JP2013023544A - Rust preventive coating, method for forming coating film, and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rust preventive coating having good rust preventiveness, a method for forming a coating film in which an article to be coated is coated with the rust preventive coating to form the coating film, and a coated article having good corrosion resistance obtained by coating the article with the rust preventive coating.SOLUTION: The rust preventive coating contains: a powdery zinc alloy containing zinc and a metal other than zinc; boron nitride; and water. The mass ratio of the boron nitride to the zinc alloy is preferably 0.001-0.46. The rust preventive coating preferably contains ion-exchanged silica obtained by bonding at least one of calcium ion and magnesium ion to silica by ion exchange.

Description

  The present invention relates to a rust preventive paint containing a zinc alloy, a method of forming a paint film by coating the rust preventive paint on an object to be coated, and a coating formed by applying the rust preventive paint to an object to be coated. It relates to goods.

Since metal materials such as steel materials are oxidized and corroded by oxygen and moisture in the atmosphere, it is necessary to coat and protect the surfaces by applying various types of plating or coating materials.
Examples of the paint include rust preventive paints containing zinc and aluminum as metal pigments. Since zinc and aluminum have a higher ionization tendency than iron, they elute prior to iron, and an effect of suppressing corrosion of iron (sacrificial anticorrosive action) is obtained.

Patent Document 1 discloses that after coating an object to be coated with an alkyl silicate-based high-concentration zinc powder coating containing zinc dust, an alkyl silicate, and a solvent such as ethylene glycol monoethyl ether having a boiling point of 156 ° C., the coating film is made into a base. An invention of a coating film curing method for treating with an aqueous substance-containing aqueous liquid is disclosed. According to the present invention, the hydrolysis and dehydration condensation reaction of the alkyl silicate is promoted by the basic substance-containing aqueous liquid, and the curing of the coating film is promoted.
In Patent Document 2, an alkyl silicate, an alcohol containing isobutyl alcohol having a boiling point of 108 ° C., water, and a solution containing hydrochloric acid are reacted to prepare an alkyl silicate hydrolysis initial condensate, and then zinc dust is added to the anticorrosion paint. And an anticorrosion coating method for applying the anticorrosion paint on the surface of a steel material as a primer is disclosed.
Patent Document 3 discloses an invention of a rust-preventing primer which contains a partially hydrolyzed and condensed alkyl silicate, zinc powder, and a thickener.
Patent Document 4 discloses an invention of a water-diluted coating composition containing a high-boiling organic liquid having a boiling point exceeding about 100 ° C. at atmospheric pressure, a particulate metal, a thickener, and a silane binder. That is, it is disclosed that water that hydrolyzes a silane binder is blended with an alkylsilicate-based zinc powder paint.

Patent Document 5 discloses an invention of a coating material made of zinc or a zinc-based alloy such as Zn-10% Al-0.1% Mg containing zinc as a main component and containing a flake-like metal powder and a liquid medium. Has been. According to the present invention, the metal powder is flaked to increase the specific surface area, so that the contact between the metal powders becomes close, and in addition to the active anticorrosive property of the metal itself, the protective barrier based on the flake shape An effect (passive anticorrosion) is also obtained, the content of the metal powder can be reduced, and the occurrence of cracks in the coating film can be suppressed.
Patent Document 6 discloses an invention of a metal powder made of an alloy of zinc and aluminum and used for mechanical plating. Rust prevention is improved by alloying aluminum with zinc, but the adhesion of the coating film is worse than with zinc alone. According to this invention, by setting the zinc content in the alloy to about 50% by mass or more, it is possible to have both good rust prevention and adhesion of the coating film.
In Patent Document 7, as in the inventions of Patent Documents 5 and 6, a metal powder made of an alloy of zinc and a non-zinc metal containing 50% by mass or more of zinc and having a flake shape as in the invention of Patent Document 5 The invention of the coating material which has favorable rust prevention property is disclosed by using this with a liquid medium.

Patent Document 8 contains at least one particulate metal and at least one binder in a liquid medium composed of water, a glycol compound and / or an organic solvent, and the particulate metal with respect to the sum of the particulate metal and the binder. The total amount of zinc and aluminum is 70 mass% or more, and the granular metal is an aluminum having a content of less than 4 mass% with respect to the granular metal, and a zinc having a content of 50 mass% or more. An invention of a corrosion-resistant coating composition for a screw configured to contain a zinc alloy whose content is 100% by mass or less with respect to the granular metal is disclosed.
Patent Document 9 includes approximately 20 to 70% by mass of water, a low-boiling organic liquid, a granular metal, an alkoxy group, and approximately 3 to 20% by mass of a silane binder and a wetting agent that are water-soluble. In addition to corrosion resistance, an invention of a coating composition having a desired coating tackiness on an object to be coated is disclosed.

