JP4947823B2 - Coated metal molded article and method for producing coated metal molded article - Google Patents

Description

  The present invention relates to a coated metal molded article and a method for producing a coated metal molded article. In particular, the manufacture of coated metal molded products and coated metal molded products that have excellent water resistance and durability even when the protective layer (uppermost layer) is omitted, and thus can exhibit excellent antirust properties stably. Regarding the method.

  Conventionally, as a rust prevention technique for iron materials, a blasting material consisting of a multilayer particle assembly including a core made of iron and zinc formed around the core is projected onto the surface of a coated metal molded product. After forming a porous coating layer (hereinafter sometimes referred to as a zinc-containing porous coating layer), the zinc-containing porous coating layer is subjected to chromate treatment, and chromic acid, dichromic acid or chromic acid Rust prevention technology that permeates chromium compounds such as salt is widely used (for example, Patent Document 1).

However, such a rust prevention technique has a problem that it is harmful to the human body because a chromate solution must be used when the chromate treatment is performed on the zinc-containing porous coating layer.
In other words, the chromate solution used for chromate treatment contains chromium compounds such as chromic acid, dichromic acid, or chromate that correspond to toxic poisons, causing liver failure, skin ulcer, rhinitis, asthma, etc. There was a problem.

Then, the highly safe antirust technique which does not use a harmful chromium type compound is disclosed (for example, patent documents 2-4).
That is, Patent Document 2 discloses that the following (A) and (B) are essential components on the surface of an iron material, the surface of which is coated with an undercoat composed mainly of at least one metal selected from zinc and aluminum. A method for producing a corrosion-resistant iron material obtained by applying a rust coating composition and curing it by room temperature treatment or heat treatment is disclosed.
(A) a compound having at least one phenolic hydroxyl group in the molecule (b) a compound having at least one siloxane bond selected from the group of predetermined silicates and predetermined silicates and / or their Condensate

Patent Document 3 discloses a composite coating of a porous coating layer of zinc or a zinc-iron alloy formed on the surface of an iron material, and a polysiloxane formed by laminating the porous coating layer and a thermosetting resin. A steel material provided with a layer is disclosed.
Examples of thermosetting resins that can be used include thermosetting polyester resins and phenol resins having an effect as a rust inhibitor.

Further, in Patent Document 4, the following (A ′) and (B ′) are essential components on the surface of an iron material coated with an undercoat composed mainly of at least one selected from zinc and aluminum. A rust-proof coating composition is applied and cured by room temperature treatment or heat treatment, and further, a top coating composition containing the following (c) as an essential component is applied as a protective layer and cured by room temperature treatment or heat treatment. A method for producing a corrosion-resistant iron material is disclosed.
(B) a compound having at least one phenolic hydroxyl group in the molecule (b) a predetermined silane compound alone, a mixture of two or more kinds, a condensable product of two or more kinds of mixtures, or a mixture thereof (c) ′) Predetermined silicates, predetermined silicates, mixtures thereof, or condensation products thereof

Japanese Patent Publication No.59-9912 (Claims) JP 2003-328151 A (Claims) JP 2002-292792 (Claims) JP-A-2004-197151 (Claims)

However, although the rust prevention technique disclosed in Patent Document 2 includes a compound having a phenolic hydroxyl group as a rust prevention agent, the rust prevention coating composition can improve rust prevention to some extent, There was a problem of insufficient water resistance.
That is, the anticorrosion coating composition layer of the cited document 2 has a two-dimensional or three-dimensional relationship between the respective composition components even though the compound having a phenolic hydroxyl group has a property of being easily eluted in water. However, there is a problem that water resistance is insufficient and it is difficult to stably obtain sufficient rust prevention properties.

In addition, the rust prevention technique disclosed in Patent Document 3 is sufficient because the composite coating layer does not substantially contain a rust preventive agent except when a phenol resin is used as the thermosetting resin. There was a problem that it was difficult to stably obtain rust prevention properties.
Moreover, even when a phenol resin having an effect as a rust preventive agent is used as a thermosetting resin, such a phenol resin has a property of being easily eluted in water, and therefore, sufficient water resistance can be obtained. There is a problem that it is difficult to stably obtain sufficient rust prevention properties due to this.
In addition, even if the thermosetting polyester resin is further added as a thermosetting resin in order to improve the water resistance, and the compounding in the composite coating layer is promoted, the thermosetting polyester is Since this is an unsaturated polyester having abundant unsaturated groups in the molecular main chain, there has been a problem that it is difficult to uniformly disperse it in other components.
Further, the thermosetting polyester contains a vinyl monomer such as styrene and a polymerization initiator as essential components in addition to the unsaturated polyester.
However, since such a polymerization initiator is preferentially captured by the phenolic resin, it is increasingly difficult to improve the water resistance by promoting the composite in the composite coating layer. It was.

On the other hand, the rust prevention technique disclosed in Patent Document 4 improves water resistance to some extent by further laminating a protective layer (uppermost layer) on the surface.
However, when the protective layer (uppermost layer) is essential in this way, not only the manufacturing process becomes complicated, but the protective layer (uppermost layer) is easily peeled off from the lower layer, resulting in insufficient durability. As a result, the water resistance became insufficient, and eventually, there was a problem that it was difficult to stably obtain a sufficient rust prevention property.

Therefore, as a result of intensive studies, the present inventors have cured a rust preventive coating containing a silicone compound, an organic resin component having a predetermined hydroxyl value, a phenolic hydroxyl group-containing compound and a crosslinking agent on the zinc-containing porous coating layer. It is found that by laminating a resin layer containing a rust preventive agent, a coated metal molded product having excellent water resistance and durability, and thus capable of stably exhibiting excellent rust resistance can be obtained. The invention has been completed.
That is, the object of the present invention is to have excellent water resistance and durability even when the protective layer (uppermost layer) is omitted, and thus can stably exhibit excellent rust prevention properties. It is another object of the present invention to provide a coated metal molded article and a method for producing the same.

According to the present invention, a zinc-containing porous coating layer (including a zinc rich paint layer) and a rust preventive paint containing the following compositions (a) to (d) are cured on the surface of a metal molded product. A coated metal molded article in which a rust inhibitor-containing resin layer is sequentially formed is provided, and the above-described problems can be solved.
(A) Silicone compound 100 parts by weight (b) Organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) (b) component crosslinking agent 0.05 to 5 parts by weight That is, according to the present invention, a predetermined hydroxyl value is obtained. By disperse | distributing the organic resin component which has with respect to a silicone compound and a phenolic hydroxyl group containing compound, the antirust coating excellent in uniformity can be obtained.
Furthermore, the organic resin components having a predetermined hydroxyl value dispersed in the anti-corrosion paint having excellent uniformity are hardened and smooth by curing them while effectively combining them with a crosslinking agent. A rust inhibitor-containing resin layer having excellent water resistance and durability can be formed.
More specifically, when a rust inhibitor-containing resin layer is formed, the silicone compound and the organic resin component having a predetermined hydroxyl value are microphase-separated in the coating film, respectively, and the zinc-containing porous coating While the organic resin component is unevenly distributed on the layer side, the silicone compound is unevenly distributed on the surface of the coating film opposite to the zinc-containing porous coating layer, which is separately found by electron microanalyzer (EPMA) elemental analysis. is doing.
In addition, such microphase separation and uneven distribution improve the adhesion and rust prevention of the rust preventive agent-containing resin layer to the metal molded product, thereby improving the water resistance and durability of the rust preventive agent containing resin layer. It has been confirmed that it contributes effectively.
Therefore, even when the protective layer (uppermost layer) is omitted, excellent rust prevention can be stably exhibited.
Further, by omitting the protective layer (uppermost layer), the problem of peeling is fundamentally solved, and more excellent durability can be obtained.
Further, since no harmful chromium-based compound is used, excellent safety can be obtained.
The silicone compound basically means a compound having a siloxane bond in the molecule, but even a compound having no siloxane bond in the molecule, such as an alkoxysilane compound, may be hydrolyzed and condensed. Any compound that can form a siloxane bond with each other is included in the silicone compound.

In forming the coated metal molded article of the present invention, the organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as the component (b) is a polyester resin and / or a phenoxy resin. It is preferable that
By comprising in this way, it becomes comparatively easy to set it as a predetermined hydroxyl value, and it can be dispersed more uniformly with respect to the silicone compound and the phenolic hydroxyl group-containing compound. It can be cured while being more unevenly distributed. Therefore, more excellent water resistance and durability can be obtained, and consequently, excellent rust prevention can be obtained more stably.

Moreover, in constituting the coated metal molded article of the present invention, the hydroxyl value of the polyester resin is preferably set to a value within the range of 4 to 20 mgKOH / g.
By comprising in this way, combined with the resin characteristics of the polyester resin, it is possible to obtain further excellent water resistance and durability, and in turn, it is possible to more stably obtain excellent rust prevention.

Moreover, in constituting the coated metal molded article of the present invention, the hydroxyl value of the phenoxy resin is preferably set to a value within the range of 200 to 300 mgKOH / g.
By comprising in this way, combined with the resin characteristics of the phenoxy resin, it is possible to obtain further excellent water resistance and durability, and in turn, excellent rust resistance can be obtained more stably.

Further, in constituting the coated metal molded article of the present invention, the organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as the component (b) is an organic resin component having water dispersibility. It is preferable.
By comprising in this way, the organic resin component having a predetermined hydroxyl value can be more uniformly dispersed in the silicone compound and the phenolic hydroxyl group-containing compound, and moreover, it can be made more unevenly distributed in the coating film. Therefore, it is possible to obtain excellent water resistance and durability, and thus excellent rust resistance can be obtained more stably.
In addition, water dispersibility means the state which can be melt | dissolved or disperse | distributed with respect to water or the aqueous solvent formed by mixing an organic solvent mainly with water.
The dispersion state generally refers to a state called an emulsion or a colloidal dispersion. The average particle diameter of the emulsion or the like is preferably a value in the range of 0.001 to 3 μm. A value within the range of 04 to 1 μm is preferable.
Further, in determining water dispersibility, even when the organic resin component is dissolved in water at a concentration of 1% by weight and left at 25 ° C. for 24 hours, the organic resin component is precipitated or phase separated. It can be based on the fact that the solution is uniform without producing.

Further, in constituting the coated metal molded article of the present invention, the weight average molecular weight of the organic resin component having a hydroxyl value as the component (b) in the range of 1 to 500 mgKOH / g is 2,000 to 50,000. It is preferable to set the value within the range.
By comprising in this way, since the organic resin component which has a predetermined hydroxyl value can be disperse | distributed more uniformly with respect to a silicone compound and a phenolic hydroxyl group containing compound, it can obtain the further outstanding water resistance. As a result, excellent rust prevention can be obtained more stably.

In constituting the coated metal molded article of the present invention, the silicone compound as component (a) is at least one selected from the group consisting of ethyl silicate, methyl silicate, ammonium silicate and methyl trimethoxysilane. preferable.
By comprising in this way, since the organic resin component which has a predetermined hydroxyl value can be hardened in the state where it was made more unevenly distributed with respect to a silicone compound and a phenolic hydroxyl group containing compound, it was further excellent in water resistance Further, durability can be obtained, and as a result, excellent rust prevention can be obtained more stably.

In forming the coated metal molded article of the present invention, the phenolic hydroxyl group-containing compound as component (c) is composed of vanadium tannate, molybdenum tannate, 3,4,5-trihydroxybenzenecarboxylic acid (hereinafter referred to as gallic acid). And may contain at least one selected from the group consisting of 3,4,5-trihydroxybenzenecarboxylic acid esters.
By comprising in this way, the more outstanding rust prevention property can be acquired.

