WO2017159430A1 - Resin-coated steel material and method for manufacturing same - Google Patents
Resin-coated steel material and method for manufacturing same Download PDFInfo
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- 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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- urethane resin
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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
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- 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
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- 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
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- 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
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- 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
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- 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
Description
本願は、2016年3月16日に、日本に出願された特願2016-052696号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a steel material (resin-coated steel material) coated with urethane resin and a method for producing the same.
This application claims priority on March 16, 2016 based on Japanese Patent Application No. 2016-052696 filed in Japan, the contents of which are incorporated herein by reference.
鋼材1の鋼種(化学組成)や形状、寸法、製品カテゴリーは、特に限定されない。後述のように、樹脂層6は、海洋のような厳しい腐食環境下で特に優れた耐久性を有するため、鋼材1は、長期間にわたって防食される必要がある製品であると好適である。例えば、鋼材1は、鋼管、鋼管杭、鋼管矢板、鋼矢板などの大型鋼製製品であると好適である。例えば、鋼材1の厚さが5mm~50mmであってもよい。鋼材1の鋼種は、普通鋼であっても、高合金鋼であってもよい。樹脂層6は、どのような鋼種の鋼材1に対しても適用可能である。例えば、鋼材1の表層が、普通鋼であっても、高合金鋼であっても、めっき金属のような非鉄金属であってもよい。 (Steel 1)
The steel type (chemical composition), shape, dimensions, and product category of the steel material 1 are not particularly limited. As will be described later, since the resin layer 6 has particularly excellent durability in a severe corrosive environment such as the ocean, the steel material 1 is preferably a product that needs to be protected against corrosion for a long period of time. For example, 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. For example, 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. For example, 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.
樹脂層6を鋼材1にしっかりと接着するために、樹脂被覆鋼材5は、プライマー層2を備えている。そのため、プライマー層2が鋼材1とウレタン樹脂層3との両方に対して親和性を持つ限りにおいて、プライマー層2の化学組成や厚さは、特に限定されない。例えば、プライマー層2が、ウレタン樹脂及びエポキシ樹脂からなる群から選択される少なくとも1種を含んでもよい。また、例えば、プライマー層2の厚さは、10~200μmであってもよい。 (Primer layer 2)
In order to firmly bond the resin layer 6 to the steel material 1, the resin-coated
鋼材1を腐食から防ぐために、樹脂被覆鋼材5は、ウレタン樹脂層3を備えている。このウレタン樹脂層3は、カーボンブラックを含む無機顔料と、ウレタン樹脂とを含む。ウレタン樹脂は、ポリオール(例えば、HO-R1-OH)の水酸基(-OH)及びイソシアネート[ジイソシアネート](例えば、OCN-R2-NCO)のイソシアネート基(-NCO)の構成原子(すなわち、ウレタン結合1つあたり1個の窒素原子と1個の炭素原子と1個の水素原子と2個の酸素原子)からなるウレタン結合(-NHCOO-)を有している。このウレタン結合によって、ウレタン樹脂では、ポリオールの分子骨格(R1)とイソシアネートの分子骨格(R2)とが結合されている。本実施形態では、ウレタン樹脂層3における質量の基準を明確にするために、ウレタン樹脂層3の質量からイソシアネートの質量(イソシアネートから供給された原子の全質量)を減じた質量を主剤(main resin)の質量と定義する。 (Urethane resin layer 3)
In order to prevent the steel material 1 from corrosion, the resin-coated
ウレタン樹脂層3は、無機顔料の1つとして、カーボンブラック(CB)を含む。カーボンブラックは、紫外線をよく吸収するため、ウレタン樹脂層3を紫外線から保護し、ウレタン樹脂層3の耐候性を高める。カーボンブラックをウレタン樹脂層3中に均一に分散させつつウレタン樹脂層3を紫外線から十分に保護するためには、カーボンブラックの質量が主剤の質量の0.2~5.0%であることが必要である。カーボンブラックの質量が主剤の質量の0.2%未満であると、ウレタン樹脂層3の耐候性が十分でない。また、カーボンブラックの質量が主剤の質量の5.0%超であると、カーボンブラックがウレタン樹脂層3中で凝集する。 (Carbon black in urethane resin 3)
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.
