WO2017159430A1 - Matériau en acier revêtu de résine et procédé pour sa fabrication - Google Patents

Matériau en acier revêtu de résine et procédé pour sa fabrication Download PDF

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Publication number
WO2017159430A1
WO2017159430A1 PCT/JP2017/008793 JP2017008793W WO2017159430A1 WO 2017159430 A1 WO2017159430 A1 WO 2017159430A1 JP 2017008793 W JP2017008793 W JP 2017008793W WO 2017159430 A1 WO2017159430 A1 WO 2017159430A1
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Prior art keywords
urethane resin
mass
layer
polyol
carbon black
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PCT/JP2017/008793
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English (en)
Japanese (ja)
Inventor
吉崎　信樹
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新日鐵住金株式会社
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Application filed by 新日鐵住金株式会社 filed Critical 新日鐵住金株式会社
Priority to JP2018505822A priority Critical patent/JP6551599B2/ja
Priority to SG11201806227RA priority patent/SG11201806227RA/en
Priority to AU2017234095A priority patent/AU2017234095B8/en
Publication of WO2017159430A1 publication Critical patent/WO2017159430A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a steel material (resin-coated steel material) coated with urethane resin and a method for producing the same.
  • Urethane resin coating is generally a non-solvent spray coating of a two-component polyurethane resin composition prepared by mixing a main agent containing various polyols and a curing agent mainly composed of an aromatic isocyanate. Formed with. Since this urethane elastomer composition has a high viscosity and a high curing speed, a thick coating of 2 mm or more can be achieved by a single coating.
  • the urethane resin composition can be applied not only to steel pipe piles but also to steel materials having complicated shapes, such as steel pipe sheet piles and steel sheet piles.
  • a highly reliable anticorrosion layer is required to prevent the wrinkles from reaching the steel material even when wrinkles occur in the anticorrosion layer.
  • the highly reliable anticorrosion layer has a thick urethane resin coating excellent in impact resistance.
  • a heavy anticorrosion coating method using this urethane resin coating is a standard anticorrosion method in Japan. Urethane resin-coated steel materials are mainly produced in factories because they require surface treatment, painting equipment, and painting technology.
  • Urethane resin is generally not a resin with good weather resistance. For this reason, it is difficult to color the urethane resin other than black in a corrosive environment. If carbon black is added to the urethane resin, a black urethane resin is obtained, and the deterioration of the urethane resin due to ultraviolet rays is suppressed by the carbon black. Therefore, even if the urethane resin is deteriorated by ultraviolet rays and the urethane resin coating is worn out, the ratio of the depth of wear to the total thickness of the urethane resin film is sufficiently small.
  • an ultraviolet absorber or an antioxidant is added to the urethane resin.
  • the urethane resin is a thermosetting resin, it is difficult for the additive to move inside the resin. Therefore, the effect that an additive prevents deterioration of urethane resin is small.
  • the coating on steel materials is used not only to protect the steel materials from corrosion but also to impart a predetermined design (appearance) to the steel materials.
  • a top coat colored in a color different from that of the lower layer is easily used.
  • the top coat is required not to be discolored by ultraviolet rays. For this reason, a fluorine-based or silicon-based topcoat is recognized as an excellent topcoat with little discoloration because bonds between molecules are not easily broken by ultraviolet rays.
  • Patent Document 1 discloses a method of coating a colored acrylic urethane resin having the same color as the colored urethane resin on the surface of the colored urethane resin in order to maintain the design for a long period of time.
  • both resins are colored in a color other than black, and weather resistance (fading resistance) is emphasized. Therefore, the polyurethane elastomer coating layer contains an aliphatic isocyanate which is inferior in corrosion resistance but has high weather resistance.
  • Patent Document 2 discloses a method of forming an acrylic urethane resin layer on an anticorrosion layer containing a urethane resin in order to prevent discoloration of the resin.
  • the weather resistance of acrylic urethane resin coating is confirmed by an accelerated weather resistance test using a sunshine weather meter.
  • a polymer polyol such as a hydroxyl-terminated polybutadiene is used as an essential component of the polyurethane resin.
  • Patent Document 3 discloses a method of applying a colored coating film other than black on a black urethane elastomer layer at a position higher than the tidal zone. In the method of Patent Document 3, an excellent aesthetic appearance can be maintained for a long time by the colored coating film.
  • the purpose of the present invention is to prevent deterioration and wear of the urethane resin coating even when it is used as a material for a structure for a long period of time in the ocean, and the urethane resin coating that allows the urethane resin to continue to prevent corrosion of steel. It is to provide steel. Another object of the present invention is to provide a method for producing such a heavy anticorrosion urethane resin-coated steel material.
  • the gist of the present invention is as follows.
  • a resin-coated steel material includes a steel material, a primer layer on the surface of the steel material, a urethane resin layer on the surface of the primer layer, and a top coat on the surface of the urethane resin layer.
  • the urethane resin layer includes an inorganic pigment containing carbon black, and a urethane resin having a urethane bond composed of a constituent atom of a hydroxyl group of a polyol and an isocyanate group of an isocyanate, and the topcoat layer is made of carbon black.
  • an acrylic urethane resin and the polyol contains a castor oil derivative having 2.7 or more hydroxyl groups per molecule and an organic composition having 2.0 hydroxyl groups per molecule, , Diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate And at least one selected from the group consisting of toluene diisocyanate derivatives, and in the urethane resin layer, the mass obtained by subtracting the mass of the isocyanate from the mass of the urethane resin layer is defined as the mass of the main agent.
  • the mass of black is 0.2 to 5.0% of the mass of the main agent
  • the mass obtained by subtracting the mass of the carbon black from the mass of the inorganic pigment is 10 to 60% of the mass of the main agent
  • the castor oil is 10 to 70% of the mass of the main agent
  • the mass of the carbon black is 0.2 to 5.0% of the mass of the top coat layer.
  • a method for producing a resin-coated steel material according to an aspect of the present invention includes: applying a primer on a surface of a steel material to form a primer layer; and a liquid mixture comprising a main agent and a curing agent on the surface of the primer layer.