JP-A-55-108473 JP-A-6-31245 JP-A-7-228801 Japanese Patent No. 3904669 Japanese Patent Laid-Open No. 61-123684 JP-A-55-119101 Japanese Patent No. 4198919 JP 2006-52361 A JP 2002-121485 A

In the inventions of Patent Documents 5 to 8, good rust prevention is obtained by using a zinc-aluminum alloy instead of the zinc powder of Patent Documents 1 to 4 as the metal powder of the pigment, and the invention of Patent Document 9 In No. 1, good coating adhesiveness is obtained by containing approximately 3 to 20% by mass of a silane binder in the coating composition, but further improvement in rust prevention is required. For example, it is required that red rust does not occur in a coated article in which a coating film is formed on a base material made of steel after 1000 hours have passed in a salt spray test.
In addition, it is necessary to form a coating film even on the surface of products that are used in combination with parts of different metals and have complicated shapes, such as bolts, nuts, washers, etc. The alloy must be uniformly dispersed.

  The present invention has been made in view of such circumstances, a rust-preventing paint having a good rust-preventing property, a method of forming a coating film by coating the rust-preventing paint on an article to be coated, and An object of the present invention is to provide a coated article having a good corrosion resistance, which is obtained by painting a rust preventive paint on an object to be coated.

As a result of diligent research, the present inventors have prepared a rust preventive paint by blending boron nitride in addition to zinc and alloys containing metals other than zinc. It has been found that the corrosion resistance is remarkably improved when a coating film is formed, and the present invention has been completed.
That is, the rust preventive paint according to the first invention contains zinc and a powdered alloy containing a metal other than zinc, boron nitride, and water.

  The anticorrosion paint according to the second invention is characterized in that, in the first invention, the mass ratio of the boron nitride to the alloy is 0.001 or more and 0.46 or less.

  The anticorrosive paint according to the third invention is characterized in that, in the first or second invention, it contains ion exchange silica obtained by binding at least one of calcium ions and magnesium ions to the silica by ion exchange. To do.

  The anticorrosive paint according to the fourth invention is characterized in that, in the third invention, the mass ratio of the ion exchange silica to the alloy is 0.015 or more and 0.35 or less.

  The rust preventive paint according to the fifth invention is any one of the first to fourth inventions, wherein at least one selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group in the molecule. It contains a silane coupling agent having individual functional groups and hydrolyzable silicon groups.

  In the first or second invention, the anticorrosive paint according to the sixth invention is at least one functional group selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group in the molecule. And a silane coupling agent having a hydrolyzable silicon group, and the mass ratio of the boron nitride to the total mass of the alloy, the boron nitride, and the silane coupling agent is 0.01 or more and 0.00. 23 or less.

  In the third or fourth invention, the rust-preventing paint according to the seventh invention is at least one functional group selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group in the molecule. And a silane coupling agent having a hydrolyzable silicon group, and the mass ratio of the boron nitride to the total mass of the alloy, the boron nitride, the silane coupling agent, and the ion-exchange silica is 0. .01 or more and 0.23 or less.

  The rust preventive paint according to the eighth invention is any one of the first to seventh inventions, wherein the polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene sorbitan fatty acid ester, and It is at least one selected from the group consisting of sorbitan fatty acid esters, and contains a surfactant having an HLB of 6 or more and 17 or less.

  In the rust preventive paint according to the ninth invention, in any one of the first to eighth inventions, the alloy contains 50% by mass or more of zinc.

  The anticorrosive paint according to the tenth invention is characterized in that, in any one of the first to ninth inventions, the metal other than zinc is aluminum.

  The rust preventive paint according to the eleventh aspect of the present invention is characterized in that, in any one of the first to tenth aspects, the alloy has a flake shape.

  A coating film forming method according to a twelfth aspect of the present invention is characterized in that a coating film is formed by applying a rust preventive paint according to any one of the first to eleventh aspects of invention onto an article to be coated.

  A coated article according to a thirteenth invention is characterized in that a rust preventive paint according to any one of the first to eleventh inventions is coated on an object to be coated.

  Since the rust preventive paint of the present invention contains boron nitride in addition to the zinc alloy, the rust preventive property is improved. This is considered to be because the thickness and strength of the coating film are maintained by containing boron nitride having a hexagonal bond structure that hardly reacts with the iron-based material.

Since the rust preventive paint of the present invention contains ion-exchanged silica obtained by binding at least one of calcium ions and magnesium ions to the silica by ion exchange, the rust-preventing property is improved. This is because during coating film formation, an oxide film such as CaSiO ₃ (or MgSiO ₃ ) is formed on the surface of the object to be coated and the surface of the zinc alloy to be protected from water, and calcium (or magnesium) elutes first. This is considered to be because the elution of zinc is suppressed, and the sacrificial anticorrosive action of the zinc alloy lasts longer.

