JP2020157689A - Corrosion resistant coating and method for forming the same - Google Patents

Abstract

To provide, in a corrosion resistant coating comprising coating a metal substrate with a metal foil formed substantially of titanium or a titanium alloy as an outermost layer, a corrosion resistant coating with suppressed hydrogen embrittlement of the metal foil, and a method for forming the same.SOLUTION: A corrosion resistant coating 10 having a corrosion resistant layer, an adhesive layer, and a metal foil is formed by providing, on a surface of a metal substrate 90 and in the order from the surface, (1) a corrosion resistant layer 14 formed substantially of an epoxy resin-based coating, (2) an adhesive layer 16 formed substantially of a tackiness agent or a bonding agent, and (3) a metal foil 18 having surface arithmetic average roughness of 3.9 μm or less and formed substantially of titanium or a titanium alloy.SELECTED DRAWING: Figure 1

Description

The present invention relates to an anticorrosion coating provided on the surface of a metal base material and a method for forming the same, and more particularly to an anticorrosion coating provided with a metal foil made of titanium or a titanium alloy on the outermost layer and a method for forming the same. Here, in the present application, the outermost layer of the anticorrosion coating provided on the surface of the metal base material is the layer farthest from the surface of the metal base material.

Steel materials are inexpensive but have excellent mechanical properties, and are used in many fields. However, they have the weakness of being easily corroded, and the technological development of anticorrosion coatings that effectively protect steel materials has been enthusiastically promoted. ing. As an anticorrosion coating that effectively protects steel materials, a technique of arranging a metal foil made of titanium or a titanium alloy in the outermost layer is attracting attention as a promising technique, and many proposals including related techniques have been made (). For example, see Patent Documents 1 to 4).

On the other hand, for marine steel structures (piers, jack-up legs, floating steel structures, marine platforms, etc.), steel structures (bridges, plants, tanks, steel towers, etc.), self-elevating workbench, ships and them. Zinc rich paint is often used to prevent corrosion of steel materials when manufacturing pipes to be installed at factories.

Inorganic zinc rich paint, which has high anticorrosion properties and is often used as an undercoat, is often packed with zinc powder and paint liquid separately. In this case, before using zinc powder and paint liquid. To make zinc rich paint and use it. However, when the zinc powder and the coating liquid are mixed, the zinc powder may scatter, and zinc is applied to the surface of the metal foil made of titanium or a titanium alloy, which is the outermost layer of the anticorrosion coating provided on the surface of the metal base material. Powder may adhere.

In addition, when welding a galvanized steel material, in order to prevent the occurrence of welding defects (zinc has a high vapor pressure, zinc vapor causes welding defects such as blow holes), the zinc-plated portion is polished. Zinc is removed, but the zinc powder produced at that time may adhere to the surface of the metal foil made of titanium or a titanium alloy.

When zinc powder or zinc powder adheres to the surface of a metal foil made of titanium or a titanium alloy and is exposed to rain or used in a marine environment to form a water film on the surface, zinc becomes the anode and titanium. Becomes the cathode, and hydrogen is generated on the surface of titanium, which is the cathode, and when the titanium occludes the hydrogen, a hard and brittle hydride is formed. Titanium hydride formed at room temperature due to contact corrosion of dissimilar metals between titanium and zinc is distributed in the range of tens to hundreds of μm from the surface of titanium or titanium alloy, so the plate of titanium or titanium alloy If the thickness is thick, there is no problem in practical use, but if the plate thickness of titanium or titanium alloy is thin (when titanium or titanium alloy is foil), the whole becomes brittle and the mechanical performance is greatly impaired. There was a problem.

Japanese Unexamined Patent Publication No. 2001-260271 Japanese Unexamined Patent Publication No. 2004-244652 Japanese Unexamined Patent Publication No. 2004-202693 Japanese Unexamined Patent Publication No. 2008-44107

The present invention has been made in view of the above points, and in the anticorrosion coating which has a metal foil substantially formed of titanium or a titanium alloy in the outermost layer and coats a metal base material, the metal foil is used. An object of the present invention is to provide an anticorrosion coating in which hydrogen embrittlement is suppressed and a method for forming the same.

The present invention solves the above-mentioned problems by the following anticorrosion coating.

That is, the aspect of the anticorrosion coating according to the present invention is that the surface of the metal substrate is approached from the side closer to the surface.
(1) Anticorrosion layer substantially formed of epoxy resin-based paint,
(2) Adhesive layer substantially formed by an adhesive or an adhesive,
(3) A metal foil substantially formed of titanium or a titanium alloy having an arithmetic mean roughness of the surface of 3.9 μm or less.
The anticorrosion coating is characterized by having the anticorrosion layer, the adhesive layer, and the metal foil in the order of.

Here, in the present application, "substantially formed" is a concept including a case where it is formed including unavoidable impurities.

It is preferable that an oxide film having a thickness of 2.1 nm or more is substantially formed on the surface of the metal foil.

The adhesive layer was selected from the group consisting of rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. It may be configured to be substantially formed of at least one adhesive or adhesive.

The adhesive used to form the adhesive layer may be solvent-based, water-based, or solvent-free, and the curing method may be thermosetting or room temperature curing. As a painting method, it is possible to use a method of painting with a painting machine such as a brush, a spray, a flow coater, or a roll coater.

The epoxy resin of the epoxy resin-based adhesive used for forming the adhesive layer is not particularly limited, and specifically, for example, a bisphenol type epoxy resin, a glycidyl ester-based epoxy resin, a glycidylamine-based epoxy resin, and a fat. Examples thereof include group epoxy resins, alicyclic epoxy resins, and epoxy resins such as novolak type epoxy resins.

Specifically, as the elastomer component of the rubber-based pressure-sensitive adhesive used for forming the adhesive layer, at least one of natural rubber, isoprene rubber, styrene isoprene rubber, butyl rubber, butadiene rubber, and chloroprene rubber is the main component. Can be mentioned.

Examples of the resin component of the acrylic resin-based adhesive used for forming the adhesive layer include an acrylic copolymer. This acrylic copolymer is composed of an acrylic acid alkyl ester obtained by reacting a monomer with a cross-linking agent such as an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent, or a cross-linkable functional group-containing monomer. Specific examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate.

As the urethane resin of the urethane resin-based adhesive used for forming the adhesive layer, specifically, for example, a self-emulsifying urethane resin or a surfactant emulsified without using a surfactant is used. Examples include emulsified forced emulsified urethane resins.

The urethane resin-based adhesive used for forming the adhesive layer is not particularly limited, and specifically, for example, polyisocyanate (aliphatic polyisocyanate, aromatic polyisocyanate, alicyclic polyisocyanate). A mixture of one or more compounds having a hydroxyl group can be used.

As the silicone resin-based adhesive used for forming the adhesive layer, either a peroxide-curable silicone-based adhesive or an addition-reaction type silicone-based adhesive can be used.

The adhesive layer includes a first adhesive layer and a second adhesive layer in order from the side closest to the surface of the metal base material, and the first adhesive layer and the second adhesive layer. It may be configured to have an extensible stretchable layer between it and the adhesive layer.

Specifically, the extendable layer is, for example, polyethylene, polypropylene, vinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyvinyl alcohol, polyvinylidene chloride, nylon, polycarbonate, ethylene vinyl acetate copolymer, and the like. An extendable resin layer substantially formed of at least one selected from the group consisting of polyimide, silicone resin, and acrylic resin, or glass fiber, nylon fiber, polyester fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, rayon fiber. , A stretchable non-woven fabric substantially formed of at least one selected from the group consisting of vinylon fiber and acrylic fiber, or urethane foam, natural rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, butadiene rubber, nitrile. It is substantially formed of at least one selected from the group consisting of rubber, ethylene propylene diene rubber (EPDM), silicone rubber, urethane rubber, and fluorine rubber.

Here, as the polyester fiber, specifically, for example, a fiber composed of any one of polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate can be mentioned.

The thickness of the metal foil is preferably 10 μm or more and 150 μm or less.

An undercoat substantially formed between the surface of the metal substrate and the anticorrosion layer using at least one of an inorganic zinc rich paint, an organic zinc rich paint, an epoxy resin paint, and a modified epoxy resin paint. A layer may be provided.

A mode of the method for forming an anticorrosion coating according to the present invention is a step of forming an anticorrosion layer on the surface of a metal base material, and an adhesive layer on a metal foil substantially formed of titanium or a titanium alloy. The metal foil member is attached to the anticorrosion layer formed in the anticorrosion layer forming step by the adhesive layer, and the metal foil member is attached to the anticorrosion layer. This is a method for forming an anticorrosion coating, characterized in that the arithmetic average roughness of the surface opposite to the adhesive layer is 3.9 μm or less.