  • the liquid mixture is cured to form a urethane resin layer, an acrylic urethane resin paint containing carbon black is applied to the surface of the urethane resin layer, and the acrylic urethane resin paint is cured to form a topcoat layer.
  • the main component includes an inorganic pigment containing carbon black and a polyol
  • the curing agent is composed of diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate derivative, and toluene diisocyanate derivative.
  • the polyol contains a castor oil derivative having 2.7 or more hydroxyl groups per molecule and an organic composition having 2.0 hydroxyl groups per molecule.
  • the mass of carbon black is the mass of the main agent.
  • the mass obtained by subtracting the mass of the carbon black from the mass of the inorganic pigment is 10 to 60% of the mass of the main agent, and the mass of the castor oil derivative is the mass of the main agent.
  • the mass of the carbon black is 0.2 to 5.0% of the mass of the acrylic urethane resin paint.
  • the top coat layer protects the urethane resin layer from the ultraviolet ray and water even in an environment exposed to ultraviolet rays and water such as the ocean, the urethane resin layer prevents the steel material from corrosion over a long period of time. Can do. Therefore, according to the above aspect of the present invention, it has high durability even under conditions exposed to water, such as the ocean, particularly in the region from the tidal zone to the mid-sea that is affected by both ultraviolet rays and moisture. A resin coating can be provided. Therefore, according to the said aspect of this invention, the low-cost structure which has high durability on the conditions exposed to water, such as the ocean, can be comprised.
  • the inventor examined a method for preventing the wear of the urethane resin due to ultraviolet rays, water, etc., and maintaining the durability of the heavy anticorrosion coating over a long period of time.
  • the inventor formed a thin film protective layer for improving the weather resistance on the surface of the urethane resin layer as the means.
  • the present inventor used an acrylic urethane resin that is considered to have high adhesion to the urethane resin layer. Since the curing speed of the urethane resin layer was fast, the top coat (thin film protective layer) was applied after the urethane resin layer was cured. However, the urethane resin-coated steel material obtained by this method cannot prevent the resin from corrosion over a long period of time. As a result of studying the reason by the present inventors, it has been found that it is difficult to stably obtain sufficient adhesion to the urethane resin layer of the top coat layer of the urethane-coated steel material.
  • the purpose of the conventional top coat was to impart the design to the steel material, and therefore, little study has been made on the adhesion of the top coat to the urethane resin.
  • the relationship between multiple factors (eg, UV and water) and adhesion in an actual environment has not been recognized.
  • a fluorine-based or silicon-based modified resin has lower adhesion to a urethane resin than a general acrylic urethane resin.
  • the adhesiveness of these modified resins in the short period in the air is sufficient for ordinary applications, the adhesiveness has hardly been discussed.
  • the present inventor examined the reason why the adhesion of the top coat layer to the urethane resin layer is not sufficient even if the top coat layer contains an acrylic urethane resin.
  • the acrylic urethane resin is bonded to the lower layer mainly by hydrogen bonding due to molecular polarity and a throwing effect due to surface irregularities. Therefore, the number of chemical bonds is relatively small between the acrylic urethane resin and the lower layer. In this case, moisture easily enters between the acrylic urethane resin and the lower layer. Therefore, even if the acrylic urethane resin has sufficient adhesion to the lower layer in the atmosphere, the adhesion of the acrylic urethane resin to the lower layer easily decreases in water. Therefore, the present inventor has studied a method in which the surface of the urethane resin layer can form a chemical bond with the acrylic urethane resin even after the urethane resin layer is cured with respect to the chemical component of the urethane resin.
  • the urethane bond is formed by the hydroxyl group (—OH) of the polyol in the main agent and the isocyanate group (—NCO) of the curing agent. Therefore, the present inventor has studied a method of leaving these functional groups, which are considered to be able to adhere the acrylic urethane resin to the urethane resin layer by urethane bonds, on the surface of the urethane resin layer. Since the isocyanate group easily reacts with water in the air, it is difficult to remain on the surface of the urethane resin layer. Although the hydroxyl group (—OH) is usually small on the surface of the urethane resin after the urethane resin is cured, it does not react with water in the air.
  • the present inventor has studied a method of leaving the hydroxyl group of the polyol in the main agent on the surface of the urethane resin layer, particularly from the viewpoint of chemical components.
  • the present inventors can sufficiently secure the adhesion of the acrylic urethane resin to the urethane resin layer when using a urethane resin containing an appropriate amount of castor oil-based polyol having 2.7 or more hydroxyl groups per molecule. I found out that I can do it.
  • the adhesion of the topcoat layer containing the acrylic urethane resin to the urethane resin layer was sufficient, and the present inventors further conducted a method in which ultraviolet rays hardly reach the interface between the topcoat layer and the urethane resin layer. investigated.
  • FIG. 1 is a schematic view of a partial cross section (single side) of a resin-coated steel material according to the present embodiment.
  • the resin-coated steel material 5 includes a steel material 1, a primer layer 2 on the surface of the steel material 1, a urethane resin layer 3 on the surface of the primer layer 2, and a surface of the urethane resin layer 3.
  • the resin layer 6 including the primer layer 2, the urethane resin layer 3, and the top coat layer 4 is formed on at least one surface of the steel material 1. That is, the resin layer 6 may be formed on both surfaces of the steel material 1. Further, the resin layer 6 may be formed on the entire surface of the steel material 1.
  • the steel type (chemical composition), shape, dimensions, and product category of the steel material 1 are not particularly limited.
  • the steel material 1 is preferably a product that needs to be protected against corrosion for a long period of time.
  • the steel material 1 is preferably a large steel product such as a steel pipe, a steel pipe pile, a steel pipe sheet pile, or a steel sheet pile.
  • the thickness of the steel material 1 may be 5 mm to 50 mm.
  • the steel type of the steel material 1 may be plain steel or high alloy steel.
  • the resin layer 6 can be applied to the steel material 1 of any steel type.
  • the surface layer of the steel material 1 may be ordinary steel, high alloy steel, or a non-ferrous metal such as a plating metal.