  Since the rust preventive paint of the present invention contains the above-mentioned silane coupling agent, silanol groups are generated by hydrolysis, and the silanol groups are bonded to the zinc alloy, so that the zinc alloy is stabilized in the rust preventive paint. At the time of forming the coating film, the silanol group is also bonded to the object to be coated, and crosslinking or the like is caused by the functional group, so that the adhesion of the coating film is also improved.

  Since the rust preventive paint of the present invention contains the above-mentioned surfactant, the zinc alloy is well dispersed in water, and a coating film can be uniformly formed on the object to be coated.

  In the coating film forming method of the present invention, a coating film is formed by applying the rust preventive paint of the present invention to an object to be coated, so that the obtained coated article has good corrosion resistance.

  Since the coated article of the present invention is formed by coating the article to be coated with the rust preventive paint of the present invention, it has good corrosion resistance.

  According to the present invention, since the rust preventive paint contains boron nitride in addition to the zinc alloy, the rust preventive property is improved, and the coated article formed by coating the rust preventive paint has good corrosion resistance.

  The anticorrosive paint according to the present invention contains zinc and a powdered alloy containing a metal other than zinc (hereinafter referred to as a zinc alloy), boron nitride, and water.

The zinc alloy powder is preferably flaky. By making it into flakes, the specific surface area increases, the contact between the powders becomes close, and in addition to the active corrosion resistance of the metal itself, a protective barrier effect (passive corrosion resistance) based on the flake shape is also obtained. The content of the zinc alloy powder can be reduced, and the occurrence of cracks in the coating film can be suppressed.
Examples of metals other than zinc include aluminum, magnesium, tin, cobalt, and manganese. Among these, it is preferable that aluminum is contained in the alloy from the viewpoint of obtaining a good sacrificial anticorrosive action and being relatively inexpensive. One or two or more metals other than zinc can be used. For example, a zinc-aluminum-magnesium alloy or the like can be used as an alloy of three metals.

  Zinc is preferably contained in the zinc alloy in an amount of 50% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more from the viewpoint of rust prevention, adhesion to an object to be coated, and cost.

It is preferable to use a zinc alloy in the form of a paste. Examples of the paste liquid include dipropylene glycol and mineral spirit.
The zinc alloy is preferably contained in the zinc alloy paste at approximately 90 to 95% by mass.
And when a zinc alloy is a zinc-aluminum alloy, it is preferable that a zinc alloy paste contains about 85-90 mass% zinc and about 3-8 mass% aluminum, and the remainder is a paste liquid.
As a specific example of the zinc alloy paste, “STAPA 4 ZnAl7” (Zn: 85% by mass, Al: 7% by mass, mineral spirit: 8% by mass), which is a Zn—Al alloy paste manufactured by Eckart, STAPA 4 ZnAl3 ”(Zn: 89 mass%, Al: 2.5 mass%, mineral spirit: 8.5 mass%) and the like. Regarding particle size, it is preferred that at least about 50% by weight of the particles have the longest dimension of less than about 15 microns.

  The anticorrosive paint of the present invention may contain a powdery single metal (flakes or non-flakes) in addition to the zinc alloy. For example, an aluminum paste containing flaky aluminum can be contained.

Boron nitride has a hexagonal crystal structure.
Addition of boron nitride to the rust preventive paint improves rust prevention. Although the detailed reason is not clear, it is thought that it is difficult to react with the iron-based material, and the thickness and strength of the coating film are maintained by containing boron nitride having the above-described bonding structure inside the coating film.
The mass ratio of boron nitride to zinc alloy (the active ingredient in the zinc alloy paste) exhibits good rust prevention properties, and increases the cost and adhesion due to the addition of low specific gravity boron nitride. From the viewpoint that the property does not deteriorate, it is preferably 0.001 or more and 0.46 or less. The lower limit is more preferably 0.02, and the upper limit is more preferably 0.14.

The rust-preventing paint of the present invention preferably contains ion-exchanged silica obtained by binding at least one of calcium and magnesium to silica through ion-exchange.
The ion exchange silica is obtained by ion exchange of at least one of calcium and magnesium on a fine porous silica support. As a manufacturing method of this ion exchange silica, for example, the manufacturing method of Japanese Patent No. 2077753 can be cited.
Examples of Ca ion-exchanged silica obtained by ion-exchange of calcium with a silica carrier include “Silo Mask 52”, “Silo Mask 55”, “SHIELDEX”, “SHIELDEX SY710” manufactured by Fuji Silysia Chemical Co., Ltd. R. Examples include “SHIELDEX C303”, “SHIELDEX AC3”, “SHIELDEX AC5” manufactured by Grace, and “HEUCOSIL CTF” manufactured by Heibach (all are trade names).