カーボンブラックを除けば、無機顔料の材質は、特に限定されない。ウレタン樹脂層3に必要とされる特性に応じて無機顔料が選択される。例えば、無機顔料が体質顔料として選択されると、無機顔料は、クレー、パーライト、カオリン、カオリンクレー、モンモリロナイト、タルク、アルミナ鉱石のような酸化鉱物を含む。クレー及びパーライトは、酸化珪素(シリカ)を含み、カオリン、カオリンクレー及びモンモリロナイトは、珪酸アルミニウムを含み、タルクは、珪酸マグネシウムを含む。そのため、例えば、無機顔料は、酸化物を含み、この酸化物が酸化珪素(シリカ)や珪酸塩(シリケート)であってもよい。無機顔料が酸化鉱物を含むと、ウレタン樹脂層3の強度が大きくなり、ウレタン樹脂層3の防食性能が高まる一方で、トップコート層4に対するウレタン樹脂層3の密着性が低下する。そのため、カーボンブラックを除く無機顔料の質量(無機顔料の質量からカーボンブラックの質量を減じた質量)は、主剤の質量の10~60%であることが必要である。この質量は、主剤の質量の15~50%であると好ましい。カーボンブラックを除く無機顔料の質量が主剤の質量の10%未満であると、ウレタン樹脂層3の強度が十分でない。また、カーボンブラックを除く無機顔料の質量が主剤の質量の60%超であると、トップコート層4に対するウレタン樹脂層3の密着性が十分でない。例えば、無機顔料がシリカを主に含む場合、無機顔料の比重は、2.6~2.7であることが多い。また、無機顔料の形状も、特に限定されない。例えば、無機鉱物が、粉砕された酸化鉱物であってもよい。 (Inorganic pigment in the urethane resin layer 3 (excluding carbon black))
Except for 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. For example, when an inorganic pigment is selected as an extender, 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). When the inorganic pigment contains an oxide mineral, the strength of the urethane resin layer 3 increases, and the anticorrosion performance of the urethane resin layer 3 increases, while the adhesion of the urethane resin layer 3 to the
ウレタン樹脂は、ポリオールの分子骨格(R1)と、イソシアネートの分子骨格(R2)と、ウレタン結合(-NHCOO-)とを含む。また、ウレタン樹脂は、未反応の水酸基(-OH)、未反応のイソシアネート基(-NCO)、ウレタン結合以外の水酸基に由来する官能基、ウレタン結合以外のイソシアネート基に由来する官能基からなる群から選択する少なくとも1種を任意に含んでもよい。ポリオールの分子骨格は、ポリオールから水酸基を除いた部分構造(骨格部)である。イソシアネートの分子骨格は、イソシアネートからイソシアネート基を除いた部分構造(骨格部)である。これらの部分構造は、ポリオール及びイソシアネートの種類に応じて変化する。 (Urethane resin in urethane resin layer 3)
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. It may optionally include at least one selected from 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. These partial structures vary depending on the types of polyol and isocyanate.
ウレタン樹脂層3は、その他の化学成分として、反応促進剤、吸水剤(吸湿剤)、チキソ付与剤、難燃剤、可塑剤からなる群から選択される少なくとも1つに由来する化学成分を含んでもよい。 (Other chemical components in urethane resin layer 3)
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.
ウレタン樹脂層3の厚さは、特に限定されない。ウレタン樹脂層3の厚さが2mm以上であると、ウレタン樹脂層3が十分な耐疵性及び防食性を有している。また、ウレタン樹脂層3の厚さが5mm以下であると、ウレタン樹脂層3中の内部応力を減らすことができ、ウレタン樹脂層3に低温における耐剥離性を付与することができる。そのため、ウレタン樹脂層3の厚さは、2~5mmであると好ましい。 (Thickness of urethane resin layer 3)
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.