  • the resin-coated steel material 5 includes the primer layer 2. Therefore, the chemical composition and thickness of the primer layer 2 are not particularly limited as long as the primer layer 2 has affinity for both the steel material 1 and the urethane resin layer 3.
  • the primer layer 2 may include at least one selected from the group consisting of a urethane resin and an epoxy resin.
  • the thickness of the primer layer 2 may be 10 to 200 ⁇ m.
  • the resin-coated steel material 5 includes a urethane resin layer 3.
  • the urethane resin layer 3 includes an inorganic pigment containing carbon black and a urethane resin.
  • the urethane resin is a component atom (ie, urethane) of a hydroxyl group (—OH) of a polyol (eg, HO—R 1 —OH) and an isocyanate group (—NCO) of an isocyanate [diisocyanate] (eg, OCN—R 2 —NCO).
  • Each bond has a urethane bond (—NHCOO—) consisting of one nitrogen atom, one carbon atom, one hydrogen atom and two oxygen atoms.
  • R 1 molecular skeleton
  • R 2 molecular skeleton
  • the mass obtained by subtracting the mass of the isocyanate (total mass of atoms supplied from the isocyanate) from the mass of the urethane resin layer 3 is the main agent (main resin). ) Mass.
  • the urethane resin layer 3 contains carbon black (CB) as one of inorganic pigments. Since carbon black absorbs ultraviolet rays well, it protects the urethane resin layer 3 from ultraviolet rays and enhances the weather resistance of the urethane resin layer 3. In order to sufficiently protect the urethane resin layer 3 from ultraviolet rays while uniformly dispersing the carbon black in the urethane resin layer 3, the mass of the carbon black is 0.2 to 5.0% of the mass of the main agent. is necessary. When the mass of the carbon black is less than 0.2% of the mass of the main agent, the weather resistance of the urethane resin layer 3 is not sufficient. Further, when the mass of the carbon black is more than 5.0% of the mass of the main agent, the carbon black aggregates in the urethane resin layer 3.
  • CB carbon black
  • the material of the inorganic pigment is not particularly limited.
  • An inorganic pigment is selected according to the characteristics required for the urethane resin layer 3.
  • the inorganic pigment includes an oxide mineral such as clay, pearlite, kaolin, kaolin clay, montmorillonite, talc, alumina ore.
  • Clay and pearlite contain silicon oxide (silica), kaolin, kaolin clay and montmorillonite contain aluminum silicate, and talc contains magnesium silicate. Therefore, for example, the inorganic pigment contains an oxide, and the oxide may be silicon oxide (silica) or silicate (silicate).
  • the mass of the inorganic pigment excluding carbon black (the mass obtained by subtracting the mass of carbon black from the mass of the inorganic pigment) needs to be 10 to 60% of the mass of the main agent. This mass is preferably 15 to 50% of the mass of the main agent.
  • the mass of the inorganic pigment excluding carbon black is less than 10% of the mass of the main agent, the strength of the urethane resin layer 3 is not sufficient.
  • the mass of the inorganic pigment excluding carbon black is more than 60% of the mass of the main agent, the adhesion of the urethane resin layer 3 to the top coat layer 4 is not sufficient.
  • the inorganic pigment mainly contains silica the specific gravity of the inorganic pigment is often 2.6 to 2.7.
  • the shape of the inorganic pigment is not particularly limited.
  • the inorganic mineral may be a ground oxide mineral.
  • the urethane resin includes a molecular skeleton (R 1 ) of polyol, a molecular skeleton (R 2 ) of isocyanate, and a urethane bond (—NHCOO—).
  • the urethane resin is a group consisting of an unreacted hydroxyl group (—OH), an unreacted isocyanate group (—NCO), a functional group derived from a hydroxyl group other than a urethane bond, and a functional group derived from an isocyanate group other than a urethane bond.
  • the molecular skeleton of the polyol is a partial structure (skeleton) obtained by removing a hydroxyl group from the polyol.
  • the molecular skeleton of isocyanate is a partial structure (skeleton part) obtained by removing isocyanate groups from isocyanate.
  • a three-dimensional network structure is formed around the molecular skeleton of the polyol molecule. Therefore, a polyol molecule having three or more hydroxyl groups can easily supply hydroxyl groups to the surface of the urethane resin layer 3. As a result, the greater the number of polyol molecules having three or more hydroxyl groups, the greater the number of hydroxyl groups at the interface between the urethane resin layer 3 and the topcoat layer 4 (hereinafter referred to as the upper interface). On the other hand, the three-dimensional network structure makes the urethane resin layer 3 brittle.
  • the castor oil derivative having 2.7 or more hydroxyl groups (functional groups) per molecule contains a sufficient amount of polyol molecules having a flexible molecular structure to supply sufficient hydroxyl groups to the surface of the urethane resin layer 3. Therefore, the polyol according to this embodiment needs to contain a castor oil derivative (hereinafter referred to as the first polyol) having 2.7 or more hydroxyl groups (functional groups) per molecule.
  • the first polyol a castor oil derivative having 2.7 or more hydroxyl groups (functional groups) per molecule.
  • the mass of the first polyol is 10 to 70% of the mass of the main agent.
  • the mass of the first polyol is particularly preferably 30 to 60% of the mass of the main agent.
  • a polyol consists only of a 1st polyol and the 2nd polyol mentioned later.
  • the first polyol is classified as a castor oil-based polyol.
  • the castor oil-based polyol includes a castor oil, a transesterification product of castor oil and a polyol, an ester compound of castor oil and a polyol, and an addition compound of these with an alkylene oxide.
  • castor oil-based polyol is a polyol that can be produced using castor oil (including castor oil-based fatty acid) as a main raw material.
  • a commercially available castor oil-based polyol can be used as the first polyol.
  • URIC H series manufactured by Ito Oil Co., Ltd. is commercially available.