A paper pattern is attached to the adhesive layer of the metal foil member in advance, and in the metal foil attaching step, the paper pattern is peeled off and the metal foil member is placed on the anticorrosion layer. The adhesive layer may be attached.

In the metal foil pasting step, the following order (1) to (4), that is,
(1) The surface is substantially formed of titanium or a titanium alloy having an arithmetic mean roughness of 3.9 μm or less and an oxide film having a thickness of 2.1 nm or more substantially formed on the surface. Metal leaf,
(2) At least one selected from the group consisting of rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. A second adhesive layer, substantially formed of adhesive or adhesive,
(3) Consists of polyethylene, polypropylene, vinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyvinyl alcohol, polyvinylidene chloride, nylon, polycarbonate, ethylene vinyl acetate copolymer, polyimide, silicone resin, acrylic resin. An extensible resin layer substantially formed by at least one selected from the group, or a group consisting of glass fiber, nylon fiber, polyester fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, rayon fiber, vinylon fiber, acrylic fiber. Stretchable non-woven fabric substantially formed of at least one selected from, or urethane foam, natural rubber, chloroprene rubber, polyethylene propylene rubber, butyl rubber, butadiene rubber, nitrile rubber, ethylene propylene diene rubber (EPDM), silicone rubber. An stretchable layer substantially formed of at least one selected from the group consisting of, urethane rubber, and fluororubber.
(4) At least one selected from the group consisting of rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. A first adhesive layer, substantially formed of an adhesive or adhesive,
The metal foil members laminated in the order of the above may be attached to the anticorrosion layer formed in the anticorrosion layer forming step by the first adhesive layer.

Here, as the polyester fiber, specifically, for example, a fiber composed of any one of polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate can be mentioned.

A paper pattern is attached to the first adhesive layer of the metal foil member in advance, and in the metal foil attaching step, the paper pattern is peeled off and the metal foil is placed on the anticorrosion layer. The first adhesive layer of the member may be attached.

According to the present invention, in the anticorrosion coating having a metal foil substantially formed of titanium or a titanium alloy in the outermost layer and coating the metal base material, the anticorrosion coating in which hydrogen embrittlement of the metal foil is suppressed is suppressed. And a method for forming the same.

Sectional drawing which shows typically the anticorrosion coating 10 which concerns on 1st Embodiment of this invention. Sectional drawing which shows typically the anticorrosion coating 20 which concerns on 2nd Embodiment of this invention. Enlarged schematic diagram schematically showing an enlarged portion of a 5 cm long notch (artificial scratch) in an anticorrosion coating sample.

Hereinafter, embodiments of the anticorrosion coating according to the present invention will be described in detail with reference to the drawings.

(1) Configuration of First Embodiment (1-1) FIG. 1 is a cross-sectional view schematically showing an anticorrosion coating 10 according to a first embodiment of the present invention.

As shown in FIG. 1, the anticorrosion coating 10 according to the first embodiment has an undercoat layer 12, an anticorrosion layer 14, and an adhesive layer 16 (adhesive layer) on the surface of the metal base material 90 from the side closer to the surface. 16A or the adhesive layer 16B) and the metal foil 18 are laminated in this order.

The metal base material 90 for which the anticorrosion coating 10 according to the first embodiment is subject to anticorrosion is not particularly limited, but specifically, for example, in addition to carbon steel, low alloy steel, stainless steel, zinc-plated steel, and aluminum. -Zinc alloy plated steel, sprayed or overlaid steel, aluminum, etc. can be mentioned.

The primer layer 12 has a role of improving the adhesive force between the surface of the metal base material 90 and the anticorrosion layer 14 and a role of suppressing the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.). It is a layer to have, and specifically, for example, at least one of inorganic zinc rich paint, organic zinc rich paint, and epoxy-based primer can be used. When an inorganic zinc rich paint or an organic zinc rich paint is used for the undercoat layer 12, it can be expected to play a role of suppressing corrosion of the steel material due to the sacrificial anticorrosion action of zinc.

It is preferable to clean the surface of the metal base material 90 before applying the undercoat layer 12 to the surface of the metal base material 90. Specifically, the surface cleaning treatment of the metal base material 90 includes, for example, a blast treatment using steel grid, steel shot, silica sand, garnet, copper shavings, etc. as a polishing material, a cleaning treatment using an electric tool, a manual tool, or the like. It can be performed by water blasting, polishing with abrasive paper, or the like.

The purpose of the surface cleaning treatment of the metal base material 90 is to improve the adhesion of the undercoat layer 12 to the surface of the metal base material 90 by removing dirt and an oxide film on the surface of the metal base material 90. To do. Another object of the present invention is to improve the adhesion of the undercoat layer 12 to the surface of the metal base material 90 by the anchor effect by providing unevenness on the surface of the metal base material 90.

The thickness of the undercoat layer 12 is from the viewpoint of suppressing the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.), and the unevenness of the surface of the metal base material 90 caused by the cleaning treatment. From the viewpoint of filling, 10 μm or more is preferable, and 20 μm or more is more preferable. Further, especially when the undercoat layer 12 containing a large amount of zinc is thickened, it may be difficult to dry or easily peel off. Therefore, the thickness of the undercoat layer 12 is preferably 100 μm or less, preferably 80 μm or less. Is more preferable. Therefore, the thickness of the undercoat layer 12 is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 80 μm or less.

Even if the anticorrosion layer 14 is provided on the surface of the metal base material 90 without providing the undercoat layer 12, the anticorrosion layer 14 adheres to the surface of the metal base material 90 with sufficient adhesive force, and the undercoat layer When the effect of suppressing the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.) is sufficiently obtained in the entire anticorrosion coating 10 even if 12 is not provided, the undercoat layer 12 It is not necessary to provide.

The anticorrosive layer 14 has a role of suppressing the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.).

The requirements for the material used for the anticorrosive layer 14 are that it is chemically stable, that it suppresses the penetration of corrosion factors (water, oxygen) and corrosion promoters (chloride ions, etc.), and that it is damp outdoors. It can be constructed even in a certain environment. From the viewpoint of these requirements, the material used for the anticorrosion layer 14 is preferably an epoxy resin, and specifically, for example, an epoxy resin paint, a modified epoxy resin paint, an ultrathick film type epoxy resin paint, and a water-based epoxy resin paint. , Solventless epoxy resin paint, and one or more kinds of epoxy resin paint containing additives (glass fiber, glass flakes, mica, etc.) can be used. Epoxy resin paints containing additives (glass fiber, glass flakes, mica, etc.) can enhance the effect of suppressing the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.).

The thickness of the anticorrosive layer 14 is preferably 20 μm or more, and more preferably 30 μm or more, from the viewpoint of suppressing the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.). preferable. On the other hand, if the thickness of the anticorrosion layer 14 becomes too thick, the residual stress during curing shrinkage may increase and cracks may occur, and the anticorrosion layer 14 tends to drip when applied to a vertical surface. The thickness of the above is preferably 5000 μm or less, and more preferably 2000 μm or less. Therefore, the thickness of the anticorrosion layer 14 is preferably 20 μm or more and 5000 μm or less, and more preferably 30 μm or more and 2000 μm or less.

The adhesive layer 16 has a role of attaching the metal foil 18 to the anticorrosion layer 14, and specifically, for example, a rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesive, and an epoxy resin-based adhesive. It can be formed by using at least one kind of pressure-sensitive adhesive or adhesive selected from the group consisting of acrylic resin-based, urethane resin-based and silicone resin-based adhesives. Here, when the adhesive layer is used for the adhesive layer 16, the adhesive layer 16 is referred to as the adhesive layer 16A, and when the adhesive layer is used for the adhesive layer 16, the adhesive layer 16 is adhered. It will be referred to as layer 16B.