したがって、本実施形態に係るウレタン樹脂層3は、カーボンブラック(CB)を含む無機顔料と、ポリオールの水酸基及びイソシアネートのイソシアネート基の構成原子からなるウレタン結合を有するウレタン樹脂とを含む。本実施形態では、ポリオールは、1分子あたり2.7個以上の水酸基(官能基)を有するひまし油誘導体(第1のポリオール)と、1分子あたり2.0個の水酸基(官能基)を有する有機組成物(第2のポリオール)とを含む。また、本実施形態では、イソシアネートが、ジフェニルメタンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート誘導体、トルエンジイソシアネート誘導体からなる群から選択される少なくとも1種を含む。さらに、本実施形態に係るウレタン樹脂層3では、ウレタン樹脂層3の質量からイソシアネートの質量を減じた質量を主剤の質量と定義すると、カーボンブラックの質量が主剤の質量の0.2~5.0%であり、無機顔料の質量からカーボンブラックの質量を減じた質量が主剤の質量の10~60%であり、ひまし油誘導体の質量が主剤の質量の10~70%である。 (Essential structure related to chemical components of urethane resin layer 3)
Therefore, the urethane resin layer 3 according to the present embodiment 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. In the present embodiment, 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. And a composition (second polyol). In the present embodiment, the isocyanate includes at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate derivatives, and toluene diisocyanate derivatives. Furthermore, in the urethane resin layer 3 according to the present embodiment, when the mass obtained by subtracting the mass of isocyanate from the mass of the urethane resin layer 3 is defined as the mass of the main agent, 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.
ウレタン樹脂層3を紫外線及び水から守るために、樹脂被覆鋼材5は、トップコート層4を備えている。このトップコート層4は、カーボンブラックと、アクリルウレタン樹脂とを含む。アクリルウレタン樹脂は、アクリルポリオール(例えば、HO-R3-OH)の水酸基(-OH)及びイソシアネート(例えば、OCN-R4-NCO)のイソシアネート基(-NCO)の構成原子)からなるウレタン結合(-NHCOO-)を有している。このウレタン結合によって、ウレタン樹脂では、ポリオールの分子骨格(R3)とイソシアネートの分子骨格(R4)とが結合されている。 (Topcoat layer 4)
In order to protect the urethane resin layer 3 from ultraviolet rays and water, the resin-coated
トップコート層4は、カーボンブラックを含む。カーボンブラックは、紫外線をよく吸収するため、ウレタン樹脂層3及びトップコート層4を紫外線から保護し、ウレタン樹脂層3及びトップコート層4の耐候性を高める。ウレタン樹脂層3を紫外線から十分に保護するためには、カーボンブラックの質量がトップコート層4の質量の0.2~5.0%であることが必要である。カーボンブラックの質量がトップコート層4の質量の0.2%未満であると、紫外線がトップコート層4を透過して上界面に到達する。そのため、上界面近傍のウレタン樹脂層3の劣化を抑制できない。また、カーボンブラックの質量がトップコート層4の質量の5.0%超であると、カーボンブラックがトップコート層4中で凝集する。この場合、さらにカーボンブラックの質量を増やしても、トップコート層4を透過する紫外線の強さは殆ど変わらない。また、トップコート層4がカーボンブラックを含むため、樹脂被覆鋼材5の表面は、黒色である。 (Carbon black in the top coat layer 4)
The
アクリルウレタン樹脂は、アクリルポリオールの分子骨格(R3)と、イソシアネートの分子骨格(R4)と、ウレタン結合(-NHCOO-)とを含む。また、アクリルウレタン樹脂は、未反応の水酸基(-OH)、未反応のイソシアネート基(-NCO)、ウレタン結合以外の水酸基に由来する官能基、ウレタン結合以外のイソシアネート基に由来する官能基からなる群から選択する少なくとも1種を任意に含んでもよい。アクリルポリオールの分子骨格は、アクリルポリオールから水酸基を除いた部分構造(骨格部)である。イソシアネートの分子骨格は、イソシアネートからイソシアネート基を除いた部分構造(骨格部)である。これらの部分構造は、アクリルポリオール及びイソシアネートの種類に応じて変化する。 (Acrylic urethane resin in top coat layer 4)
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. These partial structures change according to the kind of acrylic polyol and isocyanate.