  • URIC H-30 (hydroxyl value 155 to 165 mgKOH / g, functional group number 2.7), URIC H-52 (hydroxyl value 195 to 205 mgKOH / g, functional group number 3) as URIC H series corresponding to the first polyol
  • URIC H-57 (hydroxyl value 85 to 115 mgKOH / g, functional group number 3),
  • URIC H-73X (hydroxyl value 260 to 280 mgKOH / g, functional group number 3),
  • URIC H-81 (hydroxyl value 330 to 350 mgKOH / g, Number of functional groups 3),
  • URIC H-102 (hydroxyl value 300 to 340 mg KOH / g, functional group number 5),
  • URIC H-420 (hydroxyl value 300 to 340 mg KOH / g, functional group number 3
  • castor oil-based polyols have 2.7 or more functional groups (hydroxyl groups), a flexible molecular structure, and excellent mechanical strength. Further, the upper limit of the number of functional groups in the URIC H series is about 6. Thus, since the castor oil-based polyol having a functional group of 6.0 or less is easily available, the upper limit of the number of functional groups may be 6.0.
  • the number of functional groups (number of hydroxyl groups) of the polyol means the number of hydroxyl groups defined in JIS K 1557 and ISO 14900 and 15063.
  • Castor oil-based polyol contains chemical components or derivatives derived from castor oil in the molecular skeleton of each molecule.
  • the main component of castor oil is fatty acid glycerides.
  • a fatty acid is bonded to the hydroxyl group of glycerol by an ester bond.
  • Most of the fatty acids are ricinoleic acid (ricinoleic acid), and the remaining fatty acids are, for example, oleic acid, linoleic acid, linolenic acid, palmitic acid, stearic acid, and dihydroxy acid. Since the castor oil-based polyol has a chemical component derived from such castor oil, the molecular skeleton of the castor oil-based polyol imparts flexibility to the resin.
  • the polyol according to the present embodiment needs to include an organic composition (hereinafter, second polyol) having 2.0 hydroxyl groups (functional groups) per molecule.
  • a 2nd polyol contains the polyol product described as the number of hydroxyl groups (functional group number) being 2, and a diol compound. The amount of the second polyol is not particularly limited.
  • the mass of the second polyol is preferably 10 to 80%, more preferably 20 to 60% of the mass of the main agent.
  • a 2nd polyol can be suitably selected according to the characteristic provided to the urethane resin layer 3 additionally. For example, such characteristics include flexibility and heat resistance.
  • the specific mass of the second polyol can be determined according to this additional property. For example, as the second polyol, at least one selected from the following groups (a) to (d) can be used.
  • Castor oil-based polyol can be used as the second polyol.
  • Castor oil-based polyols corresponding to the second polyol include, for example, URIC H-62, URIC Y-202, URIC Y-403, URIC Y-406, and URIC Y-332. These products are manufactured by Ito Oil Co., Ltd. and have two functional groups (hydroxyl groups).
  • An amine polyol can be used as the second polyol.
  • the amine polyol corresponding to the second polyol include a polyol obtained by adding an alkylene oxide having 2 to 4 carbon atoms to amines.
  • Amines are classified into aromatic amines and aliphatic amines.
  • the aromatic amine include aniline, toluenediamine, diethyltoluenediamine, and 4,4'-diamino-3,3'-diethyldiphenylmethane.
  • the aromatic amine may be an aromatic monoamine or an aromatic polyamine.
  • Aliphatic amines include ethylenediamine, hexamethylenediamine, and diethylenetriamine.
  • the aliphatic amine may be an aliphatic polyamine.
  • alkylene oxide having 2 to 4 carbon atoms include ethylene oxide and propylene oxide.
  • An example of a compound of an amine and an alkylene oxide having 2 to 4 carbon atoms is N, N-bis (2-hydroxypropyl) aniline.
  • Polybutadiene polyol can be used as the second polyol.
  • Examples of the polybutadiene polyol corresponding to the second polyol include Poly bd TM R-45HT and Poly bd TM R-15HT. These products are manufactured by Idemitsu Kosan Co., Ltd. and have two functional groups (hydroxyl groups).
  • An alkylene diol can be used as the second polyol.
  • the alkylene diol corresponding to the second polyol may have, for example, a branched saturated hydrocarbon or a linear saturated hydrocarbon.
  • Specific alkylene diols having a branched saturated hydrocarbon include, for example, 2-methyl-1,3-propanediol (freezing point: ⁇ 91 ° C.), 2-methyl-1,4-butanediol (freezing point: ⁇ 30). ° C or lower), 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and the like.
  • Specific alkylene diol having a linear saturated hydrocarbon includes, for example, 1,3-propanediol.
  • the second polyol according to this embodiment may be at least one selected from the group consisting of (a) castor oil-based polyol, (b) amine polyol, (c) polybutadiene polyol, and (d) alkylene diol. . That is, a single compound, a single product, and a mixture can be used for the second polyol according to this embodiment.
  • the isocyanate according to this embodiment may be at least one selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate derivative (MDI derivative), and toluene diisocyanate derivative (TDI derivative).
  • MDI and TDI are aromatic diisocyanates and have two isocyanate groups.
  • the MDI derivative and the TDI derivative include an MDI oligomer and a TDI oligomer.
  • the isocyanate according to the present embodiment includes monomeric MDI, polymeric MDI, modified isocyanate, pure TDI isomer, isomer mixture of TDI, and blended isocyanate.
  • monomeric MDI monomeric MDI product
  • Millionate MR series polymeric MDI product
  • Coronate series polyol-modified isocyanate product
  • Millionate MTL series MDI carbodiimide-modified product
  • Coronate T-80 / T-65 / T-100 TDI product
  • Luplanate MS and MI monomeric MDI products
  • Luplanate M20S M11S, M5S
  • MM-103 M1S
  • MP-102 polymeric MDI products
  • MB-301 modified MDI products
  • Lupranate T-80 TDI product
  • isocyanate according to this embodiment a mixture of the above products may be used.
  • the ratio of the amount of isocyanate according to this embodiment to the amount of polyol according to this embodiment is defined by the number (total number) of isocyanate groups that the isocyanate has relative to the number (total number) of hydroxyl groups that the polyol has.