Further, in constituting the coated metal molded article of the present invention, when the organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as a component (b) contains a polyester resin, (d) The crosslinking agent as the component is an organic titanium compound and / or an organic zirconium compound, and the organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as the component (b) is phenoxy When a resin is included, the crosslinking agent as the component (d) is preferably a blocked isocyanate.
By constituting in this way, coupled with the respective resin characteristics in the polyester resin and phenoxy resin, it is possible to obtain a more excellent water resistance and durability by curing the rust preventive paint while making it more unevenly distributed. Rust prevention can be obtained more stably.

In forming the coated metal molded article of the present invention, the organic titanium compound is at least one selected from the group consisting of titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt, and titanium lactate. In addition to being a compound, the organic zirconium compound preferably contains a zirconium chloride compound aminocarboxylic acid.
By comprising in this way, it can harden, further unevenly distributing a rust preventive coating material, and can obtain the further outstanding water resistance and durability, and can also obtain the outstanding rust prevention property still more stably. .

Further, in constituting the coated metal molded article of the present invention, the fluorine resin compound is further contained as the component (e), and the addition amount thereof is set to 0.1% with respect to 100 parts by weight of the silicone compound as the component (a). A value within the range of 5 to 30 parts by weight is preferred.
By comprising in this way, surface characteristics, such as a slip characteristic or a torque characteristic in a rust preventive agent containing resin layer, can be adjusted efficiently.

Further, in constituting the coated metal molded article of the present invention, the rust preventive paint further contains, as the component (f), a pyrazole compound and a triazole compound, or one of them, and the addition amount thereof is (a) It is preferable to make it the value within the range of 0.1-15 weight part with respect to 100 weight part of silicone compounds as a component.
By comprising in this way, the rust prevention property in a rust preventive agent containing resin layer can be adjusted easily, especially by reaction with zinc in a zinc containing porous coating layer (including a zinc rich paint layer). White rust prevention effect can be obtained.

In forming the coated metal molded article of the present invention, the thickness of the zinc-containing porous coating layer is set to a value within the range of 3 to 10 μm, and the thickness of the rust inhibitor-containing resin layer is 1 to 15 μm. A value within the range is preferable.
By comprising in this way, while being able to exhibit the rust prevention property in a zinc containing porous coating layer and a rust preventive agent containing resin layer without excess and deficiency, durability can further be improved.

Moreover, another aspect of the present invention is a method for producing a coated metal molded product characterized by sequentially including the following steps (1) to (4).
(1) Step of preparing a metal molded product (2) Step of forming a zinc-containing porous coating layer (including a zinc rich paint layer) using a thermal spraying device (3) For the zinc-containing porous coating layer, the following The step of applying a rust-preventing paint containing the compositions (a) to (d) (4) The step of curing the rust-preventing paint and forming a rust-preventing agent-containing resin layer (a) 100 parts by weight of a silicone compound (b) Hydroxyl value Resin component whose value is within the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) (b) component crosslinking agent 0.05 to 5 parts by weight That is, in the method for producing a coated metal molded product of the present invention According to the above, even when the protective layer (top layer) is omitted, a coated metal molded product having excellent rust prevention and water resistance, excellent durability, and also excellent safety. It can be manufactured stably.

Fig.1 (a)-(d) is a figure provided in order to demonstrate the laminated structure of a covering metal molded product. FIG. 2 is a diagram for explaining the relationship between the blending amount of an organic resin component having a predetermined hydroxyl value and rust prevention. Drawing 3 is a figure offered in order to explain a manufacture flow chart of a covering metal fabrication article. FIG. 4 is a diagram provided for explaining the thermal spraying apparatus. FIG. 5 is an EPMA chart (carbon (C) distribution state) in the first embodiment. FIG. 6 is an EPMA chart (carbon (C) distribution state) in Example 3. FIG. 7 is an EPMA chart (carbon (C) distribution state) in Example 4. FIG. 8 is an EPMA chart (carbon (C) distribution status) in Example 10. FIG. 9 is an EPMA chart (carbon (C) distribution state) in Example 14.

[First Embodiment]
As illustrated in FIG. 1C, the first embodiment includes a zinc-containing porous coating layer 12 on the surface of the metal molded article 10 and an anticorrosive paint including the following compositions (a) to (d). Is a coated metal molded article formed by sequentially forming a rust inhibitor-containing resin layer 14 formed by curing
(A) Silicone compound 100 parts by weight (b) Organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) component (b) cross-linking agent 0.05 to 5 parts by weight Hereinafter, the coating of the present invention with reference to the drawings as appropriate The metal molded product will be specifically described.

1. Metal Molded Product The material of the metal molded product 10 illustrated in FIG. 1A and the like is not particularly limited, and examples thereof include carbon steel, alloy steel, stainless steel, and special steel.
In addition, the metal molded article made of such a material may be processed into a desired shape such as a plate shape or a rod shape by a method such as rolling, casting, drawing, or a building material, a construction machine, a ship, Members and parts such as bridges, automobiles, and containers may be used.
Examples of such specific parts include shavings, nails, bolts, nuts, screws, washers, clamps, pins, dowels, coils, and the like.

2. Zinc-containing porous coating layer The zinc-containing porous coating layer 12 illustrated in FIG. 1B or the like is a coating layer composed of an assembly of pressure-bonding pieces made of zinc or zinc-iron alloy, and is porous. It preferably has a structure.
This is because the zinc-containing porous coating layer having a large surface area serves as a sacrificial anticorrosive layer (anode), thereby suppressing oxidation of the metal molded product.
Furthermore, by setting it as a porous structure, it is because the rust preventive agent containing resin layer mentioned later can be laminated | stacked physically firmly.
In addition, the zinc-containing porous coating layer typically has a high specific gravity of iron or the like as a core, and zinc-coated particles having a high-hardness iron-zinc alloy in the middle as a blasting material. It can be formed by applying a large amount of projection energy, projecting it onto the surface of the metal molded product, and pressing it onto the surface of the metal molded product.

Here, the thickness of the zinc-containing porous coating layer is preferably set to a value within the range of 3 to 10 μm.
This is because when the thickness of the zinc-containing porous coating layer is less than 3 μm, the film formability may be significantly reduced, and the rust prevention and corrosion resistance of the metal molded product may be significantly reduced. It is. On the other hand, when the thickness of the zinc-containing porous coating layer exceeds 10 μm, it may be difficult to form a uniform thickness, or the adhesion to a metal molded product may be reduced. Because there is.

3. Rust Inhibitor-Containing Resin Layer (1) Basic Structure A rust inhibitor-containing resin layer 14 exemplified in FIG. 1C and the like is formed by curing a rust preventive paint containing the following compositions (a) to (d). It is a rusting agent-containing resin layer.
(A) Silicone compound 100 parts by weight (b) Organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) (b) component crosslinking agent 0.05 to 5 parts by weight More specifically, a silicone compound and a predetermined hydroxyl group It is a resin layer having a two-dimensional or three-dimensional structure in which an organic resin component having a valence and a phenolic hydroxyl group-containing compound are mixed and combined.
Since such a rust inhibitor-containing resin layer contains a phenolic hydroxyl group-containing compound as a rust inhibitor, such a compound reacts with iron to form an iron salt, forming a complex compound, and reducing oxygen transmission. be able to.
Therefore, the oxidation of the zinc-containing porous coating layer can be effectively suppressed by the rust preventive agent-containing resin layer, and as a result, excellent rust prevention property in the metal molded product can be obtained.
On the other hand, the phenolic hydroxyl group-containing compound has a problem of poor water resistance because of its high water solubility.
In this respect, according to the present invention, a rust-preventing paint having excellent uniformity can be obtained by dispersing an organic resin component having a predetermined hydroxyl value in a silicone compound and a phenolic hydroxyl group-containing compound.
Furthermore, the rust preventive paint having excellent uniformity is cured by effectively combining the rust preventive paint with a cross-linking agent, thereby being strong and smooth and having excellent water resistance and durability. Can be formed.
More specifically, when a rust inhibitor-containing resin layer is formed, the silicone compound and the organic resin component having a predetermined hydroxyl value are microphase-separated in the coating film, respectively, and the zinc-containing porous coating While the organic resin component is unevenly distributed on the layer side, the silicone compound can be unevenly distributed on the coating film surface side opposite to the zinc-containing porous coating layer.
As a result, the microphase separation and uneven distribution improve the adhesion and rust prevention properties of the resin layer containing the rust preventive agent to the metal molded product, and consequently improve the water resistance and durability of the resin layer containing the rust preventive agent. Can be made.
Therefore, even when the protective layer (uppermost layer) is omitted, excellent rust prevention can be stably exhibited.
In addition, since it is possible to omit the protective layer (uppermost layer), the problem of peeling is fundamentally solved, and more excellent durability can be obtained.
Further, since no harmful chromium-based compound is used, excellent safety can be obtained.

In addition, the structure formed by compounding a silicone compound, a phenolic hydroxyl group-containing compound or the like in the resin layer containing a rust preventive agent of the present invention typically has a low molecular weight substance (monomer or oligomer) as a starting material. Can be formed by mixing or polymerization reaction.
However, since the film formability can be effectively improved, in the state where the polymer of the silicone compound and the phenolic hydroxyl group-containing compound coexists, the low molecular weight product of the silicone compound and the phenolic hydroxyl group-containing compound is used as a starting material. It is also preferable to form them by mixing or polymerizing them.
Hereinafter, the anticorrosion paint for forming the antirust agent-containing resin layer will be specifically described for each constituent requirement.

(2) Silicone compound The anticorrosive paint in the present invention is characterized by containing a silicone compound as the component (a).
The reason for this is that the silicone compound is hydrolytically condensed while compounded with a phenolic hydroxyl group-containing compound that is a rust preventive or an organic resin component having a predetermined hydroxyl value, thereby suppressing the elution of the phenolic hydroxyl group-containing compound. This is because the water resistance of the rust inhibitor-containing resin layer can be effectively improved.
Moreover, when a rust preventive agent-containing resin layer is formed by including a predetermined amount of a silicone compound, the silicone compound and an organic resin component having a predetermined hydroxyl value are cured while being unevenly distributed in the coating film, respectively. The adhesion strength to the metal molded product can be effectively improved.
More specifically, a rich layer of an organic resin component is formed on the inner surface side of the coating film that is in direct contact with the zinc-containing porous coating layer, and a rich layer of a silicone compound is formed on the surface side of the coating film. Therefore, excellent adhesion to a metal molded product, water repellency, heat resistance and the like can be obtained as a whole coating film.
The silicone compound basically means a compound having a siloxane bond in the molecule, but even a compound having no siloxane bond in the molecule, such as an alkoxysilane compound, may be hydrolyzed and condensed. Any compound that can form a siloxane bond with each other is included in the silicone compound.

(2) -1 type Examples of the silicone compound include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, methyl silicate, ethyl silicate, lithium silicate, sodium silicate, potassium silicate, and methyltri Examples thereof include propanolammonium silicate and dimethyldipropanolammonium silicate, and these oligomers may be used.
In addition, as an alkyl group in tetraalkoxysilane etc., a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a phenyl group etc. are mentioned, for example. Moreover, as an alkoxy group in tetraalkoxysilane etc., a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
Of these, at least one selected from the group consisting of ethyl silicate, methyl silicate, ammonium silicate, and methyltrimethoxysilane is particularly preferable.
The reason for this is that these compounds are more excellent because the silicone compound, the organic resin component having a predetermined hydroxyl value, and the phenolic hydroxyl group-containing compound can be cured in an unevenly distributed state in the coating film. This is because water resistance and durability can be obtained, and as a result, excellent rust prevention can be obtained more stably.