トップコート層4の厚さは、特に限定されない。トップコート層4の厚さが30μm以上であると、トップコート層4の強度が十分であり、より確実に樹脂被覆鋼材5の耐候性を高めることができる。また、コストを低減するために、トップコート層4の厚さが100μm以下であってもよい。そのため、トップコート層4の厚さは、30~100μmであると好ましい。 (Thickness of top coat layer 4)
The thickness of the
したがって、本実施形態に係るトップコート層4は、カーボンブラックと、アクリルウレタン樹脂とを含む。また、本実施形態に係るトップコート層では、カーボンブラックの質量がトップコート層4の質量の0.2~5.0%である。 (Essential configuration related to chemical components of topcoat layer 4)
Therefore, the
本実施形態に係る樹脂被覆鋼材5では、ウレタン樹脂層3とトップコート層4との間の界面における化学的な結合点の数(強い結合の数)が多いので、この界面への水の浸入を防ぐことができ、海洋などの水にさらされる条件下においてもウレタン樹脂層3とトップコート層4との間の密着性を維持することができる。また、トップコート層4がウレタン樹脂層3を紫外線及び水から守るため、ウレタン樹脂層3によって長期にわたり鋼材1を腐食から防ぐことができる。そのため、ウレタン樹脂層3を極端に厚く形成する必要がない。結果として、本実施形態に係る樹脂被覆鋼材5によって、海洋などの水にさらされる条件下において高い耐久性を有する低コストの構造物を提供できる。 (Effect of the resin-coated
In the resin-coated
まず、鋼材の表面上にプライマーを塗布してプライマー層を形成する(下地処理)。例えば、プライマーには、2液混合タイプのウレタン樹脂またはエポキシ樹脂を用いることができる。プライマーの粘度が低いほど、鋼材表面の凹凸に対してプライマーがなじみやすい。そのため、プライマーが粘度の低い溶剤型のプライマーであると好ましい。塗布の方法は、スプレー塗装であってもよい。また、プライマー層の厚さが10~200μmとなるようにプライマーを鋼材の表面上に塗布すると好ましい。プライマー層とウレタン樹脂層との密着性をできる限り高めるために、鋼材の表面にプライマーを塗布する前に、サンド、アルミナ、グリッド、あるいはショットを用いたブラスト処理を行ってもよい。このブラスト処理により、鋼材表面のスケールや汚染物等を除去することができる。また、本実施形態に係る鋼材として、上記の樹脂被覆鋼材に係る実施形態に記載した鋼材を使用することができる。 (Primer application)
First, a primer layer is formed by applying a primer on the surface of a steel material (primary treatment). For example, a two-component mixed type urethane resin or epoxy resin can be used for the primer. The lower the viscosity of the primer, the easier it is to adapt to the irregularities on the steel surface. Therefore, the primer is preferably a solvent-type primer having a low viscosity. 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 μm. In order to enhance the adhesion between the primer layer and the urethane resin layer as much as possible, blasting using sand, alumina, grid, or shot may be performed before applying the primer to the surface of the steel material. By this blasting process, scales and contaminants on the surface of the steel material can be removed. Moreover, 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.
次に、プライマー層の表面上に主剤と硬化剤とからなる液体混合物を塗布し、この液体混合物を硬化させてウレタン樹脂層を形成する。例えば、主剤と硬化剤とを事前に混合して液体混合物を調製し、スプレーによってこの液体混合物をプライマー層の表面上に塗布してもよい。また、ウレタン樹脂層の厚さが2~5mmとなるように液体混合物をプライマー層の表面上に塗布すると好ましい。この場合、液体混合物の厚さが数mmである。液体混合物は、2液の無溶剤型塗料である。 (Application of main agent and curing agent)
Next, 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. For example, 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.