  • the ratio of the number of isocyanate groups (—NCO) to the number of hydroxyl groups (—OH) (—NCO / —OH) is preferably in the range of 0.9 to 1.2. If this ratio is 0.9 or more, the urethane resin layer 3 has sufficient hardness. Further, when the ratio (—NCO / —OH) is 1.2 or less, the urethane resin layer 3 has good quality in density.
  • a preferable range of the ratio (—NCO / —OH) is 1.0 to 1.1.
  • the urethane resin layer 3 may include a chemical component derived from at least one selected from the group consisting of a reaction accelerator, a water absorbent (humidifier), a thixotropic agent, a flame retardant, and a plasticizer as other chemical components. Good.
  • an amine compound or a metal catalyst can be used as the reaction accelerator.
  • amine compounds include triethylenediamine, bis (2-dimethylaminoethyl) ether, and N, N, N ′, N′-tetramethylhexamethylenediamine.
  • metal catalyst include dioctyltin dilaurate and stannous octoate.
  • a zeolite compound as the water absorbing agent.
  • a powdery zeolite compound there are Zeorum A-3, A-4, F-9 manufactured by Tosoh Corporation.
  • Aerosil which is dry silica manufactured by Nippon Aerosil Co., Ltd. can be used.
  • antimony trioxide aluminum hydroxide, tetrabromophenyl ether, tris (chloropropyl) phosphate (TCPP), or the like can be used.
  • TCPP tris (chloropropyl) phosphate
  • carboxylic acid esters such as phthalic acid esters, adipic acid esters, and sebacic acid esters can be used.
  • carboxylic acid esters include, for example, dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), dioctyl adipate (DOA), trioctyl trimetate (TOTM), tricresyl phosphate ( TCP).
  • the plasticizer is preferably diisononyl adipate (DINA) or diisononyl phthalate (DINP).
  • the thickness of the urethane resin layer 3 is not particularly limited. When the thickness of the urethane resin layer 3 is 2 mm or more, the urethane resin layer 3 has sufficient weather resistance and corrosion resistance. Moreover, the internal stress in the urethane resin layer 3 can be reduced as the thickness of the urethane resin layer 3 is 5 mm or less, and the peeling resistance in low temperature can be provided to the urethane resin layer 3. Therefore, the thickness of the urethane resin layer 3 is preferably 2 to 5 mm.
  • the urethane resin layer 3 includes an inorganic pigment containing carbon black (CB) and a urethane resin having a urethane bond composed of a constituent atom of a hydroxyl group of a polyol and an isocyanate group of an isocyanate.
  • the polyol is a castor oil derivative (first polyol) having 2.7 or more hydroxyl groups (functional groups) per molecule and an organic compound having 2.0 hydroxyl groups (functional groups) per molecule.
  • a composition second polyol).
  • the isocyanate includes at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate derivatives, and toluene diisocyanate derivatives.
  • the mass of carbon black is 0.2 to 5.
  • the mass obtained by subtracting the mass of carbon black from the mass of the inorganic pigment is 10 to 60% of the mass of the main agent, and the mass of the castor oil derivative is 10 to 70% of the mass of the main agent.
  • the resin-coated steel material 5 includes a top coat layer 4.
  • the top coat layer 4 includes carbon black and an acrylic urethane resin.
  • the acrylic urethane resin is a urethane bond comprising a hydroxyl group (—OH) of an acrylic polyol (eg, HO—R 3 —OH) and an isocyanate group (—NCO) of an isocyanate (eg, OCN—R 4 —NCO). (—NHCOO—).
  • the top coat layer 4 contains carbon black. Since carbon black absorbs ultraviolet rays well, it protects the urethane resin layer 3 and the topcoat layer 4 from ultraviolet rays and enhances the weather resistance of the urethane resin layer 3 and the topcoat layer 4. In order to sufficiently protect the urethane resin layer 3 from ultraviolet rays, the mass of the carbon black needs to be 0.2 to 5.0% of the mass of the topcoat layer 4. When the mass of the carbon black is less than 0.2% of the mass of the top coat layer 4, the ultraviolet rays pass through the top coat layer 4 and reach the upper interface. Therefore, deterioration of the urethane resin layer 3 in the vicinity of the upper interface cannot be suppressed.
  • the carbon black when the mass of the carbon black is more than 5.0% of the mass of the top coat layer 4, the carbon black aggregates in the top coat layer 4. In this case, even if the mass of the carbon black is further increased, the intensity of the ultraviolet rays transmitted through the top coat layer 4 is hardly changed. Moreover, since the topcoat layer 4 contains carbon black, the surface of the resin-coated steel material 5 is black.
  • the acrylic urethane resin includes an acrylic polyol molecular skeleton (R 3 ), an isocyanate molecular skeleton (R 4 ), and a urethane bond (—NHCOO—).
  • the acrylic urethane resin comprises an unreacted hydroxyl group (—OH), an unreacted isocyanate group (—NCO), a functional group derived from a hydroxyl group other than a urethane bond, and a functional group derived from an isocyanate group other than a urethane bond. At least one selected from the group may optionally be included.
  • the molecular skeleton of acrylic polyol is a partial structure (skeleton) obtained by removing hydroxyl groups from acrylic polyol.
  • the molecular skeleton of isocyanate is a partial structure (skeleton part) obtained by removing isocyanate groups from isocyanate.
  • the molecular skeleton of the acrylic polyol imparts weather resistance to the topcoat layer 4.
  • a copolymer of a methacrylate monomer or an acrylate ester and an unsaturated monomer (ethylenically unsaturated monomer) having a hydroxyl group and a double bond can be used.
  • the methacrylate monomer include methyl methacrylate and ethyl methacrylate.
  • the acrylate ester include methyl acrylate and ethyl acrylate.
  • Examples of the unsaturated monomer having a hydroxyl group and a double bond include hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.
  • the copolymerization method may be a known method.
  • a commercially available acrylic polyol can be used as the above acrylic polyol.
  • Takelac UA-702, Takelac UA-902, Takelac UA-905, etc. are acrylic polyols manufactured by Takeda Pharmaceutical Company Limited.