(2) -2 Compounding quantity Moreover, it is preferable to make the compounding quantity of a silicone compound into the value within the range of 30-80 weight% with respect to 100 weight% of whole quantity of a rust preventive agent containing resin layer.
This is because, by setting the blending amount of the silicone compound to a value within this range, elution of the phenolic hydroxyl group-containing compound can be suppressed, and the water resistance of the rust preventive agent-containing resin layer can be effectively improved. Because.
That is, when the blending amount is less than 30% by weight, uneven distribution in the coating film becomes insufficient, or it becomes difficult to effectively suppress elution of the phenolic hydroxyl group-containing compound, thereby preventing rust. This is because the water resistance of the agent-containing resin layer may be excessively lowered. On the other hand, when the blending amount exceeds 80% by weight, uneven distribution in the coating film becomes insufficient, or the blending amount of the phenolic hydroxyl group-containing compound as a rust preventive agent becomes relatively small. This is because the rust resistance may be insufficient or it may be difficult to uniformly disperse the organic resin component having a predetermined hydroxyl value.
Therefore, the blending amount of the silicone compound is more preferably set to a value within the range of 35 to 70% by weight, and within the range of 40 to 60% by weight with respect to 100% by weight of the total amount of the rust inhibitor-containing resin layer. More preferably, the value of

(3) Organic resin component having a predetermined hydroxyl value The anticorrosive paint in the present invention is characterized in that the component (b) includes an organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g. To do.
The reason for this is that by including the organic resin component having the predetermined hydroxyl value, the organic resin component having the predetermined hydroxyl value is uniformly dispersed in the silicone compound and the phenolic hydroxyl group-containing compound. This is because a paint can be obtained.
Therefore, a rust preventive-containing resin layer can be formed firmly and smoothly by curing the rust preventive paint using a cross-linking agent, which will be described later, while effectively compositing it and making it unevenly distributed in the coating film. This is because the water resistance of the rust inhibitor-containing resin layer can be effectively improved.
That is, when the value of the hydroxyl value is less than 1 mgKOH / g, uneven distribution in the coating film becomes insufficient, or the hydroxyl group contributing to dispersibility becomes excessively small, and the silicone compound is uniformly distributed. This is because it may be difficult to disperse. Moreover, it is because the hydroxyl group which contributes to bridge | crosslinking by a crosslinking agent becomes too few, and it becomes difficult to form a rust preventive agent containing resin layer firmly and smoothly. On the other hand, when the value of the hydroxyl value exceeds 500 mgKOH / g, uneven distribution in the coating film becomes insufficient, and the adhesion and durability of the anticorrosive paint are excessively lowered or precipitation is likely to occur. This is because there is a case where it becomes.
Therefore, the hydroxyl value in the organic resin component having a predetermined hydroxyl value is more preferably a value within the range of 2 to 400 mgKOH / g, and even more preferably a value within the range of 4 to 300 mgKOH / g.
In addition, the measuring method of a hydroxyl value is described in an Example.

In addition, the type of the organic resin component having a predetermined hydroxyl value in the present invention is not particularly limited. For example, polyester resin, urethane resin, phenoxy resin, epoxy resin, cellulose resin, phenol resin, acrylic resin, An alkyd resin, a polyether resin, a butyral resin, a ketone resin, and the like can be mentioned, and a polyester resin and a phenoxy resin are preferred.
The reason for this is that these organic resin components are relatively easy to achieve a predetermined hydroxyl value and can be more uniformly dispersed in the silicone compound and the phenolic hydroxyl group-containing compound. This is because it can be cured while being unevenly distributed in the coating film.
Therefore, it is because the more outstanding water resistance and durability can be obtained and by extension, the outstanding rust prevention property can be obtained stably.
Hereinafter, the polyester resin and the phenoxy resin will be described in detail.

(3) -1 Polyester resin The polybasic acid constituting the polyester resin having a predetermined hydroxyl value can be constituted as a condensate of a polybasic acid and a polyhydric alcohol. By appropriately changing the kind of the monohydric alcohol and further the third component, the hydroxyl value and the acid value can be appropriately adjusted to values within a predetermined range.

Moreover, it is preferable that the polyester resin which has a predetermined hydroxyl value is a thermoplastic polyester resin.
The reason for this is that if a thermoplastic polyester resin is used, a polyester resin having a predetermined hydroxyl value can be more uniformly dispersed in the silicone compound and the phenolic hydroxyl group-containing compound. This is because more excellent water resistance and durability can be obtained, and as a result, excellent rust prevention can be stably obtained.
Conversely, when a thermosetting polyester resin is used, an unsaturated polyester resin having an unsaturated group in the main chain of the molecule and a vinyl monomer such as styrene are copolymerized using a polymerization initiator and cured. However, such an unsaturated polyester resin may be difficult to uniformly disperse in the silicone compound and the phenolic hydroxyl group-containing compound.
Furthermore, when a thermosetting polyester resin is used, since the polymerization initiator is preferentially captured by the phenolic hydroxyl group-containing compound, in the first place, it may be difficult to stably cure the rust preventive coating. Because there is.
Therefore, the polyester resin having a hydroxyl group of the present invention is more preferably a saturated polyester resin having no unsaturated group in the main chain of the molecule.

Moreover, it is preferable to make the hydroxyl value of a polyester resin into the value within the range of 4-20 mgKOH / g.
This is because, in the case of a polyester resin, by setting the hydroxyl value within this range, it is possible to obtain further excellent water resistance and durability in combination with the resin characteristics of the polyester resin, and thus excellent rust prevention properties. This is because can be obtained more stably.
That is, when the hydroxyl value is less than 4 mgKOH / g, uneven distribution in the coating film becomes insufficient, or the hydroxyl group contributing to dispersibility becomes excessively small, and the silicone compound is uniformly dispersed. This may be difficult. Moreover, it is because the hydroxyl group which contributes to bridge | crosslinking by a crosslinking agent becomes too few, and it becomes difficult to form a rust preventive agent containing resin layer firmly and smoothly. On the other hand, when the value of the hydroxyl value exceeds 20 mgKOH / g, the adhesion and durability of the anticorrosive paint may be excessively reduced or precipitation may easily occur.
Accordingly, the hydroxyl value of the polyester resin is more preferably set to a value within the range of 5 to 15 mgKOH / g, and further preferably set to a value within the range of 5.5 to 10 mgKOH / g.
The hydroxyl value of the polyester resin described above may be a case where a polyester resin is used alone as an organic resin component having a predetermined hydroxyl value, or a case where it is used in combination with another organic resin component. This means that the hydroxyl value of the polyester resin alone is preferably set to a value within the above-described range. The same applies to the acid value described later.

Moreover, it is preferable to make the acid value of a polyester resin into the value within the range of 0.1-20 mgKOH / g.
The reason for this is that when the acid value is less than 0.1 mg KOH / g, it is difficult to cure while being unevenly distributed in the coating film, and the water resistance may decrease. is there. On the other hand, when the value of the acid value exceeds 20 mgKOH / g, uneven distribution in the coating film becomes insufficient, or the hydroxyl group contributing to dispersibility becomes excessively small, and the silicone compound and the phenolic hydroxyl group. This is because it may be difficult to uniformly disperse the contained compound.
Therefore, the acid value of the polyester resin is more preferably set to a value within the range of 1 to 10 mgKOH / g, and further preferably set to a value within the range of 1.5 to 5 mgKOH / g.
In addition, the measuring method of an acid value is described in an Example.

The polyester resin having a predetermined hydroxyl value in the present invention means a “polyester resin having a hydroxyl group” other than the linear polyester resin in which only one terminal group is a hydroxyl group.
That is, in the linear polyester resin, one terminal group is substantially a hydroxyl group. In the present invention, for such a linear polyester resin in which only one terminal group is a hydroxyl group, “predetermined It shall not be included in the “polyester resin having a hydroxyl value”.
This is because, in such a linear polyester resin in which only one terminal group is a hydroxyl group, the absolute number of hydroxyl groups is insufficient, so that it is difficult to uniformly disperse the silicone compound and the phenolic hydroxyl group-containing compound. This is because it may become.
Moreover, it is because it may become difficult to combine effectively also when making it harden | cure.
Therefore, the polyester resin having a predetermined hydroxyl value in the present invention includes, for example, a linear polyester resin having at least one hydroxyl group in the molecule, and a plurality of hydroxyl groups at a plurality of molecular terminals in addition to one terminal. Examples thereof include dendrimer-type polyester resins.
As a method for introducing such a hydroxyl group, for example, in the case of a dendrimer type polyester resin, when two or more substituents among the three or more substituents in the monomer are hydroxyl groups, The terminal group can be a hydroxyl group.
On the other hand, when the terminal group is other than a hydroxyl group, for example, when it is a carboxyl group or an ester group, the terminal group can be converted into a hydroxyl group by reaction with a glycidyl compound, hydrolysis, or the like.

(3) -2 Phenoxy resin A phenoxy resin having a predetermined hydroxyl value is a polyhydroxy ether as a high molecular weight substance of an epoxy compound. For example, bisphenols and epichlorohydrin are combined in the presence of an alkali catalyst. Obtained by condensation.
Therefore, the hydroxyl value and the acid value can be appropriately adjusted to values within a predetermined range by appropriately changing the types of the various bisphenols and epichlorohydrin and the third component.
In addition, the phenoxy resin can obtain an effect superior to the above-described polyester resin, particularly in the durability.

Moreover, it is preferable to make the hydroxyl value of a phenoxy resin into the value within the range of 200-300 mgKOH / g.
The reason for this is that, in the case of phenoxy resin, by setting the hydroxyl value within this range, in combination with the resin characteristics of phenoxy resin, it is possible to obtain further excellent water resistance and durability, and thus excellent rust resistance This is because can be obtained more stably.
That is, when the hydroxyl value is less than 200 mgKOH / g, uneven distribution in the coating film becomes insufficient, or the hydroxyl group contributing to dispersibility becomes excessively small, and the silicone compound is uniformly dispersed. This may be difficult. Moreover, it is because the hydroxyl group which contributes to bridge | crosslinking by a crosslinking agent becomes too few, and it becomes difficult to form a rust preventive agent containing resin layer firmly and smoothly. On the other hand, when the value of the hydroxyl value exceeds 300 mgKOH / g, uneven distribution in the coating film becomes insufficient, and the adhesion and durability of the anticorrosive paint are excessively lowered or precipitation occurs. It is because it may become easy.
Therefore, the hydroxyl value of the phenoxy resin is more preferably set to a value within the range of 220 to 280 mgKOH / g, and further preferably set to a value within the range of 250 to 270 mgKOH / g.
The hydroxyl value of the phenoxy resin described above may be a case where a phenoxy resin is used alone or a mixture with other organic resin components as an organic resin component having a predetermined hydroxyl value. This means that the hydroxyl value of the phenoxy resin alone is preferably set to a value within the above-mentioned range. The same applies to the acid value described later.

Moreover, it is preferable to make the acid value of a phenoxy resin into the value within the range of 30-60 mgKOH / g.
The reason for this is that when the acid value is less than 30 mgKOH / g, it becomes difficult to uniformly cure the rust preventive agent-containing resin layer while effectively unevenly distributing it, and the water resistance is lowered. This is because there are cases. On the other hand, when the value of the acid value exceeds 60 mgKOH / g, uneven distribution in the coating film becomes insufficient, or hydroxyl groups contributing to dispersibility become excessively small, and silicone compounds and phenolic hydroxyl groups are obtained. This is because it may be difficult to uniformly disperse the contained compound.
Therefore, the acid value of the phenoxy resin is more preferably set to a value within the range of 40 to 50 mgKOH / g, and further preferably set to a value within the range of 35 to 45 mgKOH / g.
In addition, the measuring method of an acid value is described in an Example.