The thickness of the adhesive layer 16 (adhesive layer 16A or adhesive layer 16B) is such that even if the metal foils 18 are wrapped together, no gap is formed (between the metal foils 18 formed by wrapping the metal foils 18). From the viewpoint of filling the step with the adhesive layer 16) and from the viewpoint of absorbing the unevenness of the surface of the anticorrosion layer 14, it is preferably 20 μm or more, and more preferably 30 μm or more. On the other hand, when the adhesive layer 16A is used for the adhesive layer 16, the thickness is preferably 7000 μm or less, preferably 5000 μm or less, because if it becomes too thick, a step becomes large and a non-adhered portion may be formed. Is more preferable. When the adhesive layer 16B is used for the adhesive layer 16, the thickness should be 100 μm or less because if it becomes too thick, excessive stress may occur during curing and the adhesive layer 16 may crack, and the curing time becomes very long. It is preferably 80 μm or less, and more preferably 80 μm or less. Therefore, when the adhesive layer 16A is used for the adhesive layer 16, the thickness is preferably 20 μm or more and 7000 μm or less, more preferably 30 μm or more and 5000 μm or less, and the adhesive layer 16B is attached to the adhesive layer 16. The thickness is preferably 20 μm or more and 100 μm or less, and more preferably 30 μm or more and 80 μm or less.

The metal foil 18 is attached on the anticorrosion layer 14 by the adhesive layer 16, and is a layer arranged on the outermost layer in the anticorrosion coating 10 of the present embodiment. The metal foil 18 is made of titanium or a titanium alloy. Titanium and a titanium alloy having a predetermined composition are metals having extremely excellent corrosion resistance. The metal foil 18 has a role of blocking the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.) and preventing ultraviolet rays from hitting the resin of the anticorrosive coating 10.

As the titanium and the titanium alloy used as the metal foil 18 of the anticorrosion coating 10 of the present embodiment, it is preferable to use one containing a small amount of additive elements from the viewpoint of ensuring spreadability and improving workability. Specifically, JIS It is preferable to use a titanium and titanium alloy satisfying the JIS Class 1 chemical composition of H 4600 (titanium and titanium alloy-plate and strip). Specifically, the chemical components (chemical components other than titanium) of titanium and the titanium alloy used as the metal foil 18 of the anticorrosion coating 10 of the present embodiment are JIS 1 type chemical components having a carbon content of 0.08 wt% or less. It is preferable that hydrogen is 0.013 wt% or less, oxygen is 0.15 wt% or less, nitrogen is 0.03 wt% or less, and iron is 0.20 wt% or less. Further, when the content of oxygen and iron is reduced, the workability when processing titanium foil is improved, so that carbon is 0.08 wt% or less, hydrogen is 0.013 wt% or less, and oxygen is 0.12 wt% or less. It is more preferable that nitrogen is 0.03 wt% or less and iron is 0.15 wt% or less, and the contents of oxygen and iron are further reduced so that carbon is 0.08 wt% or less and hydrogen is 0.013 wt% or less. It is particularly preferable that oxygen is 0.10 wt% or less, nitrogen is 0.03 wt% or less, and iron is 0.10 wt% or less.

Further, from the viewpoint of further improving the corrosion resistance of the metal foil 18, the titanium and titanium alloy used as the metal foil 18 are further added to Ni, Co, Ta, Cr, Ru, Mo, Pd, Pt, Rh, Al, V, Zr. , Sn, Si, Cu and Nb are preferably added in a total amount of 2 wt% or less. However, it should be noted that if the above-mentioned metals are added in an amount of more than 2 wt% in total, the metal foil 18 becomes hard and difficult to construct.

The surface of the metal foil 18 made of titanium or a titanium alloy has an arithmetic mean roughness (Ra) of 3.9 μm or less, preferably 1.8 μm or less, in order to prevent zinc powder from adhering to the surface. As described above in the [Background Technology] column, the surface of a metal foil made of titanium or a titanium alloy may be exposed to rain with zinc powder or zinc powder attached, or may be used in a marine environment. This is because when a water film is formed, zinc serves as an anode and titanium serves as a cathode, hydrogen is generated on the surface of titanium, which is the cathode, and when the titanium occludes the hydrogen, a hard and brittle hydride is formed.

The thickness of the metal foil 18 made of titanium or a titanium alloy is 10 μm or more from the viewpoint of surely blocking the penetration of corrosion factors (water, oxygen) and corrosion promoting factors (chloride ions, etc.) and from the viewpoint of making it difficult to tear. It is preferably 20 μm or more, and more preferably 20 μm or more. On the other hand, from the viewpoint of preventing springback and improving the adhesion to the edge portion, the thickness of the metal foil 18 is preferably 150 μm or less, and more preferably 80 μm or less. Therefore, the thickness of the metal foil 18 made of titanium or a titanium alloy is preferably 10 μm or more and 150 μm or less, and more preferably 20 μm or more and 80 μm or less.

Further, from the viewpoint of suppressing the flow of electricity on the surface of the metal foil 18 and making it difficult for hydrides to be formed, the surface of the metal foil 18 made of titanium or a titanium alloy has an oxide film having a thickness of 2.1 nm or more. Is preferably formed.

(1-2) Effect In the anticorrosion coating 10 according to the first embodiment, the metal foil 18 arranged in the outermost layer is made of titanium or a titanium alloy having a predetermined composition, and has excellent corrosion resistance. Further, the arithmetic mean roughness (Ra) of the surface of the metal foil 18 is 3.9 μm or less, and zinc powder does not easily adhere to the surface.

Therefore, in the anticorrosion coating 10 according to the first embodiment, hydrogen embrittlement of the outermost metal leaf 18 made of titanium or a titanium alloy having excellent corrosion resistance is suppressed, and the outermost metal leaf 18 is used for a long period of time. Corrosion factors (water, oxygen) and corrosion promotion due to the synergistic effect of the anticorrosion layer 14 provided under the metal foil 18 and the undercoat layer 12 provided under the metal foil 18 and the metal foil 18 as needed, which are kept sound. The penetration of factors (such as chloride ions) is strongly suppressed, and the metal substrate 90 is kept healthy for a long period of time.

(1-3) Forming Method The method for forming the anticorrosion coating 10 according to the first embodiment can be specifically formed by, for example, the following steps S1a to S1e.

(Step S1a) The surface of the metal base material 90 is cleaned. Specifically, the surface cleaning treatment of the metal base material 90 includes, for example, a blast treatment using steel grid, steel shot, silica sand, garnet, copper shavings, etc. as a polishing material, a cleaning treatment using an electric tool, a manual tool, or the like. It can be performed by water blasting, polishing with abrasive paper, or the like.
(Step S1b) The undercoat layer 12 is applied to the surface of the metal base material 90 that has been cleaned.
(Step S1c) After the undercoat layer 12 is sufficiently dried, the anticorrosion layer 14 is provided on the undercoat layer 12.
(Step S1d) After the anticorrosion layer 14 is sufficiently dried, an adhesive layer 16 (adhesive layer 16A or adhesive layer 16B) is provided on the anticorrosion layer 14.
(Step S1e) The metal foil 18 is attached to the adhesive layer 16 (adhesive layer 16A or adhesive layer 16B), and the metal foil 18 is provided on the outermost layer of the anticorrosion coating 10.

Although steps S1a and S1b are not essential steps, steps S1a and S1b are performed from the viewpoint of improving the adhesive force of the anticorrosion coating 10 to the metal substrate 90 and improving the anticorrosion performance of the anticorrosion coating 10. It is preferable to carry out the step as well.

Further, a metal foil member (not shown) produced by laminating the adhesive layer 16 (adhesive layer 16A or adhesive layer 16B) to the metal foil 18 is attached to the anticorrosion layer 14 formed in step S1c. It may be attached by the adhesive layer 16 (adhesive layer 16A or adhesive layer 16B), and steps S1d and S1e may be performed at the same time, and this is preferable from the viewpoint of workability.

When step S1d and step S1e are performed at the same time as described above, a release paper is previously attached to the adhesive layer 16 (adhesive layer 16A or adhesive layer 16B) of the metal foil member, and the release paper is attached. Workability can be further improved by peeling off the paper pattern and attaching the adhesive layer 16 (adhesive layer 16A or adhesive layer 16B) of the metal foil member onto the anticorrosion layer 14.

(2) Configuration of Second Embodiment (2-1) FIG. 2 is a cross-sectional view schematically showing the anticorrosion coating 20 according to the second embodiment of the present invention.

As shown in FIG. 2, the anticorrosion coating 20 according to the second embodiment has an undercoat layer 12, an anticorrosion layer 14, and a first adhesive layer 22 on the surface of the metal base material 90 from the side closer to the surface. (Adhesive layer 22A or adhesive layer 22B), extensible layer 24 (extensible resin layer 24A or extensible non-woven fabric 24B), second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B), metal foil 18 in that order. It is laminated with.