By blending this ion exchange silica with a rust preventive paint, when the rust preventive paint is applied to a coated object made of an iron-based material to form a coated film, the corrosion resistance of the coated object is improved. Although the detailed reason for improving the corrosion resistance is not clear, it is considered as follows. An oxide film such as CaSiO ₃ (or MgSiO ₃ ) is formed on the surface of the zinc alloy, that is, a protective film strong against water is formed, and calcium (or magnesium) has a higher ionization tendency than zinc, aluminum, and iron, Since calcium (or magnesium) elutes first, the elution of aluminum and zinc in the zinc alloy is suppressed, the storage stability of the anticorrosive paint is improved, and a coating film is formed on the object to be coated with the anticorrosive paint. When this is done, the sacrificial anticorrosive action of the zinc alloy lasts for a longer period of time, and the rust resistance of the coating film is considered to improve. That is, when the metal powder is made of an alloy of zinc and aluminum, the alloy powder to which ion-exchange silica is attached will elute in three stages in the order of calcium (or magnesium), aluminum, and zinc. It contains a mixture of powder and aluminum powder and ion-exchange silica, and in the zinc powder or aluminum powder, the elution of the metal in the coating over time is less than when it is eluted in two steps in the order of calcium (or magnesium), zinc or aluminum. It is considered that the amount is made uniform, the thickness of the coating film is kept uniform, and the sacrificial anticorrosive action of zinc lasts longer.

  The mass ratio of the Ca ion exchange silica to the zinc alloy is preferably 0.015 or more and 0.35 or less, and preferably 0.015 or more and 0 or less, from the viewpoint of obtaining rust prevention properties and good storage stability. More preferably, it is .25 or less.

  The rust preventive paint of the present invention is at least one selected from the group consisting of polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene sorbitan fatty acid ester, and sorbitan fatty acid ester. And preferably contains a surfactant having an HLB of 6 or more and 17 or less.

  Polyoxyethylene alkylamine is represented by the general formula of the following formula (1).

However, a = 1, 2, ...
b = 1, 2,
R = C _n H _{2n + 1}
n = 1, 2,

The polyoxyethylene alkyl ether is represented by the general formula of the following formula (2).
_{RO- (CH 2 CH 2 O)} n -H ··· (2)
n = 1, 2,
R = C _m H _{2m + 1}
m = 1, 2,

  Polyoxyethylene distyrenated phenyl ether is represented by the following general formula (3).

  However, n = 1, 2, ...

  The polyoxyethylene sorbitan fatty acid ester is represented by the following general formula (4).

However, a = 1, 2, ...
b = 1, 2,
c = 1, 2,
R = C _n H _{2n + 1}
n = 1, 2,

  Sorbitan fatty acid ester is represented by the following general formula (5).

However, R = C _n H _{2n + 1}
n = 1, 2,

By containing the surfactant, the dispersibility of the zinc alloy in water is improved.
From the viewpoint that this effect is effectively exhibited, the mass ratio of the surfactant to the zinc alloy is preferably 0.01 or more and 0.3 or less, and more preferably 0.01 or more and 0.2 or less. . Although the HLB is considered when determining the type and combination of surfactants, the preferred HLB range varies depending on the type and combination of surfactants, as will be described later, so it corresponds to the type and combination of surfactants. A surfactant with HLB is selected.

The anticorrosive paint of the present invention has at least one functional group selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group in the molecule and a hydrolyzable silicon group. It preferably contains a silane coupling agent.
The hydrolyzable silicon group is not particularly limited, but an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

As a silane coupling agent, when an epoxy group is included as a functional group, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy Examples include silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.
When a methacryloxy group is included as a functional group, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. may be mentioned. .
When an acryloxy group is included as a functional group, for example, 3-acryloxypropyltrimethoxysilane and the like can be mentioned.

When an amino group is included as a functional group, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl -3-aminopropyltrimethoxysilane and the like.
When a mercapto group is included as a functional group, for example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.
When a vinyl group is included as a functional group, for example, vinyltrimethoxysilane, vinyltriethoxysilane and the like can be mentioned.

  From the viewpoint of improving the coating properties and stabilizing the coating composition, the silane coupling agent preferably has an alkyl group containing an epoxy group as a functional group, particularly an alkyl group containing a glycidoxy group.