(3) -3 Mixed Resin The organic resin component having a predetermined hydroxyl value is also preferably a mixed resin of a polyester resin and a phenoxy resin.
The reason for this is that a rust-preventing agent-containing resin layer that can be cured while making it more complex, and is stronger and smoother, and further excellent in water resistance and durability, can be obtained by configuring in this way. This is because it can be formed.
In addition, it is preferable to make polyester resin: phenoxy resin (weight ratio) into the ratio in the range of 10: 90-90: 10 from a viewpoint of making it harden | cure while combining an antirust coating more effectively, 25: A ratio in the range of 75 to 75:25 is more preferable, and a ratio in the range of 40:60 to 60:40 is more preferable.
Moreover, as a hydroxyl value of this mixed resin, it is preferable to set it as the value within the range of 30-250 mgKOH / g, It is more preferable to set it as the value within the range of 50-200 mgKOH / g, 100-150 mgKOH / g More preferably, the value is within the range.
For example, the hydroxyl value of the polyester resin used is A (mg KOH / g), the blending amount is a (g), the hydroxyl value of the phenoxy resin used is B (mg KOH / g), and the blending amount is b (g). In this case, the hydroxyl value (theoretical value) of the mixed resin can be obtained as A × (a / a + b) + B × (b / a + b) (mgKOH / g).
Of course, the hydroxyl value of the mixed resin can also be measured by the method shown in the examples.

(3) -4 Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of the organic resin component which has a predetermined | prescribed hydroxyl value into the value within the range of 2,000-50,000.
This is because the organic resin component having a predetermined hydroxyl value, the silicone compound and the phenolic hydroxyl group-containing compound are obtained by setting the weight average molecular weight of the organic resin component having a predetermined hydroxyl value within the above range. This is because the water can be more uniformly dispersed, so that further excellent water resistance can be obtained, and as a result, excellent rust prevention can be obtained more stably.
That is, when the value of the weight average molecular weight is less than 2,000, not only the water resistance tends to be excessively lowered, but also chemical resistance and workability are likely to be lowered. On the other hand, when the value of the weight average molecular weight exceeds 50,000, it becomes difficult to give a sufficient hydroxyl value to the organic resin component having a predetermined hydroxyl value, and the dispersibility tends to be excessively lowered. This is because the viscosity may become excessively high, or uneven distribution in the coating film may be insufficient.
Therefore, the weight average molecular weight of the organic resin component having a predetermined hydroxyl value is more preferably set to a value in the range of 5,000 to 40,000, and a value in the range of 8,000 to 30,000. Is more preferable.
In addition, a weight average molecular weight can be measured using GPC (gel permeation chromatography, polystyrene conversion).

(3) -5 Water dispersibility It is preferable that the organic resin component having a predetermined hydroxyl value is an organic resin component having water dispersibility.
The reason for this is that by having water dispersibility, the organic resin component having a predetermined hydroxyl value can be more uniformly dispersed in the silicone compound and the phenolic hydroxyl group-containing compound. In addition, durability can be obtained, and as a result, excellent rust prevention can be obtained more stably.
On the other hand, when the rust inhibitor-containing resin layer is formed, the silicone compound and the organic resin component having a predetermined hydroxyl value are cured while being more effectively unevenly distributed in the coating film. Therefore, the adhesive force with respect to a metal molded product can be improved more effectively.

In addition, water dispersibility means the state which can be melt | dissolved or disperse | distributed with respect to water or the aqueous solvent formed by mixing an organic solvent mainly with water.
The dispersion state generally refers to a state called an emulsion or a colloidal dispersion. The average particle diameter of the emulsion or the like is preferably a value in the range of 0.001 to 3 μm. A value within the range of 04 to 1 μm is preferable.
Further, in determining water dispersibility, even when the organic resin component is dissolved in water at a concentration of 1% by weight and left at 25 ° C. for 24 hours, the organic resin component is precipitated or phase separated. It can be based on the fact that the solution is uniform without producing.

Further, when the organic resin component having a predetermined hydroxyl group is an organic resin component having water dispersibility, when the organic resin component is added to a silicone compound or the like, it may be added in the state of an aqueous dispersion. preferable.
Moreover, as solid content concentration of this water dispersion, it is preferable to set it as the value within the range of 10 to 50 weight%, It is more preferable to set it as the value within the range of 20 to 40 weight%, 25 to 35 weight% More preferably, the value is within the range of%.
Furthermore, as pH of this water dispersion, it is preferable to set it as the value within the range of 3-8, It is more preferable to set it as the value within the range of 4-7.5, and within the range of 4.5-7 More preferably, the value of

(3) -6 Compounding quantity Moreover, the compounding quantity of the organic resin component which has a predetermined | prescribed hydroxyl value is made into the value within the range of 15-200 weight part with respect to 100 weight part of silicone compounds, It is characterized by the above-mentioned.
The reason for this is that when the blending amount is less than 15 parts by weight, the absolute amount of the organic resin component is excessively reduced, and the effect of uneven distribution in the coating film becomes insufficient. This is because there is a case where the adhesion of is insufficient. As a result, the water resistance of the rust inhibitor-containing resin layer may be excessively lowered. On the other hand, when the blending amount exceeds 200 parts by weight, the blending amount of the organic resin component with respect to the silicone compound becomes excessive, resulting in insufficient distribution of these components in the coating film, and metal forming. This is because the adhesion of the coating film to the product may be insufficient. Also, when the storage stability of the rust preventive paint tends to be excessively lowered, or the proportion of the silicone compound or phenolic hydroxyl group-containing compound is relatively lowered, making it difficult to obtain sufficient rust preventive properties. Because there is.
Accordingly, the blending amount of the organic resin component having a predetermined hydroxyl value is more preferably set to a value within the range of 20 to 150 parts by weight with respect to 100 parts by weight of the silicone compound. More preferably, the value of

Then, the relationship between the compounding quantity of the organic resin component which has a predetermined hydroxyl value, and rust prevention property is demonstrated using FIG.
That is, in FIG. 2, the horizontal axis represents the blending amount (parts by weight) of a polyester resin (hydroxyl number: 5.8) as an example of an organic resin component having a predetermined hydroxyl value with respect to 100 parts by weight of the silicone compound. On the vertical axis, a characteristic curve showing the time (time) until the occurrence of rust in the SST test is shown.
Other details will be described in the examples.

As understood from the characteristic curve, as the blending amount of the organic resin component having a predetermined hydroxyl value increases, the time until rust generation in the SST test becomes longer.
More specifically, it can be seen that when the blending amount of the organic resin component having a predetermined hydroxyl value is 15 parts by weight or more, the time until rust generation in the SST test can be set to a level of about 700 hours or more.
On the other hand, it has been separately confirmed that when the blending amount of the organic resin component having a predetermined hydroxyl value exceeds 200 parts by weight, problems such as a decrease in storage stability of the anticorrosive paint tend to occur. .
Therefore, it is understood that the blending amount of the organic resin component having a predetermined hydroxyl value should be a value within the range of 15 to 200 parts by weight with respect to 100 parts by weight of the silicone compound.
As shown in the examples, it has been confirmed that similar results can be obtained even when a phenoxy resin is used as the organic resin component having a predetermined hydroxyl value.

(4) Phenolic hydroxyl group-containing compound The rust-preventing paint according to the invention is characterized by containing a phenolic hydroxyl group-containing compound as the component (c).
This is because the phenolic hydroxyl group-containing compound has a function as a catalyst for the curing reaction of the component (a) and also has a function as an excellent rust inhibitor.
That is, the phenolic hydroxyl group-containing compound reacts with iron to form an iron salt, forms a complex compound, and can reduce oxygen permeation.
Therefore, by including a phenolic hydroxyl group-containing compound in the rust preventive agent-containing resin layer, oxidation of the zinc-containing porous coating layer can be effectively suppressed, and as a result, excellent rust prevention property in metal molded products. This is because it can be obtained.
The phenolic hydroxyl group-containing compound also has an advantage of exhibiting a function as an acid catalyst in a hydrolysis condensation reaction of a silicone compound.

(4) -1 type In addition, examples of the phenolic hydroxyl group-containing compound include monovalent phenols such as phenol, cresol, thymol, bromophenol, naphthol, and anilinophenol. Pyrocatechin (catechol), resorcin, hydroquinone, orcin, urushiol, bisphenol A, binaphthol and the like. Examples of trivalent phenols include pyrogallol, phloroglucin, hydroxyhydroquinone, 3,4,5-trihydroxybenzenecarboxyl. Acid (gallic acid), 3,4,5-trihydroxybenzenecarboxylic acid ester and the like, and further polyhydric phenols include tannic acid compounds (tannic acid, vanadium tannate, molybdenum tannate, tannic acid acid). Miniumu, tannic acid tungsten) and phenol - like formaldehyde condensate (phenolic resin) and the like.
Among these, in particular, at least one selected from the group consisting of vanadium tannate, molybdenum tannate, 3,4,5-trihydroxybenzenecarboxylic acid and 3,4,5-trihydroxybenzenecarboxylic acid ester is included. It is preferable.
This is because these compounds can more effectively improve the rust prevention property of the rust inhibitor-containing resin layer.
That is, if these compounds are used, a rust-proof coating can be effectively formed by a chelate reaction with the steel material surface.
In addition, tannic acid salts such as tannic acid and vanadium tannate are not only effective as a rust preventive agent but also colored black in the rust preventive-containing resin layer when the metal molding to be coated is a steel material. It is particularly useful in that it also has an effect as an agent.
Moreover, if it is a phenol-formaldehyde condensate (phenol resin) etc., since it self-condenses, it is especially useful in the point which can further improve the film formability of a rust preventive agent containing resin layer.

(4) -2 Blending amount The blending amount of the phenolic hydroxyl group-containing compound is a value within the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the silicone compound.
The reason for this is to effectively improve the balance between rust prevention and water resistance in the rust inhibitor-containing resin layer by setting the blending amount of the phenolic hydroxyl group-containing compound to a value within this range. This is because it can.
That is, when the blending amount is less than 0.1 parts by weight, it may be difficult to obtain a sufficient effect as a rust inhibitor by the phenolic hydroxyl group-containing compound. On the other hand, when the blending amount exceeds 30 parts by weight, the phenolic hydroxyl group-containing compound tends to be excessively eluted and it may be difficult to obtain sufficient water resistance.
Therefore, the blending amount of the phenolic hydroxyl group-containing compound is more preferably set to a value within the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the silicone compound, and a value within the range of 1 to 2 parts by weight. More preferably.

(5) Crosslinking agent The rust preventive coating material in this invention is characterized by including the crosslinking agent of the organic resin component as (b) component as (d) component.
The reason for this is that by including a cross-linking agent, the anti-rust paint can be cured while being more effectively combined to be a rust preventive-containing resin layer, resulting in excellent water resistance and durability. This is because the excellent antirust property can be obtained.
More specifically, by including a crosslinking agent, the organic resin components having a predetermined hydroxyl value as the component (b) can be effectively crosslinked through the respective hydroxyl groups, thereby preventing rust. This is because it is possible to obtain a rust preventive agent-containing resin layer having excellent rust preventive properties by curing the coating composition more effectively.