In the anticorrosion coating 20 according to the second embodiment, the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B) is placed between the anticorrosive layer 14 and the metal foil 18 in order from the one closest to the anticorrosive layer 14. The point that the stretchable layer 24 (extensible resin layer 24A or the stretchable non-woven fabric 24B) and the second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B) are provided is the anticorrosion according to the first embodiment. Although different from the coating 10, the undercoat layer 12, the anticorrosion layer 14, the metal foil 18, and the metal base material 90 are the same as the anticorrosion coating 10 according to the first embodiment, so that the anticorrosion coating 20 according to the second embodiment In the description, the description of the undercoat layer 12, the anticorrosion layer 14, the metal foil 18, and the metal base material 90 will be omitted.

The first adhesive layer 22 has a role of attaching the stretchable layer 24 (extensible resin layer 24A or stretchable non-woven fabric 24B) to the anticorrosion layer 14, and specifically, for example, a rubber-based or acrylic resin-based layer. , Urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based, and silicone resin-based adhesives, formed using at least one adhesive or adhesive selected from the group. can do. Here, when the adhesive layer is used for the first adhesive layer 22, the first adhesive layer 22 is referred to as the adhesive layer 22A, and the adhesive layer is used for the first adhesive layer 22. The first adhesive layer 22 will be referred to as an adhesive layer 22B.

The thickness of the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B) is such that even if the stretchable layers 24 (extensible resin layer 24A or the stretchable non-woven fabric 24B) are wrapped with each other, no gap is generated. (The viewpoint of filling the step between the stretchable layers 24 (extensible resin layer 24A or the stretchable non-woven fabric 24B) generated by wrapping with the first adhesive layer 22) and the anticorrosion layer 14. From the viewpoint of absorbing the unevenness of the surface of the above, it is preferably 20 μm or more, and more preferably 30 μm or more. On the other hand, if the thickness of the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B) becomes too thick, the adhesion to the edge portion may deteriorate, and excessive stress may be applied during shrinkage. When the adhesive layer 22A is used for the first adhesive layer 22, the thickness of the adhesive layer 22A is preferably 3500 μm or less, more preferably 2500 μm or less, and more preferably 2500 μm or less, because cracks may occur. When the adhesive layer 22B is used for the adhesive layer 22 of No. 1, the thickness is preferably 100 μm or less, and more preferably 80 μm or less. Therefore, when the adhesive layer 22A is used for the first adhesive layer 22, the thickness is preferably 20 μm or more and 3500 μm or less, more preferably 30 μm or more and 2500 μm or less, and the first adhesive adhesion. When the adhesive layer 22B is used for the layer 22, the thickness is preferably 20 μm or more and 100 μm or less, and more preferably 30 μm or more and 80 μm or less.

The extensible layer 24 is a layer that can be expanded by receiving an external force, and has a role of preventing the metal foil 18 and the metal base material 90 from coming into contact with each other even if driftwood or the like collides with each other. Further, the expandable layer 24 also has a role of improving handleability when arranging the first adhesive layer 22 and the second adhesive layer 26.

The extensible layer 24 can be formed by using the extensible resin layer 24A which is an extensible resin layer or the extensible non-woven fabric 24B which is an extensible non-woven fabric. Specifically, for example, the extensible resin layer 24A is , Polyethylene, polypropylene, vinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyvinyl alcohol, polyvinylidene chloride, nylon, polycarbonate, ethylene vinyl acetate copolymer, polyimide, silicone resin, acrylic resin. The stretchable non-woven fabric 24B, which can be formed using at least one selected, is a glass fiber, a nylon fiber, a polyester (polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate) fiber, a polyamide fiber, a polyethylene fiber, a polypropylene. It can be formed using at least one selected from the group consisting of fibers, rayon fibers, vinylon fibers, and acrylic fibers. The stretchable layer 24 is formed by using urethane foam, natural rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, butadiene rubber, nitrile rubber, ethylene propylene diene rubber (EPDM), silicone rubber, urethane rubber, and fluorine rubber. You can also do it.

The thickness of the stretchable layer 24 (stretchable resin layer 24A or stretchable non-woven fabric 24B) is 5 μm or more from the viewpoint of preventing the metal foil 18 and the metal base material 90 from coming into contact with each other even if driftwood or the like collides with each other. It is preferable that the thickness is 10 μm or more. On the other hand, if the stretchable layer 24 (extensible resin layer 24A or stretchable non-woven fabric 24B) becomes too thick, the handleability may deteriorate. Therefore, the stretchable resin layer 24A is used for the stretchable layer 24. The thickness of the stretchable layer 24 is preferably 150 μm or less, more preferably 100 μm or less, and the thickness of the stretchable non-woven fabric 24B is preferably 300 μm or less. It is more preferable to make it 200 μm or less. Therefore, when the extensible resin layer 24A is used for the extensible layer 24, the thickness is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 100 μm or less, and the extensible non-woven fabric is applied to the extensible layer 24. When 24B is used, the thickness is preferably 5 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less.

When urethane foam, polyethylene foam, rubber, etc. are used for the stretchable layer 24, it is difficult to manufacture thin urethane foam, polyethylene foam, rubber, etc., but because it is flexible, the thickness of the stretchable layer 24 is It is preferably 50 μm or more and 5000 μm or less, and more preferably 100 μm or more and 3000 μm or less.

The second adhesive layer 26 has a role of attaching the metal foil 18 to the stretchable layer 24, and specifically, for example, a rubber-based, acrylic resin-based, urethane resin-based, and silicone resin-based pressure-sensitive adhesive. It can be formed by using at least one adhesive or adhesive selected from the group consisting of epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. Here, when the adhesive layer is used for the second adhesive layer 26, the second adhesive layer 26 is referred to as the adhesive layer 26A, and the adhesive layer is used for the second adhesive layer 26. The second adhesive layer 26 will be referred to as an adhesive layer 26B.

The thickness of the second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B) is such that the stretchable layers 24 (extensible resin layer 24A or the stretchable non-woven fabric 24B) are wrapped with each other and the metal foils 18 are laminated with each other. From the viewpoint of preventing gaps from being generated even when wrapped (steps between the stretchable layers 24 (extensible resin layer 24A or stretchable non-woven fabric 24B) formed by wrapping and metal foils 18 formed by wrapping each other). From the viewpoint of filling the step between the two with the second adhesive layer 26), it is preferably 20 μm or more, and more preferably 30 μm or more. On the other hand, if the thickness of the second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B) becomes too thick, the adhesion to the edge portion may deteriorate, and excessive stress may be applied during shrinkage. When the adhesive layer 26A is used for the second adhesive layer 26, the thickness is preferably 3500 μm or less, more preferably 2500 μm or less, and more preferably 2500 μm or less, because cracks may occur. When the adhesive layer 26B is used for the adhesive layer 26 of 2, the thickness is preferably 100 μm or less, and more preferably 80 μm or less. Therefore, when the adhesive layer 26A is used for the second adhesive layer 26, the thickness is preferably 20 μm or more and 3500 μm or less, more preferably 30 μm or more and 2500 μm or less, and the second adhesive adhesion. When the adhesive layer 26B is used for the layer 26, the thickness is preferably 20 μm or more and 100 μm or less, and more preferably 30 μm or more and 80 μm or less.

(2-2) Effect In the anticorrosion coating 20 according to the second embodiment, the metal foil 18 arranged in the outermost layer is made of titanium or a titanium alloy having a predetermined composition, and has excellent corrosion resistance. Further, the arithmetic mean roughness (Ra) of the surface of the metal foil 18 is 3.9 μm or less, and zinc powder does not easily adhere to the surface.

Therefore, in the anticorrosion coating 20 according to the second embodiment, hydrogen embrittlement of the outermost metal leaf 18 made of titanium or a titanium alloy having excellent corrosion resistance is suppressed, and the outermost metal leaf 18 is used for a long period of time. Corrosion factors (water, oxygen) and corrosion promotion due to the synergistic effect of the anticorrosion layer 14 provided under the metal foil 18 and the undercoat layer 12 provided under the metal foil 18 and the metal foil 18 as needed, which are kept sound. The penetration of factors (such as chloride ions) is strongly suppressed, and the metal substrate 90 is kept healthy for a long period of time.

Further, an extendable layer 24 is provided between the metal foil 18 and the metal base material 90, so that even if a drifting tree or the like collides, the metal foil 18 and the metal base material 90 are prevented from coming into contact with each other. Therefore, even if a drifting tree or the like collides, it is prevented that the metal foil 18 and the metal base material 90 come into contact with each other to promote corrosion.