The silanol group is generated by the hydrolysis of the silane coupling agent, and the silanol group is bonded to the zinc alloy. Therefore, it is considered that the zinc alloy is stabilized in the rust preventive coating. The silanol group is also bonded to the object to be coated, and the coating component is crosslinked or chemically bonded by the functional group, so that the adhesion of the coating film is improved.
From the viewpoint of good adhesion of the coating film and storage stability of the paint, the mass ratio of the silane coupling agent to the zinc alloy is preferably 0.01 or more and 0.9 or less, more preferably 0.25 or more and 0. .8 or less, more preferably 0.25 or more and 0.65 or less.

The anticorrosive paint of the present invention may further contain a silane compound having a hydrolyzable silicon group in the molecule and not containing the functional group of the silane coupling agent.
The hydrolyzable silicon group is not particularly limited, but an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.
And it has the haloalkyl group etc. which substituted the alkyl group which does not contain the functional group of a silane coupling agent, a phenyl group, or a part or all of the hydrogen atom with the halogen atom.
Examples of the silane compound include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane. And trifluoropropyltrimethoxysilane.
This silane compound is likely to be hydrolyzed to form silanol groups, and the silanol groups are bonded to the zinc alloy, so that the zinc alloy is considered to be stabilized in the anticorrosive paint. Since the silanol group is also bonded to the object to be coated at the time of forming the coating film, the adhesion of the coating film is also improved.
From the viewpoint of expression of this effect and the storage stability of the paint, the mass ratio of the silane compound to the zinc alloy is preferably 0.01 or more and 0.9 or less, more preferably 0.05 or more and 0.6 or less.

  In the anticorrosive paint of the present invention, the mass of boron nitride relative to the total mass of the components [boron nitride, silane coupling agent, zinc alloy, ion-exchange silica (when included in the anticorrosive paint)] that is the main component of the coating film The ratio is preferably 0.01 or more and 0.23 or less from the viewpoint that the thickness and strength of the coating film are maintained well. More preferably, it is 0.02 or more and 0.09 or less.

  The rust preventive paint of the present invention can contain an appropriate amount of water depending on the coating method, the film thickness of the coating film, the baking conditions, and the like. % Or less is preferable. In addition to the organic liquid contained as a paste liquid in the zinc alloy paste, an organic liquid can be contained in the anticorrosive paint. For example, an acid such as acetic acid can be used as the organic liquid.

The anticorrosive paint of the present invention can be obtained by mixing and stirring each component according to a normal production method. At that time, in addition to the above-described components, paint additives such as a wetting and dispersing agent, a wetting agent, an antifoaming agent, a thickening agent, and a pH adjusting agent may be blended. For example, wetting agents such as polycarboxylic acid-based wet dispersing agents, organic phosphate esters, diester sulfosuccinates such as sodium bistridecyl sulfosuccinate, silicone-based or acrylic-based additives, which are general paint additives An antifoaming agent etc. can be mix | blended.
Examples of thickeners include hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl cellulose ethers, and mixtures of these substances. Other thickeners include xanthan gum, urethane-based associative thickeners, and nonionic associative thickeners that do not contain urethane.
Examples of pH adjusters include alkali metals such as lithium and sodium (Group IA), alkaline earth metals such as strontium, calcium, barium and magnesium (Group IIA), and oxides of metals such as Group IIB such as zinc and cadmium. From the viewpoint that the coating bondability can be enhanced, oxides and hydroxides of alkali metals such as lithium and sodium are preferable. Moreover, the above-mentioned metal carbonate or nitrate may be sufficient.

  The anticorrosive paint of the present invention may contain a boron compound such as orthoboric acid, metaboric acid, tetraboric acid, boron oxide, and zinc borate. Further, phosphate, calcium nitrate, dibasic ammonium phosphate, aluminum tripolyphosphate, calcium sulfonate, 1-nitropropane, lithium carbonate (also used as a pH adjusting agent) and the like may be contained.

  Since the rust preventive paint according to the present invention contains the above-mentioned silane coupling agent and silane compound, when coated with the rust preventive paint, the adhesion between the zinc alloy and the object to be coated is good, and chromic anhydride It is not necessary to contain a water-soluble chromium compound such as sodium chromate, potassium chromate, sodium dichromate or potassium dichromate. Therefore, there is no environmental problem.

Below, the method of forming a coating film in a to-be-coated article using the rust preventive paint of this invention is explained in full detail.
The article to be coated with the anticorrosive paint of the present invention is not particularly limited, and may be a ceramic article or the like, but is suitable for an article made of an iron-based material such as steel. Can be painted. The object to be coated with the iron-based material may be in the form of an alloy or an intermetallic mixture.
Examples of the iron-based material to be coated include all products using iron-based materials, such as chains, gears, speed reducers, and linear cylinder bodies or cases. As a chain, a pair of outer plates connected by two pins and a pair of inner plates connected by two bushes are alternately connected with the pins loosely fitted to the bushes. Is mentioned. The anticorrosive paint of the present invention can also be suitably applied to automobile bolts, nuts, washers, pins, screws, and the like that may be exposed to water.