最後に、ウレタン樹脂層の表面上にカーボンブラック(CB)を含むアクリルウレタン樹脂塗料を塗布し、このアクリルウレタン樹脂を硬化させてトップコート層を形成する。例えば、カーボンブラックを含む溶剤型のアクリルポリオール(アクリルウレタン樹脂塗料の主剤)とイソシアネート(アクリルウレタン樹脂塗料の硬化剤)とを事前に混合してアクリルウレタン樹脂塗料を調整し、このアクリルウレタン樹脂塗料をスプレーによってウレタン樹脂層の表面上に塗布してもよい。また、また、トップコート層の厚さが30~100μmとなるようにアクリルウレタン樹脂塗料をウレタン樹脂層の表面上に塗布すると好ましい。このアクリルウレタン樹脂塗料では、カーボンブラックの質量がアクリルウレタン樹脂塗料の質量の0.2~5.0%である。なお、カーボンブラックの量が少ないほど、カーボンブラックのアクリルウレタン樹脂塗料中における分散性は高い。 (Application of acrylic urethane resin paint)
Finally, 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. For example, 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. Further, it is preferable to apply 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 μm. In this acrylic urethane resin paint, the mass of carbon black is 0.2 to 5.0% of the mass of the acrylic urethane resin paint. In addition, the dispersibility in the acrylic urethane resin coating material of carbon black is so high that the quantity of carbon black is small.
No.1~22の試験板を以下の手順にて作製して評価した。
6×100×150mmの鋼板の表面にグリットブラストを行い、除錆度がSa2・1/2以上になるまで錆を除去した。下地処理には、ウレタン樹脂組成の市販プライマーとして、第一工業製薬製のPG331ウレタンプライマーを用いた。このウレタンプライマーをスプレーを用いて鋼板の表面に塗装し、厚み30μmのプライマー層を鋼板の表面上に形成した。その3時間後に、高圧スプレー塗装機を用いてウレタン樹脂塗料をプライマー層の表面上に塗装し、厚み2~5mmのウレタン樹脂層を形成した。高圧スプレー塗装機には、-OHの数に対する-NCOの数の比(-NCO/-OH)が1.1になるように主剤及び硬化剤(硬化剤/主剤)をミキサーで混合して調製されたウレタン樹脂塗料を供給した。その翌日に、トップコート塗料をカップガン(スプレー)にて塗装し、厚み30~100μmのトップコート層を形成した。このトップコート塗料は、事前に主剤と硬化剤とを攪拌機で混合して調製された。 1) Preparation procedure and evaluation method of 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. For the base treatment, 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 μm was formed on the surface of the steel plate. Three hours later, 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. On the next day, a top coat paint was applied with a cup gun (spray) to form a top coat layer having a thickness of 30 to 100 μm. This top coat paint was prepared by previously mixing the main agent and the curing agent with a stirrer.
No.1~17では、ウレタン樹脂層(ウレタン樹脂塗料)の主剤成分の一つとして、1分子あたり2.7個以上の水酸基を有するひまし油系ポリオール(以下、第1のポリオール)を用いた。No.1~14では、この第1のポリオールとして、伊藤製油製のURIC H-30(水酸基価155~165mgKOH/g、官能基数2.7)を用いた。No.15~17では、第1のポリオールとして、伊藤製油製のURIC H-57(水酸基価85~115mgKOH/g、官能基数3)を用いた。No.1~17では、第1のポリオールの質量は、主剤の質量の5~80%であった。 2) Main component of urethane resin paint In Nos. 1 to 17, 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). No. In Nos. 1 to 14, 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. No. In Nos. 15 to 17, 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. No. In 1 to 17, the mass of the first polyol was 5 to 80% of the mass of the main agent.
主剤は、上記の主剤成分を混合して調製した。 Furthermore, no. In Nos. 1 to 18, an inorganic pigment was used as one of the main components of the urethane resin layer. No. In 1 to 11 and 13 to 18, 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. No. In 1 to 6 and 8 to 18, 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. No. In Nos. 1 to 18, 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.