(5) -1 Type In addition, the type of the crosslinking agent is not particularly limited, and examples thereof include an epoxy compound, an isocyanate compound, a blocked isocyanate, an aziridine compound, and an organometallic compound. It is preferable to select appropriately according to the kind of the organic resin component having a predetermined hydroxyl value as a component.
For example, when the organic resin component having a predetermined hydroxyl value as the component (b) includes a polyester resin, it is preferable to use an organic titanium compound and / or an organic zirconium compound as the crosslinking agent. .
The reason for this is that if it is an organic titanium-based compound and an organic zirconium-based compound, combined with the resin characteristics of the polyester resin, the rust preventive paint is cured while being more uniformly combined to obtain better water resistance and durability. This is because excellent anti-rust properties can be obtained more stably.
That is, the polyester resin tends to have a relatively small hydroxyl value compared to the phenoxy resin.
Therefore, originally, it is preferable to use an isocyanate compound having excellent reactivity with a hydroxyl group as a crosslinking agent.
However, when water is abundantly contained in the anticorrosive paint, an isocyanate compound (including blocked isocyanate) that is highly reactive with water results in competition between water and the hydroxyl group in the polyester resin. In some cases, the crosslinking between the polyester resins may be insufficient.
In this respect, an organic titanium compound and an organic zirconium compound having a relatively low reactivity with water can avoid such a problem and effectively cross-link polyester resins.
Furthermore, if it is an organic titanium type compound and an organic zirconium type compound, it is because the phenol-formaldehyde condensate as a silicone compound or a phenolic hydroxyl group containing compound can also be effectively condensed by the outstanding catalyst function.

Examples of the organic titanium compound include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium diisopropoxybis (acetylacetonate), titanium tetra (Acetylacetonate), titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt, titanium lactate, poly Examples thereof include hydroxy titanium stearate, di-n-butoxy titanium bis (triethanolaminate), polytitanium bis (acetylacetonate) and the like.
Among these, in particular, at least one compound selected from the group consisting of titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt, and titanium lactate is preferable.
The reason for this is that with these compounds, the rust-preventive paint can be cured while being more evenly compounded to obtain even better water resistance and durability, and as a result, excellent rust resistance can be further stabilized. It is because it can be obtained.

Examples of organic zirconium compounds include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate, zirconium butoxybis (ethylacetoacetate). ), Zirconium tetraacetylacetonate, zirconium tributoxy monostearate, zirconium chloride compound aminocarboxylic acid and the like.
Among these, it is particularly preferable to include a zirconium chloride compound aminocarboxylic acid.
The reason for this is that with such a compound, the rust-preventive paint can be cured while being more evenly compounded to obtain further excellent water resistance and durability, and as a result, excellent rust resistance can be further stabilized. This is because it can be obtained.

Moreover, when the organic resin component which has a predetermined hydroxyl value as (b) component contains a phenoxy resin, it is preferable to use block isocyanate as a crosslinking agent.
The reason for this is that blocked isocyanate, combined with the resin characteristics of phenoxy resin, can be cured while more uniformly compounding a rust preventive paint, resulting in better water resistance and durability, and thus excellent This is because the antirust property can be obtained more stably.
That is, if it is a blocked isocyanate, it is easy to react with the secondary hydroxyl group of the phenoxy resin, and when the hydroxyl group concentration is high, the crosslinking density becomes high and the coating film properties after crosslinking can be improved. It is.
The hydroxyl group in the phenoxy resin is secondary, and the hydroxyl group in the polyester resin is primary.

(5) -2 Compounding quantity Moreover, the compounding quantity of a crosslinking agent shall be a value within the range of 0.05-5 weight part with respect to 100 weight part of silicone compounds, It is characterized by the above-mentioned.
The reason for this is that by setting the blending amount of the crosslinking agent to a value within such a range, the rust preventive paint can be cured while being more uniformly combined, and further excellent rust preventive properties can be obtained.
That is, when the blending amount is less than 0.05 parts by weight, it may be difficult to sufficiently exert the crosslinking function and the catalyst function by the crosslinking agent. On the other hand, when the blending amount exceeds 5 parts by weight, it may be difficult to blend uniformly in the rust preventive paint, or the rust preventive agent-containing resin layer may be easily contracted excessively. Because.
Therefore, the blending amount of the crosslinking agent is more preferably set to a value in the range of 0.1 to 2 parts by weight with respect to 100 parts by weight of the silicone compound, and a value in the range of 0.5 to 1 part by weight More preferably.

(6) Lubricant (6) -1 Fluorine resin compound Moreover, it is preferable that the rust preventive coating material in this invention contains the fluorine resin compound as a lubricant further as (e) component.
The reason for this is that if the fluororesin compound is used, the surface characteristics such as slip characteristics or torque characteristics in the rust preventive agent-containing resin layer can be adjusted efficiently.
That is, if it is a fluororesin compound, the coefficient of friction is small, and furthermore, it is excellent in chemical resistance, weather resistance, water resistance, etc. This is because the water resistance can be improved.
The lubricity on the surface of the rust inhibitor-containing resin layer is particularly required when the coated metal molded product is an article that frequently slides with other articles such as bolts and nuts.

  Examples of such fluororesin compounds include fluorinated acrylate resins, vinylidene fluoride resins, fluorinated urethane resins, fluorinated amino resins, polytrifluoroethylene resins, polytetrafluoroethylene resins, polyhexafluoropropylene resins, fluoropolymers. Ethylene propylene copolymer resin, polychlorotrifluoroethylene resin, ethylene-tetrafluoroethylene copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin alone or A combination of two or more types can be mentioned.

(6) -2 Polyethylene compound It is also preferable to use a polyethylene compound as the lubricant.
The reason for this is that if it is a polyethylene compound, the coefficient of friction is small, and it is also excellent in chemical resistance, weather resistance, water resistance, etc. It is because it can improve also about.
Moreover, if it is a polyethylene compound, it has been confirmed that it tends to be unevenly distributed on the surface side (environment side) of the rust preventive agent-containing resin layer, and can effectively contribute to improvement of lubricity on the coating film surface. .

  Examples of the polyethylene compound include a nonionic emulsion based on polyethylene wax, a nonionic emulsion based on modified polyethylene wax, an anionic emulsion based on polyethylene wax, and an anionic system based on modified polyethylene wax. Examples of the emulsion include cationic emulsions based on polyethylene wax and cationic emulsions based on polyethylene wax, cationic emulsions based on modified polyethylene wax, and the like.

(6) -3 Blending amount The blending amount of the lubricant described above is preferably set to a value within the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the silicone compound.
This is because the surface characteristics in the rust preventive agent-containing resin layer can be adjusted more efficiently by setting the blending amount of the lubricant to a value within such a range.
That is, when the blending amount is less than 0.5 parts by weight, it may be difficult to sufficiently obtain the effect of the lubricant such as improvement in lubricity, rust prevention and water resistance. On the other hand, when the blended amount exceeds 30 parts by weight, it becomes difficult to blend uniformly in the rust preventive paint, or the rust preventive agent-containing resin layer is excessively peeled from the zinc-containing porous coating layer. It is because it may become easy to do.
Therefore, the blending amount of the lubricant is more preferably set to a value within the range of 5 to 25 parts by weight, and further preferably set to a value within the range of 10 to 20 parts by weight with respect to 100 parts by weight of the silicone compound. .

(7) Other antirust agent Moreover, it is preferable that the antirust agent coating material of this invention contains a pyrazole type compound and a triazole type compound, or any one as (f) component.
This is because these compounds can react with iron to form an iron salt, form a complex compound, and reduce oxygen permeation, as in the case of the phenolic hydroxyl group-containing compound.
Therefore, the antirust property in the antirust agent-containing resin layer can be easily adjusted.

Examples of the pyrazole compound include pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, and 3-amino-5-methylpyrazole.
Examples of the triazole compound include 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, and 3-mercapto-1,2, 4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (1 Hydrate), 6-methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyridazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine, 2-mercaptobenzo Thiazole, 2-mercaptobenzimidazole, (2-benzothiazolylthio) acetic acid, 3- [2- (benzothiazolyl) thio] propyl Etc. propionic acid.

Moreover, it is preferable to make the compounding quantity of a pyrazole type compound and a triazole type compound or any one into the value within the range of 0.1-15 weight part with respect to 100 weight part of silicone compounds.
This is because, with such a blending amount, the rust prevention property of the rust inhibitor-containing resin layer can be more easily adjusted.
That is, when the blending amount is less than 0.1 parts by weight, it may be difficult to sufficiently obtain the effect of improving the rust prevention property by the pyrazole compound or the like. On the other hand, when the blending amount exceeds 15 parts by weight, it may be difficult to blend uniformly in the rust preventive paint.
Therefore, it is more preferable that the amount of the pyrazole-based compound and the triazole-based compound, or any one of them is set to a value within a range of 0.5 to 12 parts by weight, and a value within a range of 1 to 8 parts by weight. More preferably.

(8) Silane coupling agent (8) -1 type Moreover, it is preferable that an aqueous coating-coating composition contains a silane coupling agent further.
The reason for this is that by blending a predetermined amount of such a silane coupling agent, the anchor effect between the silicone compound that is unevenly distributed in the coating film and the zinc-containing porous coating layer when applied to a metal molded product This is because it is possible to effectively improve the adhesion to the metal molded product.
The types of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycol. Sidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- ( 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like may be used alone or in combination of two or more.

(8) -2 Compounding quantity Moreover, it is preferable to make the compounding quantity of a silane coupling agent into the value within the range of 0.1-30 weight part with respect to 100 weight part of silicone compounds.
This is because when the amount of the silane coupling agent is less than 0.1 parts by weight, it may be difficult to obtain sufficient effects such as improvement in lubricity, rust prevention and water resistance. Because.
On the other hand, when the blending amount of the silane coupling agent exceeds 30 parts by weight, it may be difficult to blend uniformly in the anticorrosive paint.
Therefore, the blending amount of the silane coupling agent is more preferably set to a value in the range of 0.3 to 25 parts by weight with respect to 100 parts by weight of the silicone compound, and a value in the range of 2 to 20 parts by weight More preferably.

(9) Additive In addition, it is preferable to add a diluting solvent such as water, alcohols, water / alcohol mixtures, etc. to the anticorrosive paint in the present invention in order to adjust the viscosity during handling.
It is also preferable to add a diluting solvent such as ketones or glycols as part of the diluting solvent in order to adjust the viscosity during handling.
Furthermore, in order to improve the compatibility between the silicone compound and the organic resin component, it is also preferable to add a surfactant or a compatibilizing agent as a part of the diluent solvent.
Moreover, since the rust preventive coating material in this invention can be suitably prepared as a water dispersion coating material, it is especially preferable to use water and alcohols as a dilution solvent.
In addition, it is preferable to set it as the value within the range of 50-1200 weight part with respect to 100 weight part of silicone compounds as addition amount of a dilution solvent, and it is more preferable to set it as the value within the range of 200-800 weight part. Preferably, the value is in the range of 400 to 700 parts by weight.
In order to adjust viscosity and mechanical properties, inorganic fillers such as glass, quartz, aluminum hydroxide, alumina, kaolin, talc, calcium carbonate, calcium silicate, magnesium hydroxide, acrylic resin powder, epoxy resin powder, Organic fillers such as polyester resin powders; Colorants typified by pigments and dyes such as carbon black, Bengala, phthalocyanine blue, cream yellow, titanium dioxide; metal powders; lubricants; mold release agents; surfactants; Can be added.
Furthermore, in order to improve the film formability of the rust preventive agent-containing resin layer or improve the adhesion, for example, it is preferable to add a thermosetting resin or a metal alkoxide. More specifically, as the thermosetting resin, for example, an epoxy resin, a phenol resin, a maleimide resin, a urea resin, a polyimide resin, a vinyl ester resin, a silicone compound, or an unsaturated polyester resin may be used alone or in combination of two or more. Combinations are mentioned.
More specifically, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and glycidyl amine type epoxy resins can be used as preferred epoxy resins. Examples of the main raw material for the epoxy resin include propylene glycol, tetraphenylethane, hexahydrophthalic anhydride, bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, tetrabromobisphenol A, dimer acid, Diaminodiphenylmethane, isocyanuric acid, p-aminophenol, p-oxybenzoic acid and the like can be used.