(2-3) Forming Method The method for forming the anticorrosion coating 20 according to the second embodiment can be specifically formed by, for example, the following steps S2a to S2g.

(Step S2a) The surface of the metal base material 90 is cleaned. Specifically, the surface cleaning treatment of the metal base material 90 includes, for example, a blast treatment using steel grid, steel shot, silica sand, garnet, copper shavings, etc. as a polishing material, a cleaning treatment using an electric tool, a manual tool, or the like. It can be performed by water blasting, polishing with abrasive paper, or the like.
(Step S2b) The undercoat layer 12 is applied to the surface of the metal base material 90 that has been cleaned.
(Step S2c) After the undercoat layer 12 is sufficiently dried, the anticorrosion layer 14 is provided on the undercoat layer 12.
(Step S2d) After the anticorrosion layer 14 is sufficiently dried, a first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B) is provided on the anticorrosion layer 14.
(Step S2e) The extensible layer 24 (extensible resin layer 24A or extensible non-woven fabric 24B) is attached to the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B).
(Step S2f) A second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B) is provided on the extensible layer 24 (extensible resin layer 24A or extensible non-woven fabric 24B).
(Step S2g) The metal foil 18 is attached to the second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B), and the metal foil 18 is provided on the outermost layer of the anticorrosion coating 20.

Although steps S2a and S2b are not essential steps, steps S2a and S2b are performed from the viewpoint of improving the adhesive force of the anticorrosion coating 20 to the metal base material 90 and improving the anticorrosion performance of the anticorrosion coating 20. It is preferable to carry out the step as well.

Further, a metal foil 18, a second adhesive layer 26 (adhesive layer 26A or adhesive layer 26B), an extensible layer 24 (extensible resin layer 24A or an extensible non-woven fabric 24B), and a first adhesive layer 22 (adhesive layer 22A). A metal foil member laminated in the order of the adhesive layer 22A or the adhesive layer 22B) is attached to the anticorrosion layer 14 formed in step S2c by the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B). In addition, steps S2d to S2g may be performed at the same time, and this is preferable from the viewpoint of workability.

When steps S2d to S2g are performed at the same time as described above, the release paper is previously attached to the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B) of the metal foil member. By peeling off the release paper and attaching the first adhesive layer 22 (adhesive layer 22A or adhesive layer 22B) of the metal foil member on the anticorrosion layer 14, the workability is further improved. Can be made to.

(1) Examination of the relationship between the arithmetic mean roughness (Ra) of the surface of the titanium foil and the formation of hydrides (Examples 1 to 7, Comparative Examples 1 to 3)
The relationship between the arithmetic mean roughness (Ra) on the surface of the titanium foil and the formation of hydrides on the surface of the titanium foil was evaluated.

In Examples 1 to 3, JIS type 1 titanium foil having a size of 150 mm × 70 mm × thickness 0.1 mm was used. The arithmetic mean roughness (Ra) of the surface of the titanium foil used in Examples 1 to 3 was 0.8 μm in Example 1, 1.8 μm in Example 2, and 3.9 μm in Example 3.

In Examples 4 and 5, JIS 1 type titanium foil having a size of 150 mm × 70 mm × thickness 0.02 mm was used. The arithmetic mean roughness (Ra) of the surface of the titanium foil used in Examples 4 and 5 was 0.02 μm in Example 4 and 0.12 μm in Example 5.

In Example 6, a JIS 1 type titanium foil of 150 mm × 70 mm × 0.04 mm thickness was used, and in Example 7, a JIS 1 type titanium foil of 150 mm × 70 mm × 0.06 mm thickness was used. The arithmetic mean roughness (Ra) of the surface of the titanium foil used in Examples 6 and 7 was 0.6 μm in Example 6 and 0.7 μm in Example 7.

In Comparative Examples 1 and 2, a JIS 1 type titanium foil of 150 mm × 70 mm × 0.1 mm thickness was used, and in Comparative Example 3, a JIS 1 type titanium foil of 150 mm × 70 mm × 0.2 mm thickness was used. .. The arithmetic mean roughness (Ra) of the surface of the titanium foil used in Comparative Examples 1 to 3 was 4.7 μm in Comparative Example 1, 5.5 μm in Comparative Example 2, and 6.2 μm in Comparative Example 3.

The titanium foils of Examples 1 to 7 and Comparative Examples 1 to 3 described above are placed horizontally, zinc powder for inorganic zinc (average particle size 4 to 8 μm) is sprinkled on the surface of the titanium foil, and then washed with water. The zinc powder was removed. An immersion test was conducted in which the titanium foil subjected to this treatment was immersed in artificial seawater in a stationary state maintained at 30 ° C. in the air for 30 days. After the immersion test is completed, a small piece for observing a cross section having a size of 30 mm × 5 mm × 0.1 mm in thickness is cut out from the test piece, embedded in resin, the cross section is polished, the surface portion is etched, and the surface portion is etched 200 times with an optical microscope. The cross-sectional structure was observed at the same magnification as, and the presence or absence of hydride formation was observed. In Comparative Examples 1 to 3, white corrosion products (basic zinc chloride) were sparsely adhered to the surface of the titanium foil after the completion of the immersion test, so that the small pieces for cross-section observation were the corrosion products. It was cut out from the adhered part.

The surface roughness meter (Handysurf E-35A) manufactured by Tokyo Precision Co., Ltd. was used for the arithmetic average roughness (Ra) of the surface of the titanium foil used in Examples 1 to 7 and Comparative Examples 1 to 3 above. The thickness of the oxide film on the surface of the titanium foil used was measured by Auger electron spectroscopy using the Auger microprobe JAMP-9500F manufactured by JEOL Ltd.

The above results are shown in Table 1 below.

As shown in Table 1, in Examples 1 to 7 in which the arithmetic mean roughness Ra of the surface of the titanium foil was 3.9 μm or less, no hydride was formed on the titanium foil even after the immersion test. In "(3) Examination of the relationship between the thickness of the oxide film on the surface of the titanium foil and the formation of the hydride" described later, the condition that the zinc powder is pressed against the surface of the titanium foil is imposed, but Examples 1 to 7 and The conditions are not imposed in Comparative Examples 1 to 3, and in Examples 1 to 7, the arithmetic average roughness Ra of the titanium foil surface is 3.9 μm regardless of the thickness of the oxide film on the titanium foil surface. In the following cases, it is considered that the zinc powder on the surface of the titanium foil was removed by washing with water before the immersion test, and the zinc powder did not adhere to the surface of the titanium foil. On the other hand, in Comparative Examples 1 to 3 in which the arithmetic mean roughness Ra of the surface of the titanium foil exceeds 3.9 μm, since a hydride is formed on the titanium foil after the immersion test, the oxide film on the surface of the titanium foil The zinc powder was not removed regardless of the thickness, and it is probable that the zinc powder adhered to the surface of the titanium foil subjected to the immersion test in Comparative Examples 1 to 3.

In Examples 1 to 7 and Comparative Examples 1 to 3 described above, the relationship between the arithmetic average roughness (Ra) on the surface of the titanium foil and the formation of hydrides on the surface of the titanium foil was evaluated. As an example and a comparative example, the titanium foil is a layer provided on the outermost layer of the anticorrosion coating according to the present invention, and is an anticorrosion layer, an adhesive layer, etc. arranged between the titanium foil and a metal base material. Does not affect the formation of titanium hydrides. Therefore, the experimental results for the titanium foils of Examples 1 to 7 and Comparative Examples 1 to 3 described above can be regarded as the experimental results of the anticorrosion coating according to the present invention containing the titanium foil as a component.