It is preferable to remove foreign substances from the substrate surface by washing and / or degreasing the object to be coated. Degreasing can be performed, for example, with hexane or the like. Moreover, you may use the well-known chemical | medical agent containing a metasilicate, caustic soda, carbon tetrachloride, trichloroethylene, etc.
And as a process of the surface of a to-be-coated object, you may decide to perform the shot blast process which spouts a shot (small steel ball) toward this surface with high-pressure air, and touches this surface and finishes the surface. Furthermore, the base film may be formed on the surface of the object by plating with zinc or a zinc alloy.

  The anticorrosive paint of the present invention can be applied to an object by immersion treatment such as immersion drain (dip drain) and immersion rotation (dip spin), brush coating, spraying, or the like.

  After applying the rust preventive paint of the present invention to the article to be coated, it is preferable to heat cure the rust preventive paint. It is preferable to evaporate the volatile component of the anticorrosive paint in advance by drying before curing. The drying temperature is preferably about 100 ° C to 180 ° C. The drying time is preferably about 2 to 25 minutes.

  Heat curing of the anticorrosive paint can be performed by high temperature air oven curing, but infrared baking and induction curing can also be employed. The heat curing can be performed in a range of approximately 280 ° C to 370 ° C. The curing time is preferably about 10 minutes to 45 minutes.

From the viewpoint of the development of good corrosion resistance and cost, the coating amount of the object to be coated is preferably 5 g / m ^{2 to} 100 g / m ² , more preferably 10 g / m ^{2 to} 50 g / m ² , and even more preferably 12 g / m. ^{2 to} 40 g / m ² .

The anticorrosive paint of the present invention may be applied to an object to be coated a plurality of times.
Further, it may be overcoated using another top coating material. Examples of the top coat include those containing a silane compound such as silicate and silicate ester, colloidal silica and the like.

  In the rust preventive paint of the present invention configured as described above, the zinc alloy is well dispersed in water, the rust preventive paint has a good rust preventive property, and the rust preventive paint is applied to an object to be coated. The resulting coated article has good corrosion resistance.

  Hereinafter, although an example and a comparative example of the present invention are explained concretely, the present invention is not limited to this example.

1. Examination of surfactants We investigated surfactants added to disperse zinc alloys well in anti-corrosion paints.
The surfactants studied are as follows.
Polyoxyethylene alkylamine of the above formula (1) Trade name “Zontes AL” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
Product name "Amate 105" (manufactured by Kao Corporation)
Product name "AMIET 102" (manufactured by Kao Corporation)

Polyoxyethylene alkyl ether of the formula (2) Trade name “Marpon ACF-12” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
Product name “Marpon ACF-9” (Matsumoto Yushi Seiyaku Co., Ltd.)
Product name "Marpon B-9W" (Matsumoto Yushi Seiyaku Co., Ltd.)
Product name "Marpon ACF-7" (Matsumoto Yushi Seiyaku Co., Ltd.)
Product name "Marpon B-5" (Matsumoto Yushi Seiyaku Co., Ltd.)
Product name “Emulgen 106” (manufactured by Kao Corporation)
Product name “Emulgen 102KG” (manufactured by Kao Corporation)

Polyoxyethylene distyrenated phenyl ether of the formula (3) Trade name “Emulgen A-60” (manufactured by Kao Corporation)
Product name "Emulgen A-90" (manufactured by Kao Corporation)

Polyoxyethylene sorbitan fatty acid ester of the formula (4) Trade name “Leodol TW-S106V” (manufactured by Kao Corporation)
Product name "Leodoll TW-L120" (manufactured by Kao Corporation)

Sorbitan fatty acid ester of the formula (5) Trade name “Leodol SP-L10” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)

  The HLB of each surfactant is shown in Tables 1 to 3 below.

[Formulation Example 1]
According to the composition (shown in parts by mass) in Table 1, water, a surfactant (said “Zontes AL”), and a Zn—Al alloy paste (said “STAPA 4 ZnAl7”, manufactured by Ecart) were stirred at room temperature for 1 hour. By mixing, the composition of Formulation Example 1 was obtained.
[Composition Examples 2 to 10]
In accordance with the composition shown in Table 1, the compositions of Composition Examples 2 to 10 were obtained in the same manner as Formulation Example 1. [Composition Example 11]
A composition of Formulation Example 11 was obtained in the same manner as Formulation Example 1 except that the surfactant was not added.

[Composition Examples 12-16]
In accordance with the formulation shown in Table 2, the formulations were obtained in the same manner as in Formulation Example 1 except for Formulation Examples 12-16.