Moreover, as a preferable phenol resin, a resol type phenol resin that undergoes a self-dehydration condensation reaction or a novolac type phenol resin that undergoes a weakly acidic or alkaline condensation reaction of phenol and formalin can be used.
More specifically, orthophenol, metaphenol, paraphenol, isopropylphenol, tertiary butylphenol, paraisopropenylphenol, nonylphenol, bisphenol A, and the like are used as the phenol source.
Formaldehyde and acetaldehyde can generally be used as an aldehyde source.

As a preferred maleimide resin, a resin composition in which a compound having two or more polyfunctional maleimide groups in the molecule accounts for about 25% by weight or more is used.
Examples of such maleimide resins include 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 1,12-bismaleimide decane, and 1,6-bismaleimide- (2,2,4-trimethyl). Examples include hexane, 1,3-bismaleimide benzene, and 1,4-bismaleimide benzene.
Further, as a preferred urea resin, typically, the addition condensation reaction of urea and formaldehyde is suitable to use a secondary condensate or a high-order condensate, and there is a particular restriction on the form at the time of use. However, a dried product (so-called dry mix) obtained by dehydrating and drying a resin liquid added with α-cellulose (so-called wet mix) is used as a powder molding material together with a plasticizer, a pigment and the like. It is also possible.

(10) Thickness Moreover, it is preferable to make the thickness of a rust preventive agent containing resin layer into the value within the range of 1-15 micrometers.
This is because, when the thickness of the resin layer containing the rust preventive agent is less than 1 μm, the film forming property may be remarkably deteriorated, or the rust preventive property and corrosion resistance of the metal molded product may be remarkably deteriorated. It is. On the other hand, when the thickness of the rust preventive agent-containing resin layer exceeds 15 μm, it becomes difficult to form a uniform thickness, or the adhesion with the zinc-containing porous coating layer decreases. It is because there is a case to do.
Therefore, the thickness of the rust inhibitor-containing resin layer is more preferably set to a value in the range of 1.2 to 10 μm, and further preferably set to a value in the range of 1.5 to 5 μm.

4). Fluorine resin-containing layer (1) Basic configuration In the present invention, as exemplified in FIG. 1C, basically, the protective layer (uppermost layer) on the rust inhibitor-containing resin layer is omitted. Even if it exists, the outstanding rust prevention property, water resistance, and durability can be acquired.
On the other hand, for the purpose of further adjusting the surface characteristics such as the slip characteristics or torque characteristics of the coated metal molded product and obtaining further excellent rust prevention properties, as shown in FIG. It is also preferable to provide a fluorine-containing resin layer on the resin layer.
The type of fluororesin that constitutes the fluororesin-containing layer 16 is not particularly limited. For example, a fluoroacrylate resin, a vinylidene fluoride resin, a fluorourethane resin, a fluoroamino resin, a polytrifluoroethylene resin, Polytetrafluoroethylene resin, polyhexafluoropropylene resin, fluorinated ethylene propylene copolymer resin, polychlorotrifluoroethylene resin, ethylene-tetrafluoroethylene copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene -A single type of perfluoroalkyl vinyl ether copolymer resin or a combination of two or more types.
The organic resin constituting the fluororesin-containing layer 16 is at least one organic resin of polyester resin, polyacrylic resin, polyolefin resin, polyurethane resin, and polycarbonate resin.
The reason for this is that such an organic resin can uniformly disperse a predetermined amount of fluororesin and has high transparency, facilitating coloring with a colorant and surface modification with a lubricant. is there.
In particular, among these organic resins, when a polyester resin is used, not only the dispersion of the fluororesin is facilitated, but also a part of the carboxyl group is included, so that a partial reaction occurs with the phenol-modified silicone compound layer. And a strong interface can be formed.

Moreover, in the fluororesin containing layer 16, it is preferable to make the addition amount of a fluororesin into the value within the range of 1-200 weight part with respect to 100 weight part of organic resins.
The reason for this is that when the amount of the fluororesin added is less than 1 part by weight, the water repellency and oil repellency due to the fluororesin are significantly reduced, and as a result, the rust prevention and corrosion resistance of the metal molded product are significantly reduced. This is because there is a case of doing.
On the other hand, if the amount of the fluororesin added exceeds 200 parts by weight, it may be difficult to form a film with a uniform thickness or the dimensional accuracy of the metal molded product may be significantly reduced. Furthermore, if the amount of the fluororesin added exceeds 200 parts by weight, the adhesion between the phenol-modified silicone compound layer is lowered, and as a result, the rust prevention and corrosion resistance of the metal molded product may be lowered. It is.
Therefore, it is more preferable to set the addition amount of the fluororesin to a value within the range of 5 to 100 parts by weight and further to a value within the range of 10 to 40 parts by weight with respect to 100 parts by weight of the organic resin. preferable.

Moreover, it is preferable to make the thickness of this fluororesin content layer into the value within the range of 1-30 micrometers.
This is because when the thickness of the fluororesin-containing layer is less than 1 μm, the film formability may be remarkably lowered, or the rust prevention and corrosion resistance of the metal molded product may be remarkably lowered. . On the other hand, if the thickness of the fluororesin-containing layer exceeds 30 μm, it may be difficult to form a uniform thickness or the dimensional accuracy of the metal molded product may be significantly reduced. Furthermore, when the thickness of the fluororesin-containing layer exceeds 30 μm, the adhesion between the antirust-containing resin layer is reduced, and as a result, the rust prevention and corrosion resistance of the metal molded product may be reduced. Because.
Therefore, the thickness of the fluororesin-containing layer is more preferably set to a value within the range of 5 to 20 μm, and further preferably set to a value within the range of 8 to 10 μm.

(2) Additives Also when forming a fluororesin-containing layer, as in the case of a rust-preventing agent-containing resin layer, a diluent solvent, an inorganic filler, an organic filler, a colorant, a metal powder, a lubricant, a release agent It is preferable to add a mold agent, a surfactant, a coupling agent, a thermosetting resin, a metal alkoxide, and the like.
In particular, as a lubricant, for example, graphite, molybdenum disulfide, boron nitride, liquid paraffin, silicone oil, fluorine oil, machine oil, castor oil, oleic acid, and the like, and the amount of the lubricant added is fluorinated resin 100. A value within the range of 1 to 30 parts by weight is preferred per part by weight.
This is because the adhesiveness between the fluororesin-containing layer and the rust-preventing agent-containing resin layer can be further improved by including a predetermined amount of such a lubricant. Moreover, it is because adjustment of the water repellency and mechanical characteristics in a rust preventive agent containing resin layer becomes easy by including a predetermined amount of such a lubricant.
Therefore, it is more preferable that the addition amount of the lubricant is set to a value in the range of 2 to 25 parts by weight per 100 parts by weight of the fluororesin.
Further, as a colorant, for example, titanium oxide, titanium red, cadmium yellow, cobalt oxide, iron oxide, ferrite, metal-free phthalocyanine pigment, aluminum phthalocyanine pigment, titanium phthalocyanine pigment, iron phthalocyanine pigment, cobalt phthalocyanine pigment, nickel phthalocyanine pigment, While containing a tin phthalocyanine pigment, a copper phthalocyanine pigment, etc., it is preferable to make the addition amount of the said coloring agent into the value within the range of 1-30 weight part per 100 weight part of fluororesins.
This is because when the fluororesin-containing layer contains such a lubricant or the like in a predetermined amount, the fluororesin-containing layer can be colored, and thus the coated metal molded product can be colored. Therefore, it can adapt to the multi-use of the coated metal molded product.

[Second Embodiment]
The second embodiment includes the following steps (1) to (4) in sequence as shown in FIG. 3 in its production flow chart (S1 to S5). It is.
(1) Step of preparing a metal molded product (S1-2)
(2) Step of forming a zinc-containing porous coating layer using a thermal spraying device (S3)
(3) The process of apply | coating the antirust coating containing the following composition (a)-(d) with respect to a zinc containing porous layer (S4).
(4) Step of curing the rust preventive paint and forming a rust inhibitor-containing resin layer (S5)
(A) 100 parts by weight of silicone compound (b) Organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) (b) crosslinking agent 0.05 to 5 parts by weight Hereinafter, a coated metal molded product according to the second embodiment The manufacturing method will be specifically described while omitting the same contents as those in the first embodiment.

1. Step of Preparing Metal Molded Product Prior to forming the zinc-containing porous coating layer as shown in S3 in FIG. 3, it is preferable to clean the surface of the metal molded product in advance as shown in S1 and S2. . That is, first, as shown in S1, fats and oils are degreased using an organic solvent such as trichlorethylene and trichloroethane, or an aqueous detergent such as an alkaline detergent, to activate the surface of the metal molded product. preferable.
Next, as shown in S2, it is preferable to clean the surface of the metal molded product in advance by a physical method such as shot blasting and to form fine irregularities. This is because such a surface treatment significantly improves the adhesion between the metal molded product and the zinc-containing porous coating layer.

2. Step of Forming Zinc-Containing Porous Coating Layer Next, as shown in S3 in FIG. 3, a zinc-containing porous layer is formed on the surface of the metal molded product using a thermal spraying apparatus.
That is, for example, a blast material in which a zinc / iron alloy coating layer is formed around an iron-based core is projected onto a metal surface, which is an object to be processed, using a thermal spraying device, and the surface of the object to be processed is porous It is preferable to use a so-called blasted zinc coating method for forming a zinc-iron alloy film.
According to this blast zinc coating method, the zinc / iron alloy 106, which is a blast material, is applied to the surface of the workpiece 118 using the thermal spraying apparatus 100 shown in FIG. 4, and these are sequentially laminated. As a result, a porous zinc-containing porous coating layer 116 is formed.
The zinc-containing porous coating layer 116 is superior in adhesion to an iron-based object to be processed compared to a simple zinc coating, and also has a high surface energy and excellent wettability and permeability. have. Therefore, it is possible to exhibit excellent characteristics as a pretreatment film for subsequent plastic working or painting.
In addition, when forming the zinc-containing porous layer 116 having a predetermined thickness by performing the blast zinc coating method using the thermal spraying apparatus 100, for example, a blast material having a diameter of 100 to 500 μm is subjected to a condition for 30 to 120 minutes. Thus, it is preferable to perform blasting.

3. Next, as shown as S4 in the production flow chart of FIG. 3, the above-described compositions (a) to (d) are further applied to the metal molded article on which the zinc-containing porous coating layer is formed. Apply anti-corrosion paint.
Here, in forming the rust preventive agent-containing resin layer, in S4, for example, an application method such as an immersion method, a spray method, a spray method, or a roller method can be employed.
In particular, the dipping method is preferable because the finished surface of the rust inhibitor-containing resin layer can be easily controlled to a uniform thickness even with a simple apparatus.
Further, in forming the rust inhibitor-containing resin layer, in S4, it is preferable to dip and apply it in a state of being dissolved in water, alcohols, or a mixed solvent thereof because of easy handling.

4). Next, as shown as S5 in the production float chart of FIG. 3, the rust preventive paint applied to the zinc-containing porous coating layer is cured.
For example, it is preferable to prepolymerize after applying a rust preventive paint to the zinc-containing porous coating layer.
Next, for example, by heating at a temperature of 100 to 200 ° C. for 20 to 60 minutes, hydrolysis condensation of the silicone compound in the rust preventive paint and a crosslinking reaction between other components are promoted, and the rust preventive paint. Is preferably cured to form a rust inhibitor-containing resin layer.

