zinc composite film formed by bonding zinc powder with a binder and formed on the upper layer of the metal member;
A coating layer in which a coating paint is applied and dried on the upper layer of the zinc composite coating,
The coating paint includes a coating base material containing an organic solvent and a resin material dissolved in the organic solvent, and an extender pigment and an antirust pigment dispersed and held in the coating base material,
The rust preventive pigment is zinc phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, polyphosphorus. At least one selected from aluminum silicate, sodium silicate, potassium silicate, lithium silicate,
The extender pigment is at least one selected from talc, magnesium silicate, aluminum sulfate, and barium sulfate, and is contained in an amount of 42-50% by mass with respect to 100% by mass of the coating layer. Metal member. The rust preventive-treated metal member according to claim 1, wherein the rust preventive pigment is included in an amount of 9 to 13% by mass with respect to 100% by mass of the coat layer. 3. The rust-proof metal member according to claim 1, wherein the mass pigment has a mass cumulative particle diameter D90 of 18 μm or more according to a laser diffraction / scattering particle size distribution measurement method of the extender pigment. The organic solvent is
An aromatic solvent comprising at least one selected from toluene, xylene, and ethylbenzene;
An alcohol solvent consisting of at least one selected from ethylene glycol monobutyl ether, butanol, methanol, and phenol;
The rust-proof metal member according to any one of claims 1 to 3 , which is at least one selected from a ketone solvent consisting of at least one selected from methyl ethyl ketone and methyl butyl ketone. The rust-proof metal member according to any one of claims 1 to 4 , wherein the resin material is at least one selected from an epoxy resin, a phenol resin, and an acrylic resin. The coating paint comprises 10 to 15 parts by mass of a resin material, 4 to 6 parts by mass of the rust preventive pigment, 17 to 24 parts by mass of the extender pigment, and 50 to 59 parts by mass of the organic solvent. The metal member by which the rust prevention process was carried out as described in any one of Claims 1-5 containing. The metal hardness-treated metal member according to any one of claims 1 to 6 , wherein the coating layer has a pencil hardness of F to B. A coat paint that is a material for a coat layer formed on the upper layer of a zinc composite film formed by binding zinc powder with a binder ,
A coating base material containing an organic solvent and a resin material dissolved in the organic solvent, and an extender pigment and an antirust pigment dispersed and held in the coating base material,
The rust preventive pigment is zinc phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, polyphosphorus. At least one selected from aluminum silicate, sodium silicate, potassium silicate, lithium silicate,
The extender pigment is at least one selected from talc, magnesium silicate, aluminum sulfate, and barium sulfate, and is contained in an amount of 42 to 50 parts by mass with respect to 100 parts by mass of components other than the organic solvent in the coating paint . And coat paint. A coat paint that is a material for a coat layer formed on the upper layer of a zinc composite film formed by binding zinc powder with a binder ,
A coating base material containing an organic solvent and a resin material dissolved in the organic solvent, and an extender pigment and an antirust pigment dispersed and held in the coating base material,
The rust preventive pigment is zinc phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc polyphosphate, calcium polyphosphate, magnesium polyphosphate, polyphosphorus. At least one selected from aluminum silicate, sodium silicate, potassium silicate, lithium silicate,
The extender pigment is at least one selected from talc, magnesium silicate, aluminum sulfate, and barium sulfate, and is contained in 17 to 24 parts by mass with respect to 100 parts by mass of the coat paint. The coat paint of Claim 8 or Claim 9 containing 9-13 mass parts of said rust preventive pigments with respect to 100 mass parts of components other than the said organic solvent in the said coat paint. The coat paint according to claim 8 or 9 , comprising 4 to 6 parts by mass of the rust preventive pigment with respect to 100 parts by mass of the coat paint. The coat paint according to any one of claims 8 to 11 , wherein a value of a mass cumulative particle diameter D90 of the extender pigment measured by a laser diffraction / scattering particle size distribution measurement method is 18 µm or more.

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