[Composition Examples 17-24]
According to the formulation shown in Table 3, two or three surfactants were used, and the compositions of Formulation Examples 17 to 24 were obtained in the same manner as Formulation Example 1. In addition, in the blending examples 17-24, it mix | blends in order of water, surfactant, zinc alloy, and water, and mix | blends water twice.

[Evaluation of dispersibility]
The dispersibility in the composition of the Zn-Al alloy after preparation of the composition was evaluated as follows.
A ... very good B ... good C ... bad D ... zinc alloy repels water This evaluation result is shown in the said Tables 1-3.

From Table 1, it can be seen that in the case of the polyoxyethylene alkylamine of the formula (1), any surfactant exhibits good dispersibility (HLB 6.3 to 9.5).
In the case of the polyoxyethylene alkyl ether of the formula (2), “Marpon ACF-9” showing the same HLB13.3 has a dispersibility evaluation of C, and “Marpon B-9W” has an evaluation of B. “Marpon ACF-7” of HLB12.1 is also rated B, “Marpon B-5” and “Emulgen 106” of HLB10.9 and 10.5 are both rated A, and “ "Emulgen 102KG" is rated C. Therefore, in the case of polyoxyethylene alkyl ether, it is guessed that HLB10-13 is preferable and HLB10-11 is more preferable.
In the case of Formulation Example 11 where no surfactant is added, the dispersibility of the zinc alloy is very poor.

From Table 2, when the surfactants of formulas (3) to (5) (polyoxyethylene distyrenated phenyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester) are used alone, “Emulgen A-60” It can be seen that only (HLB12.8) is evaluation B, and the other surfactant is evaluation C.
From Table 3, dispersibility does not improve even if two surfactants of formula (3) and two surfactants of formula (4) are mixed, and the surfactants of formulas (4) and (5) It was confirmed that the evaluation was B when HLB13 to 15 was mixed and the evaluation was A when the surfactant of formula (2) was further mixed to HLB13.6.
When a rust preventive paint is prepared using a surfactant having a dispersibility evaluation of B or higher, it is considered that the zinc alloy is well dispersed in any rust preventive paint.

2. Preparation of rust preventive paint [Example 1]
In accordance with the composition (shown in parts by mass) shown in Table 4 below, a Zn—Al alloy paste (the above “STAPA 4 ZnAl7”), boron nitride (manufactured by Nippon Koken Kogyo Co., Ltd.), a surfactant (the above “Emulgen 106”) , Wetting and dispersing agent, acetic acid, silane coupling agent (“S510” manufactured by JNC Corporation, 3-glycidoxypropyltrimethoxysilane), water, thickener (“BYK-425” manufactured by Big Chemie Japan Co., Ltd.), urethane System thickener (rheology control agent)), antifoaming agent (“BYK-011” manufactured by Big Chemie Japan Co., Ltd.), and wetting agent are mixed and stirred for 4 hours to obtain the anticorrosive paint of Example 1. It was.

[Examples 2 to 5]
In accordance with the formulation shown in Table 4, Examples 2 to 5 were obtained in the same manner as Example 1.

[Examples 6 to 11]
According to the composition of Table 4, the rust preventive paints of Examples 6 to 11 were obtained in the same manner as in Example 1 except that Ca ion exchange silica (“Silo Mask 52” manufactured by Fuji Silysia Chemical Ltd.) was further added. It was.

  In Table 4, “Ca ion exchange silica / alloy”, “boron nitride / alloy”, and “silane coupling agent / alloy” are respectively Ca ion exchange silica, boron nitride, and silane coupling agent Zn—Al alloy. The mass ratio (%) to (active ingredient of Zn—Al alloy paste, 92% of Zn—Al alloy paste) is shown. “C / (a + b + c + d)” is the mass ratio of boron nitride to the total mass of Ca ion-exchanged silica (when included in the rust preventive paint), active ingredient of Zn—Al alloy paste, boron nitride, and silane coupling agent. (%).

[Comparative Examples 1-6]
According to the composition (shown in parts by mass) shown in Table 5 below, boron nitride and Ca ion exchange silica were not added, except that the “Zontes AL” was added instead of the “Emulgen 106” as a surfactant. In the same manner as in Examples 1 to 6, rust preventive paints of Comparative Examples 1 to 6 were obtained.

3. Preparation of corrosion-resistant surface-treated bolts After degreasing and shot blasting on the surface of bolts (M8: steel), the rust-preventive paints of Examples 1 to 11 and Comparative Examples 1 to 6 were used for the dip spin method. After coating and drying at 150 ° C. before curing, it was cured at 330 ° C. to form a coating film. Again, painting was performed using the same anticorrosive paint. That is, the coating was performed twice. The coating amount was 200 mg / dm ² .