5. Step of forming a fluororesin-containing layer Although not an essential step, as shown as S6 to S7 in the manufacturing flowchart of FIG. 3, a metal in which a zinc-containing porous coating layer and a rust inhibitor-containing resin layer are sequentially formed It is also preferable to form a fluororesin-containing layer on the molded product.
For example, in S6, a metal molded article in which a zinc-containing porous coating layer and a rust inhibitor-containing resin layer are sequentially formed is immersed in a bath containing a mixture of a fluororesin and an organic resin. Subsequently, in S7, for example, the fluororesin-containing layer having a predetermined thickness is formed by heating at a temperature of 150 to 200 ° C. for 30 to 60 minutes.
Thereafter, as shown as S8, it is preferable to inspect the obtained coated metal molded product.
In addition, while immersing the metal molded product in S6 or when heat-treating in S7, using a tumbler device or the like to give a predetermined vibration or rotating operation so that a plurality of coated metal molded products are not fixed. It is preferable to implement. In addition, it is also preferable that the perforated bag or the like is repeatedly moved up and down or subjected to ultrasonic vibration in a state where a plurality of coated metal molded products are accommodated in the perforated bag or the like.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Example 1]
1. Preparation of coated metal molded article An iron plate used for actual machine parts was prepared as a metal molded article, and the surface was degreased using trichlorethylene and an alkaline cleaner, and then subjected to blasting, as shown in FIG. As shown in a), fine irregularities 10 ′ were formed on the surface of the metal molded product 10.
Next, using a thermal spraying apparatus 100 as shown in FIG. 4, a blasting material 106 made of an aggregate of iron and a multilayer particle made of zinc including an iron-zinc alloy layer formed around the core. Was projected onto the iron plate surface 118 to form a zinc-containing porous coating layer 12 having a thickness of 3 μm, as shown in FIG.
Next, on the formed zinc-containing porous coating layer, using a bar coater, 100 parts by weight of ethyl silicate (N-100, manufactured by Lucite Japan Co., Ltd.) as a silicone compound, and an organic compound having a predetermined hydroxyl value 56 parts by weight of a polyester resin (Toyobo Co., Ltd., Vironal MD-1200, hydroxyl value: 5.8 mgKOH / g, acid value: 1.7 mgKOH / g) as a resin component, and tannic acid as a phenolic hydroxyl group-containing compound 1.2 parts by weight of vanadium and 0.8 parts by weight of titanium diisopropoxybis (triethanolaminate), which is an organic titanium-based compound as a crosslinking agent (manufactured by Matsumoto Kyosho Co., Ltd., ORGATICS TC-400) 8 parts by weight of polytetrafluoroethylene (made by Kitamura Co., Ltd., KD-500AS) as a fluororesin compound, It is immersed in a rust preventive paint containing 150 parts by weight of sopropanol and 370 parts by weight of water, and then heated in a heating furnace at 130 ° C. for 30 minutes to obtain a thickness as shown in FIG. A 1.93 μm rust inhibitor-containing resin layer was formed to obtain a coated metal molded product.
Note that the silicone compound may be premixed with a phenolic hydroxyl group-containing compound such as gallic acid as long as it is in a very small amount, for example, within a range of 5 to 10% by weight with respect to the total amount of the silicone resin. .
Moreover, each compounding quantity of Table 1 shows the value converted into solid content.

Moreover, the hydroxyl value of the polyester resin mentioned above was measured as follows.
That is, first, 50 g of a polyester resin was dissolved in a mixed solvent of 60 g of toluene and 60 g of ketone, 50 g of diphenylmethane-4,4′-diisocyanate was added, and reacted at 80 ° C. for 2 hours.
Next, an excess di-normal butylamine solution was added to the residual isocyanate group in the reaction solution to cause a reaction, and the remaining di-normal butyl amine was back titrated with hydrochloric acid to obtain a hydroxyl value (mgKOH / g).

Moreover, the acid value of the polyester resin mentioned above was measured as follows.
That is, first, 0.2 g of a polyester resin was dissolved in 20 ml of chloroform.
Subsequently, the obtained solution was titrated with a 0.1 N potassium hydroxide ethanol solution to obtain an acid value (mgKOH / g).

  Moreover, although the polyester resin mentioned above was added with respect to the other component in the state of an aqueous dispersion (water: n-butyl cellosolve = 89:11), the viscosity (25 degreeC) of the aqueous dispersion at this time is It was 1.6 mPa · s, the solid content concentration was 34% by weight, and the pH was 5.5.

2. Evaluation of coated metal molded product (1) Corrosion resistance evaluation by SST test Corrosion resistance of the obtained coated metal molded product (number of samples: 10) by SST test (temperature: 35 ° C, 5% concentration salt spray) based on JISZ2371 The test was performed and the time until red rust was generated was measured. The obtained results are shown in Table 1.

(2) Corrosion resistance evaluation by CCT test In addition, the obtained coated metal molded product (number of samples: 10) was subjected to an SST test (temperature: 35 ° C, 5% concentration salt spray) based on JISZ2371 for 4 hours at 60 ° C. The drying treatment is 2 hours, the wet treatment at 50 ° C. and 95% Rh is 2 hours, the combined treatment for a total of 8 hours is one cycle, and this is repeated up to 60 cycles, and the number of cycles until red rust occurs is measured. did. The obtained results are shown in Table 1.

(3) Durability Evaluation Further, the obtained coated metal molded product was subjected to a cross-cut tape peeling test based on JIS D0202.
Specifically, cellophane tape (manufactured by Nichiban Co., Ltd., CT24) was bonded on 100 square squares engraved on the rust preventive agent-containing resin layer formed on the metal molded article, and then peeled off. The evaluation was made according to the following criteria. The obtained results are shown in Table 1.
A: All 100 cells remained without peeling.
○: 95 to 99 squares remained without peeling.
Δ: 80 to 94 squares remained without peeling.
X: 0-79 squares remained without peeling.

(4) Stability evaluation of rust preventive paint Moreover, the stability of the obtained rust preventive paint was evaluated.
That is, the obtained rust preventive paint was stored in a dark room at 25 ° C. and 50% RH, the occurrence of precipitation was visually confirmed, and evaluated according to the following criteria. The obtained results are shown in Table 1.
A: Precipitation is not confirmed even after 1 month from the start of storage.
○: Precipitation was confirmed after 3 weeks from the start of storage.
Δ: Precipitation was confirmed when two weeks passed from the start of storage.
X: Precipitation was confirmed when one week passed from the start of storage.

(5) Evaluation of uneven distribution Elemental analysis using an electron beam microanalyzer (EPMA) was performed on the obtained coated metal molded product, and the component was unevenly distributed in the film thickness direction of the rust inhibitor-containing resin layer. The degree of uneven distribution was evaluated based on the following criteria.
For reference, the obtained EPMA chart (carbon (C) distribution state) is shown in FIG. Here, the relationship between the color in the EPMA chart and the abundance of carbon is such that the abundance of carbon decreases in the order of white, pink, red, yellow, green, light blue, and blue. Therefore, the abundance of carbon in the white region is relatively the largest, and the abundance of carbon in the blue region is the smallest.
Further, from the EPMA chart shown in FIG. 5, since the carbon existing region is unevenly distributed on the iron plate side of the rust inhibitor-containing resin layer, it is determined from the configuration of each component of the rust inhibitor-containing resin layer. It is understood that the polyester resin having a hydroxyl value of is unevenly distributed on the iron plate side.
Note that the EPMA chart shown in FIG. 5 is a photograph substitute diagram generated based on a photograph taken at a magnification of 2,000 times.
The reason for using such a photo substitute diagram is that when a photo is used as it is as a drawing, the quality of the photo in the gazette or the like may deteriorate and become unclear. The same applies to FIGS. 6 to 9 below.
A: It can be judged that it is clearly unevenly distributed.
○: It can be judged that it is almost clearly unevenly distributed.
Δ: It can be judged that the distribution is clearly uneven.
X: It is difficult to determine whether or not it is unevenly distributed.

[Examples 2 to 4]
In Examples 2-4, the influence of the compounding quantity of the polyester resin which has a predetermined hydroxyl value in a rust preventive agent containing resin layer was examined.
That is, the blending amount of the polyester resin having a predetermined hydroxyl value was 51 parts by weight in Example 2, 20 parts by weight in Example 3, and 150 parts by weight in Example 4 with respect to 100 parts by weight of the silicone compound. Produced and evaluated the coated metal molded articles in the same manner as in Example 1. The obtained results are shown in Table 1.
The EPMA charts (carbon (C) distribution status) in Examples 3 and 4 are shown in FIGS. 6 and 7, respectively.

[Examples 5 to 6]
In Examples 5-6, the kind of polyester resin which has a predetermined hydroxyl value was examined.
That is, the types of polyester resins having a predetermined hydroxyl value are respectively the following polyester resins. In Example 5, the blending amount is 49.5 parts by weight, and in Example 6, the blending amount is 41.25 parts by weight. A coated metal molded article was produced and evaluated in the same manner as in Example 1 except that the amount of vanadium tannate was 0.95 parts by weight. The obtained results are shown in Table 1.
Example 5: Toyobo Co., Ltd., Bironal MD-1500, hydroxyl value: 12 mgKOH / g, acid value: 1.7 mgKOH / g
Viscosity (25 ° C.) in water dispersion (water: n-butyl cellosolve = 90: 10) at the time of addition to other components: 1.6 mPa · s, solid content concentration: 30% by weight, pH: 6)
Example 6: manufactured by Toyobo Co., Ltd., Bironal MD-1480, hydroxyl value: 2.8 mgKOH / g, acid value: 2.8 mgKOH / g
Viscosity (25 ° C.) in aqueous dispersion (100% water) at the time of addition to other components: 0.9 mPa · s, solid content concentration: 25% by weight, pH: 5.5)

[Examples 7 to 8]
In Examples 7 to 8, the influence of the type of the phenolic hydroxyl group-containing compound was examined.
In other words, in Example 7, molybdenum tannate was used as the phenolic hydroxyl group-containing compound, and in Example 8, tungsten tannate was used as the phenolic hydroxyl group-containing compound. The product was manufactured and evaluated. The obtained results are shown in Table 1.

[Example 9]
In Example 9, the effect of using an organic zirconium compound instead of the organic titanium compound was examined.
That is, the coating was performed in the same manner as in Example 1 except that instead of the organic titanium compound, a zirconium chloride compound aminocarboxylic acid (manufactured by Matsumoto Kosho Co., Ltd., ORGATIZ ZB-126) was used as the organic zirconium compound. Metal molded articles were manufactured and evaluated. The obtained results are shown in Table 1.

[Examples 10 to 11]
In Examples 10-11, the influence at the time of using a polyethylene compound instead of a fluororesin compound and using other rust preventive agents together was examined.
That is, instead of polytetrafluoroethylene, a nonionic emulsion based on a modified polyethylene wax (AQUACER 531 manufactured by Big Chemi-Japan Co., Ltd.) (hereinafter sometimes referred to as “PEW”) is used. 10 was 8 parts by weight, and Example 11 was 4 parts by weight.
Further, as another rust inhibitor, 3- [2- (benzothiazolyl) thio] propionic acid (manufactured by Sanshin Chemical Co., Ltd., acid bit PBT) (hereinafter sometimes referred to as “PBT”) was used in Example 10. 8 parts by weight were added for each of No. 11 and No. 11.
Otherwise, a coated metal molded article was produced and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.
Moreover, the EPMA chart (carbon (C) distribution state) in Example 10 is shown in FIG.
From the EPMA chart shown in FIG. 8, the existence region of carbon contained in PEW is unevenly distributed on the surface side (environment side) of the rust inhibitor-containing resin layer, and PEW improves lubricity on the coating film surface. It is understood that the distribution contributes effectively. In addition, in the EPMA chart shown in FIG. 8, the carbon existing region unevenly distributed on the iron plate side of the rust preventive agent-containing resin layer indicates the distribution of carbon atoms contained in the polyester resin having a predetermined hydroxyl value.

