WO2020262366A1 - 一次防錆塗料組成物、一次防錆塗膜付き基板およびその製造方法 - Google Patents
一次防錆塗料組成物、一次防錆塗膜付き基板およびその製造方法 Download PDFInfo
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- WO2020262366A1 WO2020262366A1 PCT/JP2020/024571 JP2020024571W WO2020262366A1 WO 2020262366 A1 WO2020262366 A1 WO 2020262366A1 JP 2020024571 W JP2020024571 W JP 2020024571W WO 2020262366 A1 WO2020262366 A1 WO 2020262366A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/045—Fullerenes
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
- B05D2401/10—Organic solvent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
- B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/28—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Definitions
- the present invention relates to a primary rust preventive coating composition (shop primer), a substrate with a primary rust preventive coating film, and a method for producing the same.
- a primary rust preventive paint for the purpose of preventing rusting during construction of large steel structures such as ships, offshore structures, plants, bridges, and land tanks.
- a primary rust preventive paint an organic primary rust preventive paint such as a wash primer, a non-zinc epoxy primer, and an epoxy zinc rich primer, and an inorganic zink primary rust preventive paint containing a siloxane-based binder and zinc powder are known (for example).
- Patent Documents 1 to 4 Patent Documents 1 to 4).
- inorganic zinc primary rust preventive paints having excellent weldability are most widely used.
- the conventional inorganic zinc primary rust preventive paint contains a large amount of zinc powder for the purpose of protecting the surface of the steel sheet. If the rust preventive property of the inorganic zinc primary rust preventive paint can be further improved, the amount of zinc powder can be reduced, and as a result, for example, the cost of zinc can be reduced, which is advantageous.
- An object of the present invention is to provide a primary rust preventive coating composition capable of forming a coating film having better rust preventive properties as compared with a conventional inorganic zinc primary rust preventive paint.
- the present inventors have diligently studied to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by a primary rust preventive coating composition having the following composition, and have completed the present invention.
- the present invention relates to, for example, the following [1] to [6].
- siloxane-based binder which is a condensate of at least one compound selected from alkyl silicates and alkyl trialkoxysilanes, zinc powder (b), graphene, fullerenes and carbon nanotubes.
- the zinc powder (b) is at least one zinc powder selected from a scaly zinc powder and a spherical zinc powder.
- a primary rust preventive coating composition capable of forming a coating film having better rust preventive properties as compared with a conventional inorganic zinc primary rust preventive paint. If the rust preventive property can be further improved, the amount of zinc powder can be reduced, and as a result, for example, the cost of zinc can be reduced, which is considered to be advantageous.
- the primary rust preventive coating composition of the present invention is a siloxane-based binder (a) which is a condensate of at least one compound selected from alkyl silicates and alkyl trialkoxysilanes. ), Zinc powder (b), and at least one carbon-based nanomaterial (c) selected from graphene, fullerenes and carbon nanotubes.
- the siloxane-based binder (a) is a condensate of at least one compound selected from alkyl silicates and alkyl trialkoxysilanes, and a partially hydrolyzed condensate of the compound is preferable.
- alkyl silicate examples include tetra, such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetra-i-propyl orthosilicate, tetra-n-butyl orthosilicate, and tetra-sec-butyl orthosilicate.
- Alkyl orthosilicates examples thereof include polysilicates such as methylpolysilicates and ethylpolysilicates.
- alkyltrialkoxysilane examples include methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane.
- the number of carbon atoms of the alkoxy group contained in the alkyl silicate and the alkyl trialkoxysilane is usually 1 to 4, preferably 1 to 2.
- the number of carbon atoms of the alkyl group contained in the alkyltrialkoxysilane is usually 1 to 4, preferably 1 to 2.
- a condensate of alkyl silicate is preferable, a condensate of tetraethyl orthosilicate is more preferable, and ethyl silicate 40 (trade name; manufactured by Corcote Co., Ltd.), which is an initial condensate of tetraethyl orthosilicate, is preferable. Partially hydrolyzed condensate of is particularly preferred.
- the weight average molecular weight (Mw) of the siloxane-based binder (a) is usually 1,000 to 6,000, preferably 1,200 to 5,000, and more preferably 1,300 to 4,000. Mw is a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.
- the measurement conditions of the GPC method are as follows. A small amount of the binder sample is taken and diluted with tetrahydrofuran, and the solution is further filtered through a membrane filter to obtain a GPC measurement sample.
- Equipment Japan Waters 2695 Separation Module (Alliance GPC Multi System) -Column: Tosoh TSKgel Super H4000 TSKgel Super H2000 -Eluent: tetrahydrofuran (THF) ⁇ Flow velocity: 0.6 ml / min -Detector: Shodex RI-104 ⁇ Column constant temperature bath temperature: 40 °C ⁇ Standard substance: Polystyrene
- Mw is within the above range, it is possible to cure at room temperature (eg, 5 to 40 ° C.) in a short time when the paint is dried, and the rust prevention property of the coating film and the adhesion strength to the substrate and the topcoat coating film are improved. At the same time, the generation of blow holes (inner bubbles) during the welding process tends to be suppressed.
- Mw is at least the above lower limit value
- the curing reaction of the siloxane-based binder (a) is fast, and even when curing in a short time is required, the coating film is dried at a high temperature (eg, 200 to 400 ° C.). It is not necessary to perform heat curing of.