(2) Examination of Titanium Foil Thickness and Aroundness (Examples 8 to 13 and Example 14 (Reference Example 1))
Next, with respect to the titanium foil having an arithmetic mean roughness Ra of the surface of 3.9 μm or less, the relationship between the thickness and the wrapping property (the wrapping property of the titanium foil at the edge portion of the metal base material) was evaluated. The surface of 150 mm long equilateral angle steel (90 mm x 90 mm x 6.0 mm thick) blasted using a steel grid is spray coated with inorganic zinc rich paint to a thickness of 75 μm for 3 days at room temperature. After drying to provide an undercoat layer, an epoxy resin-based anticorrosive paint was spray-coated on the undercoat layer and dried at room temperature for 2 days to form an anticorrosion layer having a thickness of 120 μm on the surface of the substrate (the equilateral angle steel). Corresponds to the metal substrate 90 in the anticorrosion coatings 10 and 20 of the first and second embodiments described above). After that, the thicknesses are 10 μm (Example 8), 20 μm (Example 9), 40 μm (Example 10), 60 μm (Example 11), 100 μm (Example 12), 150 μm (Example 13), 180 μm (Example 13). A metal foil member constructed by previously pasting an acrylic double-sided adhesive tape (manufactured by Teraoka Seisakusho Co., Ltd., NO. 7642) on one side of the titanium foil of Example 14 (Reference Example 1) is pasted on the surface of the anticorrosion layer. I attached it. The support of the acrylic double-sided adhesive tape used is a polyethylene terephthalate film (corresponding to the stretchable resin layer 24A), and acrylic adhesives (corresponding to the adhesive layers 22A and 26A) are provided on both sides thereof. At the time of pasting, the edge portion of the equilateral angle steel was pasted by bending the metal foil member so as to fit the edge portion by hand. After the metal foil member was attached in this way, the metal foil member was crimped to the equilateral angle steel by a silicone rubber roller. After crimping, the metal leaf member was peeled off, and it was confirmed whether there was any non-adhered portion.

The arithmetic average roughness (Ra) of the surface of the titanium foil used was measured using a surface roughness meter (Handysurf E-35A) manufactured by Tokyo Precision Co., Ltd., and the surface oxidation of the titanium foil used was oxidized. The thickness of the film is measured by Auger electron spectroscopy using the Auger microprobe JAMP-9500F manufactured by JEOL Ltd.

The above results are shown in Table 2 below.

As shown in Table 2, in Examples 8 to 13 in which the thickness of the titanium foil is 10 μm or more and 150 μm or less, there is no non-adhered portion even around the edge, the wrapping property is good, and the titanium foil has an equilateral chevron shape. It adhered well to the steel.

On the other hand, Example 14 (Reference Example 1) in which the thickness of the titanium foil is 180 μm satisfies the above-mentioned condition that no hydride is generated on the surface of the titanium foil (the arithmetic average roughness Ra of the surface of the titanium foil is 3.9 μm or less). However, a non-adhered portion was observed around the edge, and the adhered state was not good, and the wrapping property was not good. Therefore, Example 14 is indicated as Reference Example 1 in parentheses.

When the thickness of the titanium foil exceeds 150 μm, the bending rigidity of the titanium foil becomes too large, and springback (a phenomenon in which the plate-shaped material returns to its original state when bent) occurs. Therefore, Example 14 (Reference) It is probable that the above phenomenon of Example 1) occurred. Therefore, it is not very preferable to use the titanium foil of Example 14 (Reference Example 1) for a member that receives a large bending.

(3) Examination of the relationship between the thickness of the oxide film on the surface of the titanium foil and the formation of hydrides (Examples 15 to 17, Example 18 (Reference Example 2))
An evaluation was carried out to confirm how the thickness of the oxide film on the surface of the titanium foil is related to the formation of hydride on the surface of the titanium foil when zinc powder adheres to the surface of the titanium foil.

Titanium foil (150 mm × 70 mm ×) having a surface arithmetic mean roughness (Ra) of 0.8 μm in JIS type 1 and a surface arithmetic mean roughness (Ra) of 3.9 μm or less as in Examples 1 to 14. The thickness (0.1 mm) was maintained at 620 ° C. in an air atmosphere to increase the thickness of the oxide film on the surface of the titanium foil. At that time, three types of samples (Examples 15 to 17) having different thicknesses of the oxide film were prepared by changing the holding time at 620 ° C. in the air atmosphere. The thicknesses of the oxide film on the surface of the titanium foils of Examples 15, 16 and 17 were 5.7 nm, 9.0 nm and 12.6 nm, respectively.

Further, a titanium foil (150 mm × 70 mm × thickness 0.1 mm) having a surface arithmetic mean roughness (Ra) of 0.8 μm as in Examples 15 to 17 in JIS type 1 is used as a mixed solution of nitric acid and hydrofluoric acid. The oxide film on the surface of the titanium foil was removed by pickling inside. The thickness of the oxide film on the surface of the titanium foil after pickling was 1.3 nm, and this sample was designated as Example 18 (Reference Example 2).

Then, the titanium foils of Examples 15 to 17 and Example 18 (Reference Example 2) produced as described above were placed horizontally, and zinc powder for inorganic zinc (average particle size 4 to 8 μm) was applied to the titanium foil. After sprinkling each on the surface, the zinc powder was strongly pressed against the titanium foil with a stainless steel roller, and the zinc powder was inlaid on the surface of the titanium foil.

This is a process for confirming how the thickness of the oxide film on the surface of the titanium foil affects the formation of hydride on the surface of the titanium foil when zinc powder adheres to the surface of the titanium foil. For example, after forming an anticorrosion coating on an offshore structure, a worker walks on the anticorrosion coating for work such as installing handrails, pipes, and wiring, and the zinc powder is strongly pressed against the titanium foil. Corresponds to.

After the work of inlaying the zinc powder on the surface of the titanium foil, it was washed with water to remove the excess zinc powder. An immersion test was conducted in which the titanium foil subjected to this treatment was immersed in artificial seawater in a stationary state maintained at 30 ° C. in the air for 30 days.

After the immersion test is completed, in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 3, it is necessary to confirm the presence or absence of hydride formation in the samples of Examples 15 to 17 and Example 18 (Reference Example 2). Cross-sectional structure observation was performed. In Example 18 (Reference Example 2), white corrosion products (basic zinc chloride) were sparsely adhered to the surface of the titanium foil after the completion of the immersion test, so that the small pieces for cross-section observation were corroded. It was cut out from the part where the product was attached.

The arithmetic mean roughness (Ra) and the thickness of the oxide film on the surface of the titanium foil (titanium foil before the immersion test) used were determined in Examples 1 to 7, Comparative Examples 1 to 3 and Examples 8 to 13. The measurement was carried out in the same manner as in Example 14 (Reference Example 1).

The above results are shown in Table 3 below.

As described above, zinc powder is inlaid on the surfaces of the titanium foils of Examples 15 to 17 and Example 18 (Reference Example 2), and even after the surfaces are washed with water, the inlaid zinc powder is the surface of the titanium foil. It is thought that it will stay in.

However, as shown in Table 3, no hydride was formed on the surface of the titanium foils of Examples 15 to 17 after the completion of the immersion test. It is considered that this is because the thickness of the oxide film on the surface of the titanium foil of Examples 15 to 17 is as large as 5.7 nm to 12.6 nm, so that electricity does not easily flow to the surface of the titanium foil and the generation of hydrogen is suppressed. Be done.

On the other hand, a small amount of hydride is formed on the surface of the titanium foil of Example 18. It is considered that this is because the thickness of the oxide film on the surface of the titanium foil of Reference Example 1 is as small as 1.3 nm, so that electricity easily flows on the surface of the titanium foil and the generation of hydrogen cannot be suppressed. In Example 18, since hydride was generated, it is shown in parentheses as Reference Example 2.

When the film thickness of the oxide film on the surface of the titanium foil is small as in Example 18 (Reference Example 2), it is assumed that the worker will press the zinc powder on the titanium foil for the construction of marine structures. It is considered to be somewhat unsuitable for use.

In Examples 15 to 17 and Example 18 (Reference Example 2) described above, the relationship between the thickness of the oxide film on the surface of the titanium foil and the formation of hydride on the surface of the titanium foil was evaluated. As an example, only the titanium foil, which is one of the constituent elements of the anticorrosion coating according to the present invention, is taken out and an experiment is conducted. The titanium foil is a layer provided on the outermost layer of the anticorrosion coating according to the present invention. Since the anticorrosion layer and the adhesive layer arranged between the titanium foil and the metal base material do not affect the formation of the titanium hydride, Examples 15 to 17 and Example 18 (Reference Example 2). The experimental result of titanium foil can be regarded as the experimental result of the anticorrosion coating according to the present invention containing titanium foil as a constituent element.

(4) Examination of the effect of suppressing the progress of peeling (Examples 19 to 36, Examples 37 to 42 (Reference Examples 3 to 8))
From the results of Examples 1 to 18 and Comparative Examples 1 to 3 described above, it is possible to obtain a titanium foil in which hydrides are less likely to be formed on the surface of the titanium foil and the titanium foil has good adhesion even around the edge of the metal base material. Specific examples of the conditions include a thickness of 20 μm or more and 80 μm or less, a surface arithmetic mean roughness (Ra) of 1.8 μm or less, and a surface oxide film thickness of 2.1 nm or more.