[Example 12]
In Example 12, the effect of adding a silane coupling agent was examined.
That is, 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., KBM-403) (hereinafter sometimes referred to as “3-GPTES”) as a silane coupling agent is 100 weights of silicone compound. A coated metal molded article was produced and evaluated in the same manner as in Example 10 except that 2 parts by weight was added to the part. The obtained results are shown in Table 1.

[Example 13]
In Example 13, the effect of changing the conditions examined in the above-described example in combination with a plurality of conditions was examined.
That is, as shown in Table 1, a coated metal molded article was produced and evaluated in the same manner as in Example 1 except that a plurality of conditions were changed. The obtained results are shown in Table 1.

[Example 14]
In Example 14, the effect of using an organic resin component having a predetermined hydroxyl value as a phenoxy resin was examined.
That is, as an organic resin component having a predetermined hydroxyl group, a phenoxy resin (manufactured by InChem Co., Ltd., PKHW-34, hydroxyl value: 250 mgKOH / g, acid value: 47 mgKOH / g) is used, and a water-dispersed block is used as a crosslinking agent. A coated metal molded article was produced and evaluated in the same manner as in Example 1 except that isocyanate (Elastolone BN-11, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. The obtained results are shown in Table 1.
In addition, the viscosity (25 degreeC) in the water dispersion (100% of water) at the time of addition to the other component of the phenoxy resin described above is 1200 mPa · s, the solid content concentration is 34% by weight, and the pH is 7. 3.
In addition, the EPMA chart (carbon (C) distribution state) in Example 14 is shown in FIG.

[Examples 15 to 17]
In Examples 15-17, the influence of the compounding quantity of the phenoxy resin which has a predetermined hydroxyl value in a rust preventive agent containing resin layer was examined.
That is, the blending amount of the phenoxy resin having a predetermined hydroxyl value was 51 parts by weight in Example 15, 20 parts by weight in Example 16, and 150 parts by weight in Example 17 with respect to 100 parts by weight of the silicone compound. Were manufactured and evaluated in the same manner as in Example 14, respectively. The obtained results are shown in Table 1.

[Examples 18 to 19]
In Examples 18 to 19, the type of phenoxy resin having a predetermined hydroxyl value was examined.
That is, a coated metal molded article was produced and evaluated in the same manner as in Example 14 except that the phenoxy resin having a predetermined hydroxyl value was changed to the following phenoxy resin. The obtained results are shown in Table 1.
Example 18: InChem Co., Ltd., PKHW-35, hydroxyl value 260 mgKOH / g, acid value: 57 mgKOH / g
Viscosity (25 ° C.) in aqueous dispersion (100% water) at the time of addition to other components: 2500 Pa · s, solid content concentration: 31 wt%, pH: 7.3
Example 19: InChem Co., PKHW-38, hydroxyl value 240 mgKOH / g, acid value: 50 mgKOH / g
Viscosity (25 ° C.) in aqueous dispersion (100% water) at the time of addition to other components: 5000 Pa · s, solid content concentration: 33 wt%, pH: 7.3

[Example 20]
In Example 20, the influence of using a mixed resin of a polyester resin having a predetermined hydroxyl value and a phenoxy resin having a predetermined hydroxyl value as an organic resin component having a predetermined hydroxyl value was examined.
That is, as an organic resin component having a predetermined hydroxyl value, Vylonal MD-1200, which is a polyester resin used in Example 1, and phenoxy resin PKHW-34 used in Example 14 are 50:50 (weight ratio). A coated metal molded article was produced and evaluated in the same manner as in Example 14 except that the total amount was 56 parts by weight with respect to 100 parts by weight of the silicone compound. The obtained results are shown in Table 1.
The above-mentioned mixed resin had a hydroxyl value of 127.9 mgKOH / g and an acid value of 24.4 mgKOH / g.
Moreover, the viscosity (25 degreeC) in the water dispersion (100% of water) at the time of the addition to the other component of the mixed resin mentioned above is 3100 Pa.s, solid content concentration is 34 weight%, pH is 6. It was 5.

[Comparative Examples 1-2]
In Comparative Examples 1 and 2, the effect of using an organic resin component having no predetermined hydroxyl value was examined.
That is, as the organic resin component not having a predetermined hydroxyl value, except that the following aqueous urethane resin and aqueous urethane acrylic resin were used, respectively, a coated metal molded article was produced in the same manner as in Example 2 and Example 1, respectively. evaluated. The obtained results are shown in Table 1.
Comparative Example 1: DSM NeoResins Co., Ltd., R-9660, hydroxyl value: 0.5 mgKOH / g, acid value: 30 mgKOH / g
Viscosity (25 ° C.) in aqueous dispersion upon addition to other components: 300 mPa · s, solid content concentration: 33% by weight, pH: 8.3)
Comparative Example 2: DSM NeoResins, R-9699, hydroxyl value: 0.8 mgKOH / g, acid value: 15 mgKOH / g
Viscosity (25 ° C.) in aqueous dispersion upon addition to other components: 100 mPa · s, solid content concentration: 40% by weight, pH: 8.3)

[Comparative Examples 3 to 4]
In Comparative Examples 3-4, the influence of the compounding quantity of the polyester resin which has a predetermined hydroxyl value in a rust preventive agent containing resin layer was examined.
That is, the blending amount of the polyester resin having a predetermined hydroxyl value was 10 parts by weight in Comparative Example 3 and 250 parts by weight in Comparative Example 4 with respect to 100 parts by weight of the silicone compound, respectively. A coated metal molded product was manufactured and evaluated. The obtained results are shown in Table 1.

[Comparative Example 5]
In Comparative Example 5, the effect of not using a crosslinking agent was examined.
That is, a coated metal molded article was produced and evaluated in the same manner as in Example 1 except that no crosslinking agent was used. The obtained results are shown in Table 1.

As described above in detail, according to the present invention, an anticorrosive paint comprising a silicone compound, an organic resin component having a predetermined hydroxyl value, a phenolic hydroxyl group-containing compound and a crosslinking agent on the zinc-containing porous coating layer. By laminating a resin layer containing a rust inhibitor that is cured while unevenly distributing components in the coating film, it has excellent water resistance and durability, and thus can exhibit excellent rust resistance stably. Coated metal moldings can be obtained.
As a result, even when the protective layer (uppermost layer) is omitted, it is possible to stably exhibit excellent rust prevention properties and to obtain a coated metal molded product having excellent stability.
Therefore, the coated metal molded article of the present invention can be widely used in fields requiring rust prevention such as building materials, construction machines, ships, bridges, automobiles and the like.

10: Metal molded product, 12: Zinc-containing porous coating layer, 14: Rust-containing resin layer, 16: Fluorine resin-containing layer, 20: Coated metal molded product, 100: Thermal spray device, 106: Blasting material, 118 : Iron plate

Claims (14)

A zinc-containing porous coating layer and a rust-preventing agent-containing resin layer as the uppermost layer obtained by curing a rust-preventing paint containing the following compositions (a) to (d) are sequentially formed on the surface of the metal molded product. In the formed coated metal molded product, the component (b) is unevenly distributed on the zinc-containing porous coating layer side of the rust-preventing agent-containing resin layer, while the zinc-containing porosity of the rust-preventing agent-containing resin layer is A coated metal molded article, wherein the component (a) is unevenly distributed on the opposite side of the porous coating layer.
(A) Silicone compound 100 parts by weight (b) Organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) (b) crosslinking agent 0.05 to 5 parts by weight   2. The organic resin component having a hydroxyl value in the range of 1 to 500 mg KOH / g as the component (b) is a polyester resin or a phenoxy resin, or any one thereof. Coated metal molded product.   The coated metal molded article according to claim 2, wherein the hydroxyl value of the polyester resin is set to a value in the range of 4 to 20 mgKOH / g.   The coated metal molded article according to claim 2, wherein the hydroxyl value of the phenoxy resin is set to a value in the range of 200 to 300 mgKOH / g.   5. The organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as the component (b) is an organic resin component having water dispersibility. The coated metal molded article according to one item.   The weight average molecular weight of the organic resin component having a hydroxyl value as the component (b) in the range of 1 to 500 mgKOH / g is set to a value in the range of 2,000 to 50,000. The coated metal molded article according to any one of Items 1 to 5.   The coated metal according to any one of claims 1 to 6, wherein the silicone compound as the component (a) is at least one selected from the group consisting of ethyl silicate, methyl silicate, and ammonium silicate. Molding.   The phenolic hydroxyl group-containing compound as the component (c) is selected from the group consisting of vanadium tannate, molybdenum tannate, 3,4,5-trihydroxybenzenecarboxylic acid and 3,4,5-trihydroxybenzenecarboxylic acid ester. The coated metal molded article according to any one of claims 1 to 7, which is at least one selected.   When the organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as the component (b) includes a polyester resin, the crosslinking agent as the component (d) is an organic titanium compound and an organic compound. In the case where the zirconium-based compound or any one of them and the organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g as the component (b) contains a phenoxy resin, the component (d) The coated metal molded article according to any one of claims 2 to 8, wherein the crosslinking agent as a component is a blocked isocyanate.   The organic titanium compound is at least one compound selected from the group consisting of titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt, and titanium lactate, and the organic zirconium compound is chlorinated. The coated metal molded article according to claim 9, comprising a zirconium compound aminocarboxylic acid.   The rust preventive paint further contains a fluororesin compound as the component (e), and the addition amount thereof is in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the silicone compound as the component (a). The coated metal molded product according to any one of claims 1 to 10, wherein the coated metal molded product is a value within the range.   The rust preventive paint further contains, as a component (f), a pyrazole compound and a triazole compound, or any one of them, and an addition amount thereof with respect to 100 parts by weight of the silicone compound as the component (a), It is set as the value within the range of 0.1-15 weight part, The coated metal molded product as described in any one of Claims 1-11 characterized by the above-mentioned.   The thickness of the zinc-containing porous coating layer is set to a value within a range of 3 to 10 µm, and the thickness of the rust inhibitor-containing resin layer is set to a value within a range of 1 to 15 µm. The coated metal molded article according to any one of Items 1 to 12. The manufacturing method of the covering metal molded product characterized by including the process of following (1)-(4) sequentially.
(1) Step of preparing a metal molded product (2) Step of forming a zinc-containing porous coating layer using a thermal spraying device (3) For the zinc-containing porous coating layer, the following compositions (a) to (d) (4) A rust preventive-containing resin layer as an uppermost layer formed by curing the rust preventive paint, wherein the zinc-containing porous coating layer of the rust preventive-containing resin layer While the component (b) is unevenly distributed on the side, the antirust agent-containing resin layer formed by unevenly distributing the component (a) on the opposite side of the zinc-containing porous coating layer of the antirust agent-containing resin layer is formed. Step (a) 100 parts by weight of silicone compound (b) Organic resin component having a hydroxyl value in the range of 1 to 500 mgKOH / g
15 to 200 parts by weight (c) phenolic hydroxyl group-containing compound 0.1 to 30 parts by weight (d) (b) crosslinking agent 0.05 to 5 parts by weight

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