No.1~14及び18では、ポリメリックMDI(Cr-MDI)(硬化剤)として、東ソー株式会社製のミリオネートMR-200を用いた。また、No.15~17では、TDI(硬化剤)として東ソー株式会社製のCORONATE T-100を用いた。 3) Urethane resin paint curing agent In 1 to 14 and 18, Millionate MR-200 manufactured by Tosoh Corporation was used as the polymeric MDI (Cr-MDI) (curing agent). No. In Nos. 15 to 17, CORONATE T-100 manufactured by Tosoh Corporation was used as TDI (curing agent).
No.1~6では、トップコート層(トップコート塗料)として、日本ペイント社製のnaxマイティラックG-2(アクリルウレタン(1))を用いた。No.7~15及び18では、トップコート層として、Jotun社製Hardtop XP(アクリルウレタン(2))を用いた。これら2種類の塗料は、一般的なアクリルウレタン樹脂塗料であり、アクリルポリオール(主剤)と1,6-ヘキサメチレンジイソシアネートホモポリマー(HDI系イソシアネート硬化剤)と着色塗料と光安定剤とが混合されている。No.1~15及び18では、着色塗料としてカーボンブラックが用いられ、カーボンブラックの質量がトップコート塗料の0.5%であった。また、No.16では、トップコート層として、Jotun社製Hardtop XP(アクリルウレタン(3))を用いた。このNo.16では、着色塗料として青色塗料が用いられた。No.17では、日本ペイント社製のデュフロン100(フッ素系塗料)を用いた。 6) 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. 1 to 15 and 18, carbon black was used as the colored paint, and the mass of the carbon black was 0.5% of the top coat paint. No. In No. 16, Hardtop XP (acrylic urethane (3)) manufactured by Jotun was used as the topcoat layer. This No. In No. 16, a blue paint was used as the colored paint. No. In No. 17, Duflon 100 (fluorine-based paint) manufactured by Nippon Paint Co., Ltd. was used.
No.19は、特許文献1に開示された発明例(第1表の2行目)に相当する再現試験である。No.20は、特許文献2に開示された実施例1に相当する再現試験である。No.21は、特許文献2に開示された実施例1のアクリルウレタン塗料にカーボンブラックを加えた試験である。No.22は、特許文献3に開示された実施例に相当する再現試験である。 7) No. 19-22
No. 19 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.
また、No.19~22では、硬化剤として、以下のMDIを使用した。No.19及び22では、MDIとして、東ソー(株)製のミリオネートMTを使用した。No.20及び21では、粗MDI(Cr-MDI)として、東ソー(株)製のミリオネートMR-100を使用した。
さらに、No.19~22では、ゼオライトとして、東ソー(株)製のゼオラムA-4を使用し、可塑剤としてジオクチルフタレートを使用した。
トップコート塗料について、No.19~21では、アクリルウレタン塗料(アクリルウレタン)として、日本ペイント製のハイポン50上塗を使用した。No.22では、フッ素系塗料(フッ素)として、デュフロン100を使用した。なお、上述のように、No.21では、ハイポン50上塗にカーボンブラックが添加されている。 No. In 19-22, the following polyols were used as the main component. No. In No. 19, NIPPOLLAN 141 (hydroxyl value: 102 to 108 KOHmg / g) manufactured by Tosoh Corporation was used as the polyester polyol. No. In Nos. 20 to 22, Poly bd ™ R-45HT manufactured by Idemitsu Kosan was used as the polybutadiene polyol. No. In Nos. 20 and 21, N, N bis (2-hydroxypropyl) aniline was used as the aromatic amine-based polyol.
No. In 19-22, the following MDI was used as a curing agent. No. In 19 and 22, Millionate MT manufactured by Tosoh Corporation was used as MDI. No. In 20 and 21, Millionate MR-100 manufactured by Tosoh Corporation was used as the crude MDI (Cr-MDI).
Furthermore, no. In 19-22, Zeolum A-4 manufactured by Tosoh Corporation was used as the zeolite, and dioctyl phthalate was used as the plasticizer.