Using a titanium foil satisfying this condition, a titanium foil having a thickness of 40 μm, a surface arithmetic mean roughness (Ra) of 0.68 μm, and a surface oxide film thickness of 2.1 nm was used as an undercoat layer. Various anticorrosion coating samples were prepared by changing the anticorrosion layer and the adhesive layer. As the metal substrate, a steel plate having a thickness of 150 mm × 70 mm × thickness 0.1 mm blasted using a steel grid was used.

Then, a cut (artificial scratch) having a length of 5 cm is made in the prepared anticorrosion coating sample, and an immersion test is performed. After the immersion test is completed, the left and right peeling lengths centered on the cut (artificial scratch) (see FIG. 3) The maximum value of is measured, and the one having a peeling length of 10 mm or less is evaluated as passing, and the one having a peeling length longer than 10 mm is evaluated as failing. It was confirmed that even if there was, peeling did not progress easily. FIG. 3 is an enlarged schematic view schematically showing a portion in which a notch (artificial scratch) having a length of 5 cm is made in the anticorrosion coating sample, in which reference numeral 50 is an anticorrosion coating and reference numeral 52 is a notch (human). (Scratch), and reference numeral 54 is a peeling region. Reference numeral 56 indicates a peeling length, and the length of the arrow pointed to by reference numeral 56 indicates the peeling length.

Hereinafter, the configuration of each anticorrosion coating sample, experimental conditions, measured peeling length, and the like will be specifically described.

(4-1) Example 19
On the surface of a 150 mm × 70 mm × 0.1 mm thick steel sheet blasted using a steel grid, an inorganic zinc rich paint was spray-coated to a thickness of 75 μm and dried at room temperature for 3 days to provide an undercoat layer. After that, an epoxy resin-based anticorrosive paint was spray-coated on the undercoat layer and dried at room temperature for 2 days to form an anticorrosive layer having a film thickness of 120 μm on the surface of the substrate.

Next, after applying an epoxy resin adhesive with a brush to a thickness of 35 μm, the thickness is 40 μm, the surface arithmetic mean roughness (Ra) is 0.6 μm, and the thickness of the oxide film on the surface is 2.1 nm. Titanium foil was attached to the surface of the formed anticorrosion layer and adhered with a silicone rubber roller to prepare an anticorrosion coating sample. A notch (artificial scratch) 52 reaching the steel plate substrate was formed in the prepared anticorrosion coating sample with a mini drill so as to have a length of 5 cm. An anticorrosion coating sample having a notch (artificial wound) 52 was immersed in a 3% NaCl aqueous solution at 50 ° C. for 100 days for an immersion test. After the immersion test was completed, the anticorrosion coating was peeled off, and the maximum value of the left and right peeling lengths 56 (see FIG. 3) centered on the notch (artificial scratch) 52 was measured and found to be 6.1 mm, which was acceptable.

(4-2) Examples 20 to 22
Except for changing the adhesive to which the titanium foil is attached to a urethane resin adhesive (Example 20), a silicone resin adhesive (Example 21), and an acrylic resin adhesive (Example 22). In the same manner as in Example 19, each of the anticorrosion coating samples of Examples 20 to 22 was prepared and subjected to a dipping test, and the maximum value of the left and right peeling lengths 56 (see FIG. 3) centered on the notch (artificial scratch) 52. 20 was 7.8 mm, Example 21 was 7.7 mm, and Example 22 was 7.1 mm, all of which were acceptable.

(4-3) Examples 23 to 26
Acrylic resin-based pressure-sensitive adhesive sheet (Example 23), urethane resin-based pressure-sensitive adhesive sheet (Example 24), silicone resin-based pressure-sensitive adhesive sheet (Example 25), and rubber-based adhesive are used as the adhesive to attach the titanium foil. In the same manner as in Example 19 except that the agent sheet (Example 26) was changed, each anticorrosion coating sample of Examples 23 to 26 was prepared and an immersion test was performed, centering on the notch (artificial wound) 52. When the maximum values of the left and right peeling lengths 56 (see FIG. 3) were measured, Example 23 was 6.5 mm, Example 24 was 6.7 mm, Example 25 was 7.0 mm, and Example 26 was 6.3 mm. And all passed.

(4-4) Examples 27 to 31
The undercoat layer was composed of organic zinc rich paint 75 μm (Example 27), epoxy resin paint 50 μm (Example 28), modified epoxy resin paint 50 μm (Example 29), etching primer 15 μm (Example 30), and no undercoat layer. Except for the change to (Example 31), each of the anticorrosion coating samples of Examples 27 to 31 was prepared and subjected to a dipping test in the same manner as in Example 19, and the left and right sides centered on the notch (artificial wound) 52. When the maximum value of the peeling length 56 (see FIG. 3) was measured, Example 27 was 5.1 mm, Example 28 was 4.8 mm, Example 29 was 7.0 mm, and Example 30 was 9.5 mm. Example 31 was 9.2 mm, and all passed.

(4-5) Examples 32 to 34
Except that the anticorrosion layer was changed to 800 μm of epoxy resin paint containing glass fiber (GF) (Example 32), 120 μm of modified epoxy resin paint (33), and 2000 μm of ultra-thick epoxy resin paint (34). In the same manner as in Example 19, each of the anticorrosion coating samples of Examples 32 to 34 was prepared and subjected to a dipping test, and the maximum left and right peeling length 56 (see FIG. 3) centered on the notch (artificial scratch) 52 was performed. When the values were measured, Example 32 was 6.6 mm, Example 33 was 6.0 mm, and Example 34 was 3.2 mm, all of which were acceptable.

(4-6) Examples 35, 36
Double-sided tape (acrylic resin-based adhesive double-sided tape 1) (Example 35) with acrylic resin-based adhesive on both sides of the polyethylene film, acrylic resin-based adhesive on polyester fiber non-woven fabric Anticorrosion coating samples of Examples 35 and 36 were prepared in the same manner as in Example 19 except that the double-sided tape to which the adhesive was attached (acrylic resin-based adhesive double-sided tape 2) (Example 36) was changed. An immersion test was performed to measure the maximum value of the left and right peeling lengths 56 (see FIG. 3) centered on the notch (artificial scratch) 52. As a result, Example 35 was 5.1 mm and Example 36 was 5.0 mm. Yes, both passed.

The adhesive used in Examples 35 and 36 contains an extensible layer (extensible resin layer or extensible non-woven fabric), and the extensible layer used in Example 35 is an extensible resin layer. The extensible layer used in Example 36 is a non-woven fabric made of polyester fiber, which is an extensible non-woven fabric.

Instead of the extensible layer used in Examples 35 and 36, polypropylene, vinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyvinyl alcohol, polyvinylidene chloride, nylon, polycarbonate, ethylene vinyl acetate copolymer , At least one extendable resin layer selected from the group consisting of polyimide, silicone resin, acrylic resin, or glass fiber, nylon fiber, polyester (polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate) fiber, polyamide fiber, At least one stretchable non-woven fabric selected from the group consisting of polyethylene fiber, polypropylene fiber, rayon fiber, vinylon fiber, acrylic fiber, or urethane foam, natural rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, butadiene rubber, nitrile rubber. Even if at least one stretchable layer selected from the group consisting of ethylene propylene diene rubber (EPDM), silicone rubber, urethane rubber, and fluorine rubber is used as the stretchable layer, they do not react with moisture. Moreover, since water does not permeate through the interface or water vapor does not pass through, it is considered that the corrosion factor and the corrosion promoting factor are hard to infiltrate, and the same effect as in Examples 35 and 36 can be obtained.

(4-7) Examples 37 and 38 (Reference Examples 3 and 4)
Examples except that the adhesive for attaching the titanium foil was changed to a vinyl acetate adhesive (Example 37 (Reference Example 3)) and a nitrile rubber adhesive (Example 38 (Reference Example 4)). In the same manner as in 19, each anticorrosion coating sample of Examples 37 and 38 (Reference Examples 3 and 4) was prepared and subjected to an immersion test, and the left and right peeling lengths 56 centering on the notch (artificial scratch) 52 (Fig. When the maximum value of (see 3) was measured, it was 15.2 mm in Example 37 (Reference Example 3) and 20.5 mm in Example 38 (Reference Example 4), both of which had a notch (artificial scratch). No good results were obtained regarding the difficulty of progress of peeling.

Since the vinyl acetate-based adhesive used in Example 37 (Reference Example 3) decomposes by reacting with moisture, the titanium foil is peeled off after the immersion test, and therefore the peeling length after the immersion test is long. It is probable that it has become.