  • the isocyanate group of the isocyanate is chemically bonded to the hydroxyl group of the urethane resin layer 3 at the upper interface. This chemical bond (urethane bond) increases the adhesion between the urethane resin layer 3 and the topcoat layer 4.
  • the isocyanate according to this embodiment may be a prepolymer produced from an aliphatic isocyanate. Examples of the aliphatic isocyanate include xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Further, for example, the prepolymer may include a compound obtained by adding an aliphatic isocyanate to a polyether polyol.
  • a polyether polyol is a polyalkylene polyol having 2 to 3 active hydrogen groups (hydroxyl groups) in one molecule obtained by polymerizing an alkylene oxide to the polyol in the presence of an alkali catalyst or the like. May be.
  • the polyol used for this polymerization include propylene glycol, butanediol, neopentyl glycol, hexanediol, glycerin, and trimethylolpropane.
  • polymerization a propylene oxide, ethylene oxide, a butylene oxide, etc. are mentioned.
  • a urethane prepolymer having an aliphatic isocyanate at the terminal can be produced.
  • a urethane prepolymer can be used.
  • 1,6-hexamethylene diisocyanate homopolymer that can be produced from HDI can be used.
  • the molecular skeleton of the aliphatic isocyanate is larger than the molecular skeleton of the aromatic isocyanate.
  • the aromatic isocyanate include diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI).
  • the top coat layer 4 may contain an ultraviolet absorber or a light stabilizer.
  • a hindered amine light stabilizer can be used as the light stabilizer.
  • this hindered amine light stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-benzyl -7,7,9,9-tetramethyl-3-octyl 1,3,8-triazaspiro [4,5] undecane-2,4-dione.
  • Sankyo LS-292 and Sanol LS-765 made by Sankyo Co., Ltd. can be used as products containing bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.
  • Sanol LS-770 manufactured by Sankyo Co., Ltd. can be used.
  • Sanol LS manufactured by Sankyo Co., Ltd. -1114 is available.
  • the thickness of the top coat layer 4 is not particularly limited. When the thickness of the top coat layer 4 is 30 ⁇ m or more, the strength of the top coat layer 4 is sufficient, and the weather resistance of the resin-coated steel material 5 can be more reliably improved. In order to reduce the cost, the thickness of the topcoat layer 4 may be 100 ⁇ m or less. Therefore, the thickness of the top coat layer 4 is preferably 30 to 100 ⁇ m.
  • the topcoat layer 4 according to this embodiment includes carbon black and an acrylic urethane resin.
  • the mass of carbon black is 0.2 to 5.0% of the mass of the top coat layer 4.
  • the resin-coated steel material 5 according to the present embodiment since the number of chemical bonding points (the number of strong bonds) at the interface between the urethane resin layer 3 and the topcoat layer 4 is large, water enters the interface. The adhesion between the urethane resin layer 3 and the top coat layer 4 can be maintained even under conditions of exposure to water such as the ocean. Further, since the top coat layer 4 protects the urethane resin layer 3 from ultraviolet rays and water, the urethane resin layer 3 can prevent the steel material 1 from corrosion over a long period of time. Therefore, it is not necessary to form the urethane resin layer 3 extremely thick. As a result, the resin-coated steel material 5 according to the present embodiment can provide a low-cost structure having high durability under conditions exposed to water such as the ocean.
  • the depth at which the piles are driven is changed for each normal construction.
  • the adhesion between the resins is easily maintained for a long time, but at a position lower than the tidal band, the adhesion between the resins decreases in a short period of time.
  • the adhesion between the urethane resin layer 3 and the topcoat layer 4 can be maintained even at a position lower than the tidal zone. Therefore, in the resin-coated steel material 5 according to the present embodiment, it is not necessary to consider the area to which the resin layer 6 or the topcoat layer 4 is applied. Therefore, the resin-coated steel material 5 according to the present embodiment is suitably used for steel pipe piles. can do.
  • a primer layer is formed by applying a primer on the surface of a steel material (primary treatment).
  • a primer for example, a two-component mixed type urethane resin or epoxy resin can be used for the primer.
  • the application method may be spray coating.
  • the primer is preferably applied on the surface of the steel material so that the primer layer has a thickness of 10 to 200 ⁇ m.
  • blasting using sand, alumina, grid, or shot may be performed before applying the primer to the surface of the steel material.
  • blasting process scales and contaminants on the surface of the steel material can be removed.
  • the steel materials described in the embodiments according to the resin-coated steel materials can be used as the steel materials according to the present embodiment.
  • a liquid mixture comprising a main agent and a curing agent is applied on the surface of the primer layer, and the liquid mixture is cured to form a urethane resin layer.
  • the liquid mixture may be prepared by premixing the main agent and the curing agent, and this liquid mixture may be applied onto the surface of the primer layer by spraying. Further, it is preferable to apply the liquid mixture on the surface of the primer layer so that the thickness of the urethane resin layer is 2 to 5 mm. In this case, the thickness of the liquid mixture is a few mm.
  • the liquid mixture is a two-component solventless paint.
  • the liquid mixture according to the present embodiment is a two-component polyurethane resin composition composed of a main agent and a curing agent, and urethane polymerization starts by mixing the two components.
  • the main agent contains an inorganic pigment containing carbon black (CB) and a polyol.
  • the polyol is a castor oil derivative having a hydroxyl group (functional group) of 2.7 or more per molecule (hereinafter referred to as a first polyol) and an organic composition having 2.0 hydroxyl groups per molecule (hereinafter referred to as a second polymer). Polyol).
  • the first polyol is a polyol that can be derived from castor oil as a raw material.
  • the mass of the first polyol is 10 to 70% of the mass (total mass) of the main agent.
  • the mass of the inorganic pigment excluding carbon black is 10 to 60% of the mass of the main agent.
  • the mass of carbon black is 0.2 to 5.0% of the main agent.
  • the polyol is preferably composed of only the first polyol and the second polyol.
  • the curing agent includes at least one selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate derivative (MDI derivative), and toluene diisocyanate derivative (TDI derivative).