For top coat paint, In 19-21, Nippon Paint's Hypon 50 topcoat was used as the acrylic urethane paint (acrylic urethane). No. In No. 22,
No.2~5、8~10及び13~15では、本発明に係る条件を満たすため、試験板が水環境下においてもトップコート層のウレタン樹脂層に対する密着性に優れていた。そのため、これらの試験板は、初期密着性に優れており、水環境及び紫外線と水との複合環境における両試験後でも十分な密着力を維持していた。一方、No.7では、試験板が十分な初期密着性を有していなかった。No.1、11、17及び18では、浸漬試験及び複合サイクル試験後に試験板が十分な密着力を維持できなかった。No.6,12及び16では、複合サイクル試験後に試験板が十分な密着力を維持できなかった。No.7では、養生中にウレタン樹脂の物性が低下したものと考えられる。No.1、11、17及び18では、トップコート層とウレタン樹脂層との界面に水が侵入してウレタン樹脂層とトップコート層との界面の結合が切断されたと考えられる。また、No.6,12及び16では、トップコート層を紫外線が透過してトップコート層とウレタン樹脂層との界面が顕著に劣化したと考えられる。 No. 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.
No. In Nos. 2 to 5, 8 to 10, and 13 to 15, since the conditions according to the present invention were satisfied, the test plate was excellent in adhesion to the urethane resin layer of the top coat layer even in an aqueous environment. Therefore, these test plates were excellent in initial adhesion, and maintained sufficient adhesion even after both tests in a water environment and a combined environment of ultraviolet light and water. On the other hand, no. In No. 7, the test plate did not have sufficient initial adhesion. No. In 1, 11, 17, and 18, the 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.
2 プライマー層
3 ウレタン樹脂層
4 トップコート層
5 樹脂被覆鋼材
6 樹脂層 DESCRIPTION OF SYMBOLS 1 Steel material 2 Primer layer 3
Claims (2)
- 鋼材と、
前記鋼材の表面上のプライマー層と、
前記プライマー層の表面上のウレタン樹脂層と、
前記ウレタン樹脂層の表面上のトップコート層と、
を備え、
前記ウレタン樹脂層は、カーボンブラックを含む無機顔料と、ポリオールの水酸基及びイソシアネートのイソシアネート基の構成原子からなるウレタン結合を有するウレタン樹脂とを含み、
前記トップコート層は、カーボンブラックと、アクリルウレタン樹脂とを含み、
前記ポリオールは、1分子あたり2.7個以上の水酸基を有するひまし油誘導体と、1分子あたり2.0個の水酸基を有する有機組成物とを含み、
前記イソシアネートは、ジフェニルメタンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート誘導体、トルエンジイソシアネート誘導体からなる群から選択される少なくとも1種を含み、
前記ウレタン樹脂層では、前記ウレタン樹脂層の質量から前記イソシアネートの質量を減じた質量を主剤の質量と定義すると、前記カーボンブラックの質量が前記主剤の質量の0.2~5.0%であり、前記無機顔料の質量から前記カーボンブラックの質量を減じた質量が前記主剤の質量の10~60%であり、前記ひまし油誘導体の質量が前記主剤の質量の10~70%であり、
前記トップコート層では、前記カーボンブラックの質量が前記トップコート層の質量の0.2~5.0%である
ことを特徴とする樹脂被覆鋼材。 Steel,
A primer layer on the surface of the steel material;
A urethane resin layer on the surface of the primer layer;
A topcoat layer on the surface of the urethane resin layer;
With
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,
The top coat layer includes carbon black and an acrylic urethane resin,
The polyol includes 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 isocyanate includes at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate derivative, toluene diisocyanate derivative,
In the urethane resin layer, when 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 the carbon 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, and the mass of the castor oil derivative is 10 to 70% of the mass of the main agent.