Further, the nitrile rubber adhesive used in Example 38 (Reference Example 4) has a good affinity with water, and water permeates through the interface, so that corrosion factors and corrosion promoting factors easily infiltrate. It is probable that the peeling length after the immersion test became longer.

(4-8) Example 39 (Reference Example 5)
An anticorrosion coating sample of Example 39 (Reference Example 5) was prepared and subjected to a dipping test in the same manner as in Example 19 except that the undercoat layer was changed to an oil-based rust preventive paint of 35 μm, and a notch (artificial scratch) 52 was performed. The maximum value of the left and right peeling lengths 56 (see FIG. 3) centered on the above was measured and found to be 23.0 mm. If there is a notch (artificial scratch), it is good that the peeling does not progress easily. No results were obtained.

The oil-based rust preventive paint used in Example 39 (Reference Example 5) has a weak adhesive force and a weak corrosion resistance, so that corrosion factors and corrosion promoting factors easily infiltrate, and therefore, the peeling length after the immersion test becomes long. It is thought that it has become longer.

(4-9) Examples 40 to 42 (Reference Examples 6 to 8)
The anticorrosion layer was 35 μm of rubber chloride resin paint (Example 40 (Reference Example 6)), 50 μm of acrylic silicone resin paint (Example 41 (Reference Example 7)), and 35 μm of fluororesin-based paint (Example 42 (Reference Example 8)). ), Each of the anticorrosion coating samples of Examples 40 to 42 (Reference Examples 6 to 8) was prepared and subjected to a dipping test in the same manner as in Example 19, with the notch (artificial scratch) 52 as the center. When the maximum value of the left and right peeling lengths 56 (see FIG. 3) was measured, it was 18.8 mm in Example 40 (Reference Example 6) and 20.6 mm in Example 41 (Reference Example 7). 42 (Reference Example 8) was 22.3 mm, and in each case, when there was a notch (artificial scratch), good results were not obtained regarding the difficulty of progress of peeling.

The rubber chloride resin paint used in Example 40 (Reference Example 6), the acrylic silicone resin paint used in Example 41 (Reference Example 7), and the fluororesin paint used in Example 42 (Reference Example 8) are Since water vapor is allowed to pass through, corrosion factors and corrosion promoting factors are likely to infiltrate, and it is considered that the peeling length after the immersion test is long.

(4-10) Composition of Anticorrosion Coating Samples of Examples 19 to 36 and Examples 37 to 42 (Reference Examples 3 to 8) and Summary of Experimental Results Table 4 below shows Examples 19 to 36 and Examples 37 to 37 to The composition and experimental results of the anticorrosion coating sample of 42 (Reference Examples 3 to 8) are summarized. When the peeling length is acceptable (peeling length is 10 mm or less), it is marked with ◯, and when it is rejected (peeling length is more than 10 mm), it is marked with x.

Since the results of Examples 37 to 42 are unsuitable for the peeling length, they are shown in parentheses as Reference Examples 3 to 8, respectively.

10, 20, 50 ... Anticorrosion coating 12 ... Undercoat layer 14 ... Anticorrosion layer 16 ... Adhesive layer 16A, 22A, 26A ... Adhesive layer 16B, 22B, 26B ... Adhesive layer 18 ... Metal foil 22 ... First adhesive adhesion Layer 24 ... Stretchable layer 24A ... Stretchable resin layer 24B ... Stretchable non-woven fabric 26 ... Second adhesive layer 52 ... Cut (artificial scratch)
54 ... Peeling area 56 ... Peeling length 90 ... Metal substrate

Claims (11)

On the surface of the metal substrate, from the side closer to the surface
(1) Anticorrosion layer substantially formed of epoxy resin-based paint,
(2) Adhesive layer substantially formed by an adhesive or an adhesive,
(3) A metal foil substantially formed of titanium or a titanium alloy having an arithmetic mean roughness of the surface of 3.9 μm or less.
The anticorrosion coating comprising the anticorrosion layer, the adhesive layer, and the metal foil in the order of. The anticorrosion coating according to claim 1, wherein an oxide film having a thickness of 2.1 nm or more is substantially formed on the surface of the metal foil. The adhesive layer was selected from the group consisting of rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. The anticorrosion coating according to claim 1 or 2, characterized in that it is substantially formed of at least one adhesive or adhesive. The adhesive layer includes a first adhesive layer and a second adhesive layer in order from the side closest to the surface of the metal base material, and the first adhesive layer and the second adhesive layer. The anticorrosion coating according to any one of claims 1 to 3, wherein an stretchable layer is provided between the adhesive layer and the adhesive layer. The expandable layer includes polyethylene, polypropylene, vinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyvinyl alcohol, polyvinylidene chloride, nylon, polycarbonate, ethylene vinyl acetate copolymer, polyimide, silicone resin, and acrylic. An extendable resin layer substantially formed of at least one selected from the group consisting of resins, or glass fiber, nylon fiber, polyester fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, rayon fiber, vinylon fiber, acrylic fiber. An stretchable non-woven fabric substantially formed of at least one selected from the group consisting of, or urethane foam, natural rubber, chloroprene rubber, ethylene propylene rubber, butyl rubber, butadiene rubber, nitrile rubber, ethylene propylene diene rubber. The anticorrosion coating according to claim 4, wherein the anticorrosion coating is substantially formed of at least one selected from the group consisting of (EPDM), silicone rubber, urethane rubber, and fluorine rubber. The anticorrosion coating according to any one of claims 1 to 5, wherein the thickness of the metal foil is 10 μm or more and 150 μm or less. An undercoat substantially formed between the surface of the metal substrate and the anticorrosion layer using at least one of an inorganic zinc rich paint, an organic zinc rich paint, an epoxy resin-based paint, and a modified epoxy resin-based paint. The anticorrosion coating according to any one of claims 1 to 6, wherein a layer is provided. An anticorrosion layer forming process for forming an anticorrosion layer on the surface of a metal substrate,
A metal foil member produced by laminating an adhesive layer to a metal foil substantially formed of titanium or a titanium alloy is applied to the anticorrosion layer formed in the anticorrosion layer forming step. The metal foil pasting process and
Have,
A method for forming an anticorrosion coating, wherein the arithmetic mean roughness of the surface of the metal foil opposite to the adhesive layer is 3.9 μm or less. A paper pattern is previously attached to the adhesive layer of the metal foil member, and in the metal foil attaching step, the paper pattern is peeled off and the metal foil member is placed on the anticorrosion layer. The method for forming an anticorrosion coating according to claim 8, wherein the adhesive layer is attached. In the metal foil pasting step, the following order (1) to (4), that is,
(1) The surface is substantially formed of titanium or a titanium alloy having an arithmetic mean roughness of 3.9 μm or less and an oxide film having a thickness of 2.1 nm or more substantially formed on the surface. Metal leaf,
(2) At least one selected from the group consisting of rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. A second adhesive layer, substantially formed of adhesive or adhesive,
(3) Consists of polyethylene, polypropylene, vinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyvinyl alcohol, polyvinylidene chloride, nylon, polycarbonate, ethylene vinyl acetate copolymer, polyimide, silicone resin, acrylic resin. An extensible resin layer substantially formed by at least one selected from the group, or a group consisting of glass fiber, nylon fiber, polyester fiber, polyamide fiber, polyethylene fiber, polypropylene fiber, rayon fiber, vinylon fiber, acrylic fiber. Stretchable non-woven fabric substantially formed of at least one selected from, or urethane foam, natural rubber, chloroprene rubber, polyethylene propylene rubber, butyl rubber, butadiene rubber, nitrile rubber, ethylene propylene diene rubber (EPDM), silicone rubber. An stretchable layer substantially formed of at least one selected from the group consisting of, urethane rubber, and fluororubber.
(4) At least one selected from the group consisting of rubber-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives, and epoxy resin-based, acrylic resin-based, urethane resin-based and silicone resin-based adhesives. A first adhesive layer, substantially formed of an adhesive or adhesive,
8. The method according to claim 8 or 9, wherein the metal foil members laminated in the order of the above are attached to the anticorrosion layer formed in the anticorrosion layer forming step by the first adhesive layer. Method of forming anticorrosion coating. A paper pattern is previously attached to the first adhesive layer of the metal foil member, and in the metal foil attaching step, the paper pattern is peeled off and the metal is placed on the anticorrosion layer. The method for forming an anticorrosion coating according to claim 10, wherein the first adhesive layer of the foil member is attached.

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