  • the inorganic pigment described in the embodiment according to the resin-coated steel material can be used as the inorganic pigment.
  • the mass of the inorganic pigment excluding carbon black is 10 to 60% of the mass of the main agent.
  • the mass of the inorganic pigment is reduced, the viscosity of the main agent can be reduced, and thus the coating efficiency can be increased.
  • the mass of the inorganic pigment is increased, the strength of the urethane resin layer can be increased. Therefore, the mass of the inorganic pigment excluding carbon black may be 15 to 50% of the mass of the main agent.
  • the first polyol described in the embodiment according to the resin-coated steel material can be used as the first polyol.
  • the mass of the first polyol is 10 to 70% of the mass of the main agent.
  • the mass of the first polyol is particularly preferably 30 to 60% of the mass of the main agent.
  • the upper limit of the number of hydroxyl groups in the first polyol may be 6.0.
  • the number of functional groups (number of hydroxyl groups) of the polyol means the number of hydroxyl groups defined in JIS K 1557 and ISO 14900 and 15063.
  • the second polyol described in the embodiment relating to the resin-coated steel material can be used as the second polyol.
  • the mass of the second polyol is preferably 10 to 80% of the mass of the main agent, and more preferably 20 to 60% of the mass of the main agent.
  • the isocyanate in the urethane resin layer 3 described in the embodiment according to the resin-coated steel material can be used as the isocyanate.
  • the ratio of the number of isocyanate groups (—NCO) derived from isocyanate to the number of hydroxyl groups (—OH) derived from polyol (—NCO / —OH) is in the range of 0.9 to 1.2. It is preferable to mix the main agent and the curing agent (that is, isocyanate) so as to be. As the amount of curing agent increases, the amount of foaming in the liquid mixture increases.
  • the ratio (—NCO / —OH) may be 1.0 to 1.1 in order to further increase productivity or yield.
  • the main agent may contain a chemical component derived from at least one selected from the group consisting of a reaction accelerator, a water absorbing agent, a thixotropic agent, a flame retardant, and a plasticizer.
  • an acrylic urethane resin paint containing carbon black (CB) is applied on the surface of the urethane resin layer, and the acrylic urethane resin is cured to form a topcoat layer.
  • CB carbon black
  • a solvent-type acrylic polyol containing carbon black (main component of acrylic urethane resin paint) and isocyanate (curing agent of acrylic urethane resin paint) are mixed in advance to prepare an acrylic urethane resin paint, and this acrylic urethane resin paint May be applied onto the surface of the urethane resin layer by spraying.
  • an acrylic urethane resin coating on the surface of the urethane resin layer so that the thickness of the topcoat layer is 30 to 100 ⁇ m.
  • the mass of carbon black is 0.2 to 5.0% of the mass of the acrylic urethane resin paint.
  • the dispersibility in the acrylic urethane resin coating material of carbon black is so high that the quantity of carbon black is small.
  • the acrylic resin paint contains acrylic polyol and isocyanate in addition to carbon black.
  • the acrylic polyol described in the embodiment relating to the resin-coated steel material can be used as the acrylic polyol.
  • the isocyanate in the topcoat layer 4 described in embodiment which concerns on said resin-coated steel material can be used as isocyanate.
  • the acrylic resin paint may contain an ultraviolet absorber or a light stabilizer as an optional chemical component. In this embodiment, the light stabilizer described in the embodiment according to the resin-coated steel material can be used as the light stabilizer.
  • the mass of the main agent in the present embodiment is equivalent to the mass of the main agent in the embodiment according to the resin-coated steel material.
  • the mass of the acrylic urethane resin paint in this embodiment is equivalent to the mass of the topcoat layer 4 of the embodiment according to the above resin-coated steel material.
  • the method for producing a resin-coated steel material according to this embodiment can provide a resin-coated steel material that can prevent the steel material from being corroded for a long period of time by the urethane resin layer even under conditions exposed to water such as the ocean.
  • test plate 1 to 22 test plates were prepared and evaluated by the following procedure.
  • Grit blasting was performed on the surface of a 6 ⁇ 100 ⁇ 150 mm steel plate, and rust was removed until the degree of rust removal was Sa2 ⁇ 1/2 or more.
  • PG331 urethane primer manufactured by Daiichi Kogyo Seiyaku was used as a commercially available primer of urethane resin composition. This urethane primer was applied to the surface of the steel plate using a spray, and a primer layer having a thickness of 30 ⁇ m was formed on the surface of the steel plate.
  • a urethane resin coating was applied on the surface of the primer layer using a high-pressure spray coating machine to form a urethane resin layer having a thickness of 2 to 5 mm.
  • the high-pressure spray coater is prepared by mixing the main agent and curing agent (curing agent / main agent) with a mixer so that the ratio of -NCO number to -OH number (-NCO / -OH) is 1.1. Supplied urethane resin paint.
  • a top coat paint was applied with a cup gun (spray) to form a top coat layer having a thickness of 30 to 100 ⁇ m. This top coat paint was prepared by previously mixing the main agent and the curing agent with a stirrer.
  • test plate was cured for one week and then cut into a size of 75 ⁇ 150 mm.
  • the back and side surfaces of the cut test plate were sealed with an epoxy resin.
  • a seawater immersion test at 40 ° C. specified in ISO 20340 and a combined cycle test for 175 days were performed on the test piece after sealing.
  • a combination (cycle) of a wet weathering test for 3 days with QUV, a cooling to ⁇ 20 ° C. for 1 day, and a salt spray for 3 days is repeated.
  • test piece For each test piece after the test (initial adhesion), after the seawater immersion test, and after the combined cycle test, the adhesion of the topcoat layer to the urethane resin layer was measured using a dolly having a diameter of 20 mm (test cylinder). Evaluation was performed with a pull-off tester. With respect to this evaluation result, a test piece having an adhesion strength of 5 MPa or more was judged to be good, and a test piece having an adhesion strength of less than 5 MPa was judged to be defective.
  • a castor oil-based polyol (hereinafter referred to as the first polyol) having 2.7 or more hydroxyl groups per molecule was used as one of the main components of the urethane resin layer (urethane resin paint).