4). Production of Corrosion Resistant Surface Treatment Plate After degreasing the surface of a cold-rolled steel plate (SPCC-SD, manufactured by Nippon Test Panel Co., Ltd., 0.8 mm × 70 mm × 150 mm), Examples 1 to 11 and Comparative Example 1 The film was coated by dip spin method using -6 anticorrosive paint, dried at 150 ° C. before curing, and then cured at 330 ° C. to form a coating film. Again, painting was performed using the same anticorrosive paint. That is, the coating was performed twice. The coating amount was 200 mg / dm ² .

5. Performance evaluation [salt spray test (corrosion resistance evaluation test)]
About the above-mentioned corrosion-resistant surface treatment bolt and corrosion-resistant surface treatment plate, the salt spray test was done based on "JIS-K5600-7-1". The presence or absence of the occurrence of red rust with respect to the elapsed time was evaluated as follows. The results are shown in Table 4 above.
A: No red rust occurs after 1200 hours B: No red rust occurs after 1000 hours C: Slight red rust occurs after 1000 hours D: Red rust occurs before 500 hours

[Summary]
From the said Table 4 and Table 5, the anticorrosion paint of Examples 1-5 containing boron nitride, and the anticorrosion paint of Examples 6-11 containing boron nitride and Ca ion exchange silica (Zn-Al of boron nitride) When the coating film is formed using a mass ratio to the alloy of 2% to 46%), when the coating film is formed using the anticorrosion paint of Comparative Examples 1 to 6 that does not contain boron nitride and Ca ion exchange silica ( It can be seen that the corrosion resistance of both the corrosion-resistant surface-treated bolt and the corrosion-resistant surface-treated plate is improved as compared with the case where red rust is generated before 500 hours have elapsed.
Among the anti-corrosion paints of Examples 1 to 5, the anti-corrosion surface-treated bolts and the anti-corrosion surface-treated plates have the above-mentioned mass ratios of 4% to 14%. doing.
And the anticorrosion paint of Examples 6-11 containing both boron nitride and Ca ion exchange silica has further improved corrosion resistance.

From the above, the rust preventive paint of the present invention containing boron nitride and ion exchange silica has good rust preventive properties, and the coated article formed by coating the rust preventive paint on the object to be coated has good corrosion resistance. Was confirmed.
In addition, since the anticorrosive paint of the present invention contains the above-mentioned surfactant, it was also confirmed that the zinc alloy was well dispersed in water and a coating film could be uniformly formed on the surface of the object to be coated.

Claims (13)

A powdered alloy containing zinc and a metal other than zinc; and
Boron nitride,
An anticorrosive paint characterized by containing water.   The rust preventive paint according to claim 1, wherein a mass ratio of the boron nitride to the alloy is 0.001 or more and 0.46 or less.   The rust preventive paint according to claim 1 or 2, comprising ion-exchanged silica obtained by binding at least one of calcium ions and magnesium ions to the silica by ion exchange.   The rust preventive paint according to claim 3, wherein a mass ratio of the ion exchange silica to the alloy is 0.015 or more and 0.35 or less.   Contains a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group in the molecule and a hydrolyzable silicon group The rust preventive paint according to any one of claims 1 to 4. Containing a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group and a hydrolyzable silicon group in the molecule; ,
The rust prevention according to claim 1 or 2, wherein a mass ratio of the boron nitride to a total mass of the alloy, the boron nitride, and the silane coupling agent is 0.01 or more and 0.23 or less. paint. Containing a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, a methacryloxy group, an acryloxy group, an amino group, a mercapto group, and a vinyl group and a hydrolyzable silicon group in the molecule; ,
5. The mass ratio of the boron nitride to the total mass of the alloy, the boron nitride, the silane coupling agent, and the ion-exchange silica is 0.01 or more and 0.23 or less. Anticorrosive paint as described in 1.   It is at least one selected from the group consisting of polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene sorbitan fatty acid ester, and sorbitan fatty acid ester, and HLB is 6 or more and 17 The rust preventive paint according to any one of claims 1 to 7, further comprising a surfactant which is:   The rust preventive paint according to any one of claims 1 to 8, wherein the alloy contains 50 mass% or more of zinc.   The rust preventive paint according to any one of claims 1 to 9, wherein the metal other than zinc is aluminum.   The rust preventive paint according to any one of claims 1 to 10, wherein the alloy has a flake shape.   A coating film forming method, wherein a coating film is formed by coating the object to be coated with the rust preventive paint according to any one of claims 1 to 11.   A coated article obtained by coating the article to be coated with the rust preventive paint according to any one of claims 1 to 11.