- Mw is not more than the upper limit value, the rust preventive property of the coating film tends to be excellent.
- the siloxane-based binder (a) can be produced by a conventionally known method. For example, hydrochloric acid or the like is added to a mixed solution of at least one compound selected from alkyl silicates and alkyl trialkoxysilanes or an initial condensate thereof and an organic solvent, and the mixture is stirred to produce a partially hydrolyzed condensate. Thereby, the siloxane-based binder (a) can be prepared.
- the SiO 2 equivalent amount of the siloxane-based binder (a) is usually 2 to 40% by mass, preferably 3 to 30% by mass, and more preferably 5 to 5 to the total amount of the coating composition. It is 15% by mass. Such an embodiment is preferable from the viewpoint of film forming property of the composition and rust prevention property of the formed coating film.
- the content ratio of the siloxane-based binder (a) in the coating material obtained by mixing the main agent component and the pigment paste component is adjusted within the above range. Is preferable.
- the composition of the present invention may contain a binder other than the siloxane-based binder (a) as long as the object and effect of the present invention are not impaired.
- binders include polyvinyl butyral resin.
- examples of commercially available polyvinyl butyral resins include Eslek B BM-2 (trade name; manufactured by Sekisui Chemical Co., Ltd.).
- Zinc powder is a powder of metallic zinc or an alloy mainly composed of zinc (eg, an alloy of zinc with at least one selected from aluminum, magnesium and tin, specifically, a zinc-aluminum alloy, Zinc-tin alloy) powder.
- zinc powder (b) include scaly zinc powder and spherical zinc powder.
- the scaly zinc powder preferably has a median diameter (D50) of 30 ⁇ m or less and an average thickness of 1 ⁇ m or less, a median diameter (D50) of 5 to 20 ⁇ m, and an average thickness of 0.2 to 0.2. 0.9 ⁇ m is more preferable.
- the aspect ratio (median diameter / average thickness) represented by the ratio of the median diameter (D50) to the average thickness is preferably 10 to 150, more preferably 20 to 100.
- the median diameter can be measured using a laser scattering diffraction type particle size distribution measuring device, for example, "SALD 2200" (trade name; manufactured by Shimadzu Corporation). For the average thickness, observe the scaly zinc powder using a scanning electron microscope (SEM), for example, "XL-30” (trade name: manufactured by Phillips), and determine the thickness of tens to hundreds of powder particles. It can be calculated by measuring and calculating the average value.
- SALD 2200 trade name; manufactured by Shimadzu Corporation
- SEM scanning electron microscope
- XL-30 trade name: manufactured by Phillips
- STANDART Zinc Flake GTT STANDART Zinc Flake G
- STANDART Zinc Flake AT trade name; manufactured by ECKART GmbH
- STAPA 4 ZNAL7 alloy of zinc and aluminum; trade name; ECKART).
- STAPA 4 ZNSN30 alloy of zinc and tin; trade name; manufactured by ECKART GmbH
- spherical in the spherical zinc powder means that the shape is spherical, and although there is no specified range, the aspect ratio is preferably 1 to 3. Spherical zinc powder is cheaper than scaly zinc powder, and its use can reduce the cost of the coating composition. The aspect ratio can be measured in the same manner as the scaly zinc powder.
- the median diameter (D50) of the spherical zinc powder is preferably 2 to 15 ⁇ m, more preferably 2 to 7 ⁇ m.
- the median diameter can be measured using a laser scattering diffraction type particle size distribution measuring device, for example, "SALD 2200" (trade name; manufactured by Shimadzu Corporation).
- SALD 2200 trade name; manufactured by Shimadzu Corporation
- F-2000 trade name; manufactured by Honjo Chemical Co., Ltd.
- the zinc powder (b) it is preferable to use the scaly zinc powder and the spherical zinc powder in combination because good rust prevention properties can be obtained in the combined system of the zinc powder (b) and the carbon-based nanomaterial (c). ..
- the content ratio of the scaly zinc powder in the zinc powder (b) is preferably 3 to 45% by mass, more preferably 6 to 35% by mass, and further preferably 10 to 25% by mass.
- Such an embodiment is preferable in that a coating film having further excellent rust prevention property, top coat property, and weldability / cutting property can be formed.
- One type or two or more types of zinc powder (b) can be used.
- the content ratio of the zinc powder (b) in the solid content of the coating composition is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and further preferably 25 to 75% by mass. is there.
- the solid content refers to the total component obtained by adding the SiO 2 equivalent of the siloxane-based binder (a) and the components other than the siloxane-based binder (a) excluding the solvent. Such an embodiment is preferable in terms of rust prevention and weldability.
- the content ratio of zinc powder (b) in the solid content of the paint obtained by mixing the main agent component and the pigment paste component is adjusted to the above range. It is preferable to do so.
- the zinc powder (b) is carbon-based together with the zinc powder (b). Since the nanomaterial (c) is used, good rust prevention can be obtained. Further, the cost of zinc can be reduced by the amount of reducing the amount of zinc powder (b), and the viscosity of the obtained coating composition can be appropriately maintained even if the amount of other pigment components is increased. For example, when the amount of potassium feldspar is increased by the amount of the zinc powder (b) decreased, the weldability can be expected to be improved.
- the composition of the present invention has excellent rust preventive properties, top coat properties, and welding of steel plates even when the amount of zinc powder (b) is smaller than that of the conventional inorganic zinc primary rust preventive coating composition. -It is possible to form a coating film having excellent weldability and cutability in the cutting process.
- the content ratio of the zinc powder (b) in the solid content of the coating composition is preferably 55% by mass or less, more preferably 10 to 55% by mass, still more preferably 15 to 55% by mass. Even more preferably, it is 25 to 55% by mass, and particularly preferably 30 to 55% by mass.
- the carbon-based nanomaterial (c) is at least one selected from graphene, fullerenes and carbon nanotubes.
- graphene the carbon-based nanomaterial in the present invention means that the sheet thickness is nano-sized, and the particle size may exceed the nano-sized.
- carbon nanotubes it means that the diameter is nano-sized, and the fiber length may exceed the nano-sized.
- Graphene is a monatomic sheet (graphene sheet) in which multiple carbon atoms are bonded in a planar and hexagonal lattice pattern.
- a graphene sheet in which a large number of graphene sheets are laminated is called graphite, but the graphene in the present invention is not only a graphene sheet consisting of only one layer in which carbon atoms are arranged in a plane, but the sheet has several to 100 layers. It also includes substances that are laminated and commercially named graphene.
- the particle size of graphene varies, it is preferable to use graphene having a median diameter (D50) of 1 to 10 ⁇ m in the composition of the present invention. The median diameter can be measured with a laser scattering diffraction type particle size distribution measuring device, for example, "SALD 2200" (trade name; manufactured by Shimadzu Corporation).
- Fullerene refers to a closed-shell hollow molecule consisting of a plurality of carbon atoms, for example, a closed-shell hollow molecule composed of a five-membered ring and a six-membered ring formed by covalent bonds of a plurality of carbon atoms. The diameter is 0.5-2 nm.
- fullerenes include C 60 fullerenes and C 70 fullerenes.
- the "carbon nanotube” is a carbon material having a shape in which a graphene sheet is wound in a tubular shape.
- Examples thereof include multi-walled carbon nanotubes.
- Carbon nanotubes have a diameter in the nanometer region, for example 0.4-50 nm.
- Examples of commercially available graphene products include Genable 1031 and Genable 1231 (trade name; manufactured by Applied Graphene Materials plc) and Graphene Division in NMP (trade name: manufactured by ACS Material).
- Examples of commercially available fullerenes include Fullerene C60 (trade name: manufactured by Tokyo Chemical Industry Co., Ltd.), C60 fullerene, and C70 fullerene (trade name: manufactured by Honjo Chemical Co., Ltd.).
- Commercially available carbon nanotubes include, for example, single-walled nanotubes, double-walled nanotubes, multi-walled nanotubes (trade name: manufactured by Honjo Chemical Co., Ltd.), Carbon Nanotube Single-walled, Carbon Nanotube Multi-walled, and Carbon Nanotube Allied. (Product name: manufactured by Tokyo Kasei Kogyo Co., Ltd.).
- carbon-based nanomaterial (c) further improves the rust prevention property
- graphene is a sheet-like substance (graphene sheet) having a sheet thickness of nano-order, and the graphene sheet is applied in the coating film. It is considered that the graphene sheets are oriented substantially parallel to the film surface and that there are many layers of graphene sheets in the thickness direction of the coating film. Therefore, it is considered that the graphene sheet exerts a shielding effect against moisture and the like, and the rust prevention property is improved. Further, since fullerenes and carbon nanotubes have high conductivity, it is considered that the sacrificial anticorrosion effect of zinc is more effectively exhibited.
- the content of the carbon-based nanomaterial (c) with respect to 100 parts by mass of the zinc powder (b) is preferably 0.0001 to 0.7 parts by mass, more preferably 0.002 to 0.5 parts. It is a mass part.
- this content is in the above range, it is preferable in terms of rust prevention.
- excellent rust prevention can be obtained by using a trace amount of carbon-based nanomaterial (c) as described above, which is advantageous from the viewpoint of cost. If this content exceeds the above range, the electrocorrosion-preventing action becomes excessive, zinc consumption increases, and rust-preventive properties may be insufficient. If this content is less than the above range, the electrocorrosion-proofing action of the coating film is insufficient, which may also be insufficient in rust-proofing property.
- the content ratio of the carbon-based nanomaterial (c) in the solid content of the coating composition is preferably 0.0001 to 0.3% by mass, more preferably 0.0007 to 0.25% by mass. Is.
- the composition of the present invention is, for example, a rust preventive pigment other than zinc powder (b), a conductive material other than zinc powder (b) and a carbon-based nanomaterial (c), and an inorganic material other than the above (b) and (c). It may contain a pigment component such as powder, glass powder, molybdenum, or molybdenum compound.
- the composition of the present invention may contain a rust preventive pigment other than the zinc powder (b) for the purpose of auxiliary ensuring the rust preventive property of the coating film.
- a rust preventive pigment include zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, aluminum zinc phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, and calcium phosphite compounds.
- Examples of commercially available products of the rust preventive pigment include zinc phosphate-based (aluminum) compound: LF Bowsei CP-Z (trade name: manufactured by Kikuchi Color Co., Ltd.) and aluminum zinc phosphate-based compound: LF Bowsei PM-.
- 303W (trade name: manufactured by Kikuchi Color Co., Ltd.), zinc phosphate-based (calcium) compound: Protectex YM-70 (trade name: manufactured by Taihei Chemical Industry Co., Ltd.), zinc phosphate-based (strontium) compound : Protectex YM-92NS (trade name: manufactured by Taihei Kagaku Sangyo Co., Ltd.), aluminum tripolyphosphate compound: K White # 84 (trade name: manufactured by Teika Co., Ltd.), cyanamide zinc-based compound: LF Bowsei ZK-32 ( Product name: Kikuchi Color Co., Ltd.).
- One kind or two or more kinds of the rust preventive pigments can be used.
- composition of the present invention may contain a conductive material other than the zinc powder (b) and the carbon-based nanomaterial (c) for the purpose of supplementing the anticorrosion action of the carbon-based nanomaterial (c).
- a conductive material other than the zinc powder (b) and the carbon-based nanomaterial (c) for the purpose of supplementing the anticorrosion action of the carbon-based nanomaterial (c).
- the conductive material include zinc oxide, metal powder other than zinc powder (b), and carbon powder other than carbon-based nanomaterial (c).
- Examples of the commercially available zinc oxide product include zinc oxide type 1 (manufactured by Sakai Chemical Industry Co., Ltd.) and zinc oxide type 3 (manufactured by HakusuiTech Co., Ltd., Sakai Chemical Industry Co., Ltd.).
- Examples of the metal powder include Fe—Si powder, Fe—Mn powder, Fe—Cr powder, magnetic iron powder, and iron phosphate.
- Examples of commercially available products of the metal powder include ferrosilicon (trade name: manufactured by Kinsei Matek Co., Ltd.), ferromanganese (trade name: manufactured by Kinsei Matek Co., Ltd.), and ferrochrome (trade name: manufactured by Kinsei Matek Co., Ltd.). ), Iron powder (trade name; manufactured by Kinsei Matek Co., Ltd.), Ferrofos 2132 (trade name; manufactured by Occidental Chemical Corporation).
- Examples of the carbon powder include carbon black used as a coloring pigment, and examples of commercially available carbon black products include Mitsubishi Carbon Black MA-100 (trade name; manufactured by Mitsubishi Chemical Corporation). Further, as the carbon powder, graphite is also mentioned, and as a commercially available product of graphite, for example, earthy graphite (trade name; manufactured by Nishimura Graphite Co., Ltd.) can be mentioned.
- the content of the conductive material other than the above (b) and (c) is preferably 0 to 60 parts by mass, more preferably 2 to 2 to 100 parts by mass with respect to 100 parts by mass of the zinc powder (b). It is 50 parts by mass.
- Such an embodiment is preferable in that the electrocorrosion-proof effect of the coating film is enhanced and the rust-preventive property is improved.
- the composition of the present invention may further contain an inorganic powder other than the zinc powder (b) and the carbon-based nanomaterial (c).
- an inorganic powder for example, zinc oxide compound powder (however, zinc oxide, zinc phosphate compound, zinc phosphite compound, cyanamide zinc compound), mineral powder, alkali glass powder, and thermal decomposition gas are generated. Inorganic compound powder to be used.
- the zinc compound powder is considered to have an action of adjusting the activity of the oxidation reaction such as the degree of ionization (production of Zn 2+ ) of the zinc powder (b).
- the composition of the present invention contains a zinc compound powder, it is possible to impart more appropriate rust preventive properties to the composition.
- the zinc compound powder include powders of zinc chloride, zinc sulfide, zinc sulfate and the like.
- Examples of commercially available zinc compound powders include "Sachtolich HD (zinc sulfide; trade name; manufactured by Sachleben Chemie GmbH)” and “zinc chloride (manufactured by Nagai Pharmaceutical Co., Ltd.)".
- mineral powder examples include titanium mineral powder, silica powder, soda feldspar, potassium feldspar, zirconium silicate, wollastonite, and diatomaceous earth.
- Commercially available mineral powders include, for example, rutile flower S (manufactured by Kinseimatec Co., Ltd.), ilmenite powder (manufactured by Kinseimatec Co., Ltd.), A-PAX (manufactured by Kinseimatec Co., Ltd.), and ceramic powder OF-T.
- the alkaline glass powder has the effect that the alkali metal ions contained in the glass powder activate zinc and stabilize the arc during welding of the steel sheet.
- the alkaline glass powder include those obtained by crushing commonly used flat glass or bottle glass to about 5 ⁇ m to prepare a glass powder, and adjusting the pH of the glass powder to 8 or less by acid cleaning.
- Examples of commercially available alkaline glass powders include APS-325 (trade name; manufactured by Puremic Co., Ltd.).
- the inorganic compound powder that generates a pyrolysis gas is a powder of an inorganic compound that generates a gas (eg CO 2 , F 2 ) by thermal decomposition (eg, thermal decomposition at 500 to 1,500 ° C.).
- the inorganic compound powder was generated from a gas generated from an organic component contained in a binder or the like in a molten pool at the time of welding when a steel plate having a coating film formed from a coating composition containing the powder was welded. It has an action of removing air bubbles from the molten pool together with the gas derived from the inorganic compound powder.
- Examples of the inorganic compound powder that generates a pyrolysis gas include calcium fluoride, calcium carbonate, magnesium carbonate, and strontium carbonate.
- Examples of commercially available products of the inorganic compound powder include fluorite 400 mesh (trade name: manufactured by Kinsei Matek Co., Ltd.), Super SS (trade name: manufactured by Maruo Calcium Co., Ltd.), and magnesium carbonate (trade name; manufactured by Tomita Pharmaceutical Co., Ltd.). (Manufactured by Honjo Chemical Co., Ltd.), Strontium carbonate A (trade name; manufactured by Honjo Chemical Co., Ltd.).
- the content of the pigment component can be increased.
- the content of potassium feldspar may be increased in order to improve weldability.
- the content ratio of potassium feldspar in the solid content of the coating composition is preferably 5 to 45% by mass, more preferably 10 to 43% by mass.
- the amount of zinc powder (b) is reduced in the present invention for example, when the amount of zinc powder (b) in the solid content of the coating composition is 55% by mass or less
- the potassium orthoclase in the solid content of the coating composition The content ratio is preferably 30 to 40% by mass.
- the composition of the present invention may contain a glass powder having a softening point of 400 to 800 ° C. and having a total content of Li 2 O, Na 2 O and K 2 O of 12% by mass or less.
- the glass powder acts as an antioxidant for zinc when the coating film is heated at a high temperature, for example 400-900 ° C.
- the glass powder is, for example, a compound obtained by heating and melting a compound constituting glass at about 1,000 to 1,100 ° C. for a predetermined time, cooling it, and then sizing it into a powder by a pulverizer.
- the components constituting the glass include SiO 2 , B 2 O 3 , Al 2 O 3 , ZnO, BaO, MgO, CaO, SrO, Bo 2 O 3 , Li 2 O, Na 2 O, K 2 O, and so on.
- Examples thereof include PbO, P 2 O 5 , In 2 O 3 , SnO, CuO, Ag 2 O, V 2 O 5 , and TeO 2 .
- PbO can also be used as a compound constituting glass, but it is desirable not to use it because it may have an adverse effect on the environment.
- the glass powder contains the above-mentioned compounds in a desired ratio in order to obtain various glass characteristics such as softening point, coefficient of thermal expansion, dielectric constant, transparency, and hue.
- the composition of the present invention may contain one or both of molybdenum (metal molybdenum) and molybdenum compounds. These act as zinc antioxidants (so-called white rust inhibitors).
- the zinc or zinc alloy in the coating film reacts with water, oxygen, and carbon dioxide gas to cause powdery white rust (zinc oxide) on the coating surface. , A mixture of zinc hydroxide, zinc carbonate, etc.) may be produced.
- a topcoat coating film made of a topcoat coating film is formed on the surface of the coating film on which white rust is generated, the adhesion between the coating films may decrease.
- it is necessary to remove the white rust on the surface of the rust preventive coating film by an appropriate means before applying the top coat, but depending on the customer's request and specific application, it is necessary to remove it. Such removal work may not be allowed at all.
- the composition of the present invention contains one or both of molybdenum (metal molybdenum) and molybdenum compound as zinc antioxidants (so-called white rust inhibitors). It is preferable to do so.
- molybdate compound examples include molybdate compounds other than the above-mentioned aluminum-zinc phosphomolybdate compound.
- silicate molybdate alkali metal salt of molybdate, alkali metal salt of phosphomolybdate, alkali metal salt of silicate molybdate, alkaline earth metal salt of molybdate, alkaline earth metal salt of phosphomolybdate, silicate molybdate Alkaline earth metal salt, manganese salt of molybdate, manganese salt of phosphomolybdate, manganese salt of silicolybdate, basic nitrogen-containing compound salt of molybdate, basic nitrogen-containing compound salt of phosphomolybdate, silicate molybdate Basic nitrogen-containing compound salt of.
- molybdenum compounds can be used.
- the total content of molybdenum and molybdenum compound is preferably 0.05 to 5.0 parts by mass, more preferably 0.05 parts by mass with respect to 100 parts by mass of the zinc powder (b). It is 0.3 to 3.0 parts by mass, more preferably 0.5 to 2.0 parts by mass.
- the content is within the above range, a sufficient antioxidant effect of zinc can be obtained, and the rust preventive property of the coating film can be maintained by preventing a decrease in the activity of the rust preventive ability of the zinc powder (b).
- the composition of the present invention may contain additives.
- Additives are materials used to improve or retain the performance of paints and coatings.
- the additive include a settling inhibitor, a desiccant, a fluidity modifier, a defoaming agent, a dispersant, a color separation inhibitor, a skinning inhibitor, a plasticizer, and an ultraviolet absorber.
- One kind or two or more kinds of additives can be used.
- sedimentation inhibitor examples include organic bentonite-based, polyethylene oxide-based, fumed silica-based, and amide-based sedimentation inhibitors.
- Commercially available anti-settling agents include, for example, TIXOGEL MPZ (trade name: Rockwood Clay Additives GmbH), Disparon 4200-20 (trade name; Kusumoto Kasei Co., Ltd.), Disparon A630-20X (trade name; Kusumoto Kasei). (Manufactured by Nippon Aerosil Co., Ltd.), AEROSIL 200 (trade name; manufactured by Nippon Aerosil Co., Ltd.).
- the content ratio of the sedimentation inhibitor is usually 0.5 to 5.0% by mass, preferably 1.0 to 4.% in the pigment paste component. It is 0% by mass.
- the content ratio of the anti-precipitation agent is within the above range, the pigment component is less precipitated, which is preferable in terms of workability when mixing the pigment paste component and the main agent component.
- the composition of the present invention is an organic solvent because the dispersibility of the zinc powder (b) is improved, the coating film has good compatibility with the steel sheet in the coating process, and a coating film having excellent adhesion to the steel sheet can be obtained. Is preferably contained.
- organic solvent examples include organic solvents usually used in the coating field, such as alcohol solvents, ester solvents, ketone solvents, aromatic solvents, and glycol solvents.
- Examples of the alcohol solvent include methanol, ethanol, propanol and butanol.
- Examples of the ester solvent include ethyl acetate and butyl acetate.
- Examples of the ketone solvent include methyl isobutyl ketone and cyclohexanenon.
- Examples of the aromatic solvent include benzene, xylene and toluene.
- Examples of the glycol-based solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. One kind or two or more kinds of organic solvents can be used.
- the content ratio of the organic solvent is usually 30 to 90% by mass, preferably 40 to 85% by mass, and more preferably 45 to 80% by mass.
- the composition of the present invention is preferably such an organic solvent type composition.
- the composition of the present invention is a two-component composition described later, it is preferable to adjust the content ratio of the organic solvent in the coating material obtained by mixing the main agent component and the pigment paste component within the above range.
- the primary rust preventive coating composition of the present invention is usually used as a two-component composition. That is, the coating composition is usually composed of a main ingredient (vehicle) and a pigment paste component. It is preferable to store the main ingredient and the pigment paste component in separate containers before use, and to prepare a primary rust preventive paint by sufficiently stirring and mixing them immediately before use.
- the main ingredient usually contains an organic solvent in addition to the siloxane-based binder (a).
- the main component may be prepared by mixing a siloxane-based binder (a) and an organic solvent; at least one compound selected from alkyl silicates and alkyl trialkoxysilanes or an initial condensate thereof, and an organic solvent. It may be prepared by adding hydrochloric acid or the like to the mixed solution with and stirring to generate a partially hydrolyzed condensate. Further, the main agent component may contain a binder other than the siloxane-based binder (a).
- the pigment paste component usually contains an organic solvent in addition to zinc powder (b) and carbon-based nanomaterial (c).
- the pigment paste component is prepared by mixing, for example, zinc powder (b), carbon-based nanomaterial (c), an organic solvent and, if necessary, other components according to a conventional method.
- Other components include, for example, rust preventive pigments other than zinc powder (b), conductive materials other than zinc powder (b) and carbon-based nanomaterial (c), and inorganic powders other than the above (b) and (c).
- the blending ratio of the main agent component and the pigment paste component is appropriately adjusted so that the content ratios of the mixed siloxane-based binder (a), zinc powder (b), carbon-based nanomaterial (c) and organic solvent are within the above-mentioned ranges. Can be set.
- the substrate with a primary rust preventive coating of the present invention has a substrate such as a steel plate and a primary rust preventive coating film formed on the surface of the substrate and composed of the primary rust preventive coating composition of the present invention.
- the average dry film thickness of the primary rust preventive coating film is usually 30 ⁇ m or less, preferably 5 to 25 ⁇ m, more preferably 5 to 17 ⁇ m, and particularly preferably 5 to 10 ⁇ m.
- the average dry film thickness can be measured, for example, by using an electromagnetic film thickness meter.
- the composition of the present invention uses the carbon-based nanomaterial (c) together with the zinc powder (b), the amount of the zinc powder (b) is reduced and the average dry film thickness of the primary rust preventive coating film is reduced. Good rust prevention is obtained even when (for example, 5 to 10 ⁇ m) or when the substrate with the primary rust preventive coating of the present invention is exposed to the outdoors for a long period of time such as 3 months. be able to. If the average dry film thickness of the primary rust preventive coating film is reduced, the processing speed can be increased in the welding / cutting process of the substrate (steel plate) with the primary rust preventive coating film, which is advantageous in terms of productivity.
- the method for producing a substrate with a primary rust preventive coating of the present invention includes a step of applying the primary rust preventive coating composition of the present invention (painting step) on a substrate surface such as a steel plate, and curing the coated coating composition. It has a step (curing step) of forming a primary rust preventive coating film.
- the composition of the present invention in the case of a two-component composition, a coating material obtained by mixing a main component and a pigment paste component
- a conventionally known method such as air spray or airless spray.
- the surface of the substrate is coated to form an uncured coating film.
- a line painting machine As a painting machine, a line painting machine is generally used when painting paint at a shipyard, a steel mill, etc.
- the line coating machine controls the film thickness according to the line speed, the coating pressure of the air spray and airless spray installed inside the coating machine, and the coating conditions of the spray tip size (caliber).
- the curing temperature (drying temperature) in the curing step is usually 5 to 40 ° C, preferably 10 to 30 ° C.
- the composition of the present invention is suitable for use in the pretreatment of steel sheets performed in the steel sheet processing process in large steel structures such as ships, offshore structures, plants, bridges and land tanks.
- the substrate with the primary rust preventive coating film of the present invention can simultaneously improve the rust preventive property and the weldability.
- Mw 2,500.
- the measurement conditions of GPC are as follows. A small amount of the condensate sample was taken, diluted with tetrahydrofuran, and the solution was further filtered through a membrane filter to obtain a GPC measurement sample.
- Preparation Example 2-1 Preparation of pigment paste component 1.0 part of TIXOGEL MPZ (trade name; manufactured by Rockwood Clay Additives GmbH) as an anti-settling agent and 18.3 as an inorganic powder other than (b) and (c).
- Part of Ceramic Powder OF-T Product Name: Kinsei Matek Co., Ltd., Cali Nagaishi
- Super SS Product Name: Maruo Calcium Co., Ltd.
- (b) and (c) 1.0 parts of zinc oxide 3 types (trade name: manufactured by HakusuiTech Co., Ltd.) as conductive materials other than, 6.1 parts of xylene as an organic solvent, 5.7 parts of butyl acetate and 8.4 parts.
- Preparation Examples 2-2 to 2-19 Preparation of Pigment Paste Component
- the pigment paste component was prepared in the same manner as in Preparation Example 2-1 except that the compounding composition was changed as shown in Table 1.
- the carbon-based nanomaterial (c) was added when the organic solvent was added.
- -Fullrene C60 C 60 full- wallene, purity 99.0% or more, manufactured by Tokyo Kasei Kogyo Co., Ltd.
- -Soil graphite graphite, manufactured by Nishimura Graphene Co., Ltd.
- the primary rust preventive paint was applied to the blasted surface of the sandblasted plate (JIS G3101, SS400, dimensions: 150 mm ⁇ 70 mm ⁇ 2.3 mm) using a line coating machine.
- the test plate is dried in a thermostatic chamber at a temperature of 23 ° C. and a relative humidity of 50% for one week, and a test plate composed of a primary rust preventive coating film having an average dry thickness of 8 ⁇ m and the treated plate is formed. Created.
- the average dry film thickness was measured using an electromagnetic film thickness meter "LE-370" (trade name; manufactured by Kett Science Laboratory Co., Ltd.).
- test plate was installed on an outdoor exposure table (on the premises of Otake Research Institute of China Paint Co., Ltd.) and left for a certain period of time.
- the test plate was fixed in a state in which the painted surface of the test plate faced the south side and the test plate was tilted at 45 degrees with respect to the horizontal.
- the area ratio (%) of the rusted test plate surface and the white rusted test plate surface to the entire surface of the test plate after being left for 1 month and 3 months was measured to determine the rusted state and the white rust.
- the state of occurrence was evaluated.
- the evaluation criteria are as follows.
- ⁇ Evaluation criteria for rust condition (ASTM D610)> 10: No rust is observed, or the area ratio of rust is 0.01% or less 9: Very slight rust, or the area ratio of rust is more than 0.01% and 0.03% or less 8: Slight Rust or rust area ratio exceeds 0.03% and 0.1% or less 7: Rust area ratio exceeds 0.1% and 0.3% or less 6: Clear spot rust or rust Area ratio is more than 0.3% and less than 1% 5: Rust area ratio is more than 1% and less than 3% 4: Rust area ratio is more than 3% and less than 10% 3: Rust area ratio Is more than 10% and 1/6 (16%) or less 2: Rust area ratio is more than 1/6 (16%) and 1/3 (33%) or less 1: Rust area ratio is 1/3 ( More than 33%) and less than 1/2 (50%) 0: Rust area ratio is more than 1/2 (50%) and up to 100%
Abstract
Description
本発明は、例えば以下の[1]~[6]に関する。
[2]亜鉛粉末(b)が、鱗片状亜鉛粉末および球状亜鉛粉末から選択される少なくとも1種の亜鉛粉末である前記[1]に記載の一次防錆塗料組成物。
[3]亜鉛粉末(b)100質量部に対する炭素系ナノ材料(c)の含有量が、0.0001~0.7質量部である前記[1]または[2]に記載の一次防錆塗料組成物。
[4]炭素系ナノ材料(c)が、グラフェンを含む前記[1]~[3]のいずれかに記載の一次防錆塗料組成物。
[5]基板と、前記基板表面に形成された、前記[1]~[4]のいずれかに記載の一次防錆塗料組成物からなる一次防錆塗膜とを有する一次防錆塗膜付き基板。
[6]基板表面に、前記[1]~[4]のいずれかに記載の一次防錆塗料組成物を塗装する工程、および塗装された前記一次防錆塗料組成物を硬化させて一次防錆塗膜を形成する工程を有する、一次防錆塗膜付き基板の製造方法。
[一次防錆塗料組成物]
本発明の一次防錆塗料組成物(以下「本発明の組成物」ともいう)は、アルキルシリケートおよびアルキルトリアルコキシシランから選択される少なくとも1種の化合物の縮合物であるシロキサン系結合剤(a)と、亜鉛粉末(b)と、グラフェン、フラーレンおよびカーボンナノチューブから選択される少なくとも1種の炭素系ナノ材料(c)とを含有する。
シロキサン系結合剤(a)は、アルキルシリケートおよびアルキルトリアルコキシシランから選択される少なくとも1種の化合物の縮合物であり、前記化合物の部分加水分解縮合物が好ましい。
・装置:日本ウォーターズ社製 2695セパレ-ションモジュール
(Aliance GPC マルチシステム)
・カラム:東ソー社製 TSKgel Super H4000
TSKgel Super H2000
・溶離液:テトラヒドロフラン(THF)
・流速:0.6ml/min
・検出器:Shodex RI-104
・カラム恒温槽温度:40℃
・標準物質:ポリスチレン
本発明の組成物において、シロキサン系結合剤(a)のSiO2換算量は、塗料組成物の全量に対し、通常は2~40質量%、好ましくは3~30質量%、より好ましくは5~15質量%である。このような態様であると、組成物の造膜性および形成される塗膜の防錆性の観点から好ましい。
本発明の組成物は、本発明の目的および効果を損なわない範囲で、シロキサン系結合剤(a)以外の他の結合剤を含有してもよい。他の結合剤としては、例えば、ポリビニルブチラール樹脂が挙げられる。ポリビニルブチラール樹脂の市販品としては、例えば、エスレックB BM-2(商品名;積水化学工業(株)製)が挙げられる。
「亜鉛粉末」とは、金属亜鉛の粉末、または亜鉛を主体とする合金(例:亜鉛とアルミニウム、マグネシウムおよび錫から選択される少なくとも1種との合金、具体的には、亜鉛-アルミニウム合金、亜鉛-錫合金)の粉末を意味する。
亜鉛粉末(b)としては、例えば、鱗片状亜鉛粉末、球状亜鉛粉末が挙げられる。
球状亜鉛粉末の市販品としては、例えば、F-2000(商品名;本荘ケミカル(株)製)が挙げられる。
亜鉛粉末(b)は1種または2種以上用いることができる。
炭素系ナノ材料(c)は、グラフェン、フラーレンおよびカーボンナノチューブから選択される少なくとも1種である。本発明における炭素系ナノ材料は、「グラフェン」の場合はシート厚さがナノサイズであることを指し、粒子径はナノサイズを超えていてもよい。同様に、「カーボンナノチューブ」の場合は直径がナノサイズであることを指し、繊維長はナノサイズを超えていてもよい。
また、フラーレンおよびカーボンナノチューブは、高い導電性を有しているため、亜鉛の犠牲防食効果をより効果的に発揮させると考えられる。これは、亜鉛から放出された電子が、より効果的に鋼板などの基材表面に到達することが可能となり、鋼板が腐食から保護されることを意味する。またフラーレン、カーボンナノチューブはナノオーダーのサイズであるため、少量の添加で塗膜中に均一に分散し、この導電性の効果を得ることができる。このため、防錆性が向上すると考えられる。
本発明の組成物は、例えば、亜鉛粉末(b)以外の防錆顔料、亜鉛粉末(b)および炭素系ナノ材料(c)以外の導電性材料、前記(b)および(c)以外の無機粉末、ガラス粉末、モリブデン、モリブデン化合物などの顔料成分を含有してもよい。
本発明の組成物は、補助的に塗膜の防錆性を確保する目的で、亜鉛粉末(b)以外の防錆顔料を含有してもよい。前記防錆顔料としては、例えば、リン酸亜鉛系化合物、リン酸カルシウム系化合物、リン酸アルミニウム系化合物、リンモリブデン酸アルミニウム亜鉛系化合物、リン酸マグネシウム系化合物、亜リン酸亜鉛系化合物、亜リン酸カルシウム系化合物、亜リン酸アルミニウム系化合物、亜リン酸ストロンチウム系化合物、トリポリリン酸アルミニウム系化合物、シアナミド亜鉛系化合物、ホウ酸塩化合物、ニトロ化合物、複合酸化物が挙げられる。
前記防錆顔料は1種または2種以上用いることができる。
本発明の組成物は、炭素系ナノ材料(c)の電気防食作用を補う目的で、亜鉛粉末(b)および炭素系ナノ材料(c)以外の導電性材料を含有してもよい。前記導電性材料としては、例えば、酸化亜鉛、亜鉛粉末(b)以外の金属粉末、炭素系ナノ材料(c)以外の炭素粉末が挙げられる。
前記金属粉末としては、例えば、Fe-Si粉、Fe-Mn粉、Fe-Cr粉、磁鉄粉、リン化鉄が挙げられる。前記金属粉末の市販品としては、例えば、フェロシリコン(商品名;キンセイマテック(株)製)、フェロマンガン(商品名;キンセイマテック(株)製)、フェロクロム(商品名;キンセイマテック(株)製)、砂鉄粉(商品名;キンセイマテック(株)製)、フェロフォス2132(商品名;オキシデンタルケミカルコーポレーション製)が挙げられる。
本発明の組成物において、前記(b)および(c)以外の導電性材料の含有量は、亜鉛粉末(b)100質量部に対して、好ましくは0~60質量部、より好ましくは2~50質量部である。このような態様であると、塗膜の電気防食効果を高め、防錆性を向上させる点で好ましい。
本発明の組成物は、亜鉛粉末(b)および炭素系ナノ材料(c)以外の無機粉末をさらに含有してもよい。前記無機粉末としては、例えば、亜鉛化合物粉末(ただし、酸化亜鉛、リン酸亜鉛系化合物、亜リン酸亜鉛系化合物、シアナミド亜鉛系化合物を除く)、鉱物粉末、アルカリガラス粉末、熱分解ガスを発生する無機化合物粉末が挙げられる。
本発明の組成物は、400~800℃の軟化点を有し、Li2O、Na2OおよびK2Oの含有量の合計が12質量%以下であるガラス粉末を含有してもよい。前記ガラス粉末は、塗膜が高温、例えば400~900℃で加熱された際に亜鉛の酸化防止剤として作用する。
本発明の組成物は、モリブデン(金属モリブデン)、モリブデン化合物の一方または双方を含有してもよい。これらは、亜