  • URIC H-30 (hydroxyl value 155 to 165 mg KOH / g, functional group number 2.7) manufactured by Ito Oil Co., Ltd. was used as the first polyol.
  • URIC H-57 (hydroxyl value 85 to 115 mgKOH / g, functional group number 3) manufactured by Ito Oil Co., Ltd. was used as the first polyol.
  • the mass of the first polyol was 5 to 80% of the mass of the main agent.
  • a polyol having 2.0 hydroxyl groups per molecule (hereinafter referred to as a second polyol) was used as one of the main components of the urethane resin layer.
  • URIC Y-403 (hydroxyl value 150 to 170 mgKOH / g, functional group number 2) manufactured by Ito Oil Co., Ltd., which is a representative example of castor oil-based polyol, was used as the second polyol.
  • 3-methyl-1,5-pentanediol which is a typical example of a diol polyol, was used as the second polyol.
  • N, N-bis (2-hydroxypropyl) aniline which is a representative example of an aromatic amine polyol
  • Poly bd TM R-15HT manufactured by Idemitsu Kosan Co., Ltd. which is a representative example of a polybutadiene-based polyol, was used as the second polyol.
  • No. 18 uses two types of second polyols.
  • an inorganic pigment was used as one of the main components of the urethane resin layer.
  • carbon black (CB) was used as one of the inorganic pigments (ultraviolet resistant color pigments).
  • the mass of the carbon black was 0.5 to 5.0% of the mass of the main agent.
  • clay was used as one of the inorganic pigments (inorganic extender pigments). The mass of this clay was 10 to 60% of the mass of the main agent.
  • Zeorum A-4 (zeolite) manufactured by Tosoh Corporation was used as a hygroscopic agent, hexabromobenzene was used as a flame retardant, and diisononyl phthalate was used as a plasticizer. Further, as other chemical components, a curing catalyst (dioctyltin dilaurate) and a thixotropic agent (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.) were used. The main agent was prepared by mixing the above main agent components.
  • Top coat paint In Nos. 1 to 6, nax mighty rack G-2 (acrylic urethane (1)) manufactured by Nippon Paint Co., Ltd. was used as the top coat layer (top coat paint). No. In 7 to 15 and 18, Hardtop XP (acrylic urethane (2)) manufactured by Jotun was used as the topcoat layer.
  • These two types of paints are general acrylic urethane resin paints, in which an acrylic polyol (main agent), 1,6-hexamethylene diisocyanate homopolymer (HDI isocyanate curing agent), a colored paint, and a light stabilizer are mixed. ing. No. In Nos.
  • No. 19-22 is a reproduction test corresponding to the invention example (second line of Table 1) disclosed in Patent Document 1.
  • No. 20 is a reproduction test corresponding to Example 1 disclosed in Patent Document 2.
  • No. 21 is a test in which carbon black was added to the acrylic urethane paint of Example 1 disclosed in Patent Document 2.
  • No. 22 is a reproduction test corresponding to the example disclosed in Patent Document 3.
  • Tables 1 to 3 show the experimental conditions 1 to 18 and the evaluation results. An underlined number or letter in the columns of Tables 1 and 3 indicates that the conditions according to the present invention are not satisfied.
  • test plate could not maintain sufficient adhesion after the immersion test and the combined cycle test.
  • No. In 6, 12, and 16 the test plate could not maintain sufficient adhesion after the combined cycle test.
  • No. In No. 7 it is considered that the physical properties of the urethane resin were lowered during curing.
  • No. In 1, 11, 17, and 18, it is considered that water entered the interface between the top coat layer and the urethane resin layer, and the bond at the interface between the urethane resin layer and the top coat layer was broken.
  • No. In Nos. 6, 12 and 16 it is considered that ultraviolet rays were transmitted through the top coat layer and the interface between the top coat layer and the urethane resin layer was significantly deteriorated.
  • No. Tables 4 and 5 show the experimental conditions and evaluation results of 19-22.
  • the urethane resin layer did not contain a chemical component derived from a castor oil-based polyol having 2.7 or more hydroxyl groups per molecule, so that the test plate had sufficient adhesion after the immersion test and the combined cycle test. could not be maintained.
  • no. In No. 20 since neither a color pigment nor carbon black was added to the top coat layer, the surface of the urethane resin layer was greatly deteriorated, and the top coat layer was easily peeled off from the urethane resin layer.
  • a resin-coated steel material in which the resin coating can prevent the steel material from being corroded over a long period of time even under a severe corrosive environment such as the ocean, and a manufacturing method thereof.

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Abstract

L'invention concerne un matériau en acier revêtu de résine, lequel matériau comporte un matériau en acier, une couche d'apprêt sur la surface du matériau en acier, une couche de résine d'uréthane sur la surface de la couche d'apprêt, et une couche de revêtement supérieure sur la surface de la couche de résine d'uréthane. La couche de résine d'uréthane contient un dérivé d'huile de ricin ayant au moins 2,7 groupes hydroxyle par molécule, et une résine d'uréthane obtenue par la polymérisation d'un isocyanate et d'une composition organique ayant 2,0 groupes hydroxyle par molécule. La couche de revêtement supérieure contient une résine d'uréthane acrylique.
PCT/JP2017/008793 2016-03-16 2017-03-06 Matériau en acier revêtu de résine et procédé pour sa fabrication WO2017159430A1 (fr)

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JPH04310274A (ja) * 1991-04-05 1992-11-02 Nippon Steel Corp ポリウレタン被覆構造物
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JP2021055083A (ja) * 2019-10-01 2021-04-08 株式会社エフコンサルタント 被覆材、及び被膜形成方法
JP7366872B2 (ja) 2019-10-01 2023-10-23 株式会社エフコンサルタント 被覆材、及び被膜形成方法

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SG11201806227RA (en) 2018-08-30
AU2017234095B8 (en) 2019-04-18
AU2017234095B2 (en) 2019-04-11
JP6551599B2 (ja) 2019-07-31
AU2017234095A1 (en) 2018-08-16

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