In the topcoat layer, a resin-coated steel material, wherein the mass of the carbon black is 0.2 to 5.0% of the mass of the topcoat layer. - 鋼材の表面上にプライマーを塗布してプライマー層を形成し、
前記プライマー層の表面上に主剤と硬化剤とからなる液体混合物を塗布し、前記液体混合物を硬化させてウレタン樹脂層を形成し、
前記ウレタン樹脂層の表面上にカーボンブラックを含むアクリルウレタン樹脂塗料を塗布し、前記アクリルウレタン樹脂塗料を硬化させてトップコート層を形成する
樹脂被覆鋼材の製造方法であって、
前記主剤は、カーボンブラックを含む無機顔料と、ポリオールとを含み、
前記硬化剤は、ジフェニルメタンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート誘導体、トルエンジイソシアネート誘導体からなる群から選択される少なくとも1種を含み、
前記ポリオールは、1分子あたり2.7個以上の水酸基を有するひまし油誘導体と、1分子あたり2.0個の水酸基を有する有機組成物とを含み、
前記主剤では、カーボンブラックの質量が前記主剤の質量の0.2~5.0%であり、前記無機顔料の質量から前記カーボンブラックの質量を減じた質量が前記主剤の質量の10~60%であり、前記ひまし油誘導体の質量が前記主剤の質量の10~70%であり、
前記アクリルウレタン樹脂塗料では、前記カーボンブラックの質量が前記アクリルウレタン樹脂塗料の質量の0.2~5.0%である
ことを特徴とする樹脂被覆鋼材の製造方法。 Apply a primer on the surface of the steel material to form a primer layer,
Applying a liquid mixture composed of a main agent and a curing agent on the surface of the primer layer, curing the liquid mixture to form a urethane resin layer,
Applying an acrylic urethane resin paint containing carbon black on the surface of the urethane resin layer, curing the acrylic urethane resin paint to form a topcoat layer,
The main agent contains an inorganic pigment containing carbon black and a polyol,
The curing agent includes at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate derivative, toluene diisocyanate derivative,
The polyol includes a castor oil derivative having 2.7 or more hydroxyl groups per molecule and an organic composition having 2.0 hydroxyl groups per molecule,
In the main agent, the mass of the carbon black is 0.2 to 5.0% of the mass of the main agent, and 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 mass of the castor oil derivative is 10 to 70% of the mass of the main agent,
In the acrylic urethane resin paint, the mass of the carbon black is 0.2 to 5.0% of the mass of the acrylic urethane resin paint.
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JPH0478530A (en) * | 1990-07-20 | 1992-03-12 | Nippon Steel Corp | Colored top coat-coated heavy-duty corrosion-resistant steel material |
JPH04310274A (en) * | 1991-04-05 | 1992-11-02 | Nippon Steel Corp | Polyurethane coating structure |
JPH06126887A (en) * | 1992-10-14 | 1994-05-10 | Nippon Steel Corp | Colored polyurethane-coated steel material |
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JP2001347603A (en) * | 2000-06-08 | 2001-12-18 | Nippon Steel Corp | Heavy corrosion-resistant coated steel material |
CN100368492C (en) * | 2003-04-30 | 2008-02-13 | 新日本制铁株式会社 | Heavy-duty anticorrosive coated steel material with excellent resistance against separation and corrosion |
JP4416167B2 (en) * | 2005-03-08 | 2010-02-17 | 新日本製鐵株式会社 | Chemically treated ground treatment agent for anticorrosion coated steel, chemical groundwork treatment method for anticorrosive coated steel, and anticorrosive coated steel |
JP6196506B2 (en) * | 2013-09-12 | 2017-09-13 | 日鉄住金防蝕株式会社 | Two-component reactive polyurethane elastomer composition, method for lining inner surface of metal tube using the same, coated steel material, and coated tube |
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JPH0478530A (en) * | 1990-07-20 | 1992-03-12 | Nippon Steel Corp | Colored top coat-coated heavy-duty corrosion-resistant steel material |
JPH04310274A (en) * | 1991-04-05 | 1992-11-02 | Nippon Steel Corp | Polyurethane coating structure |
JPH06126887A (en) * | 1992-10-14 | 1994-05-10 | Nippon Steel Corp | Colored polyurethane-coated steel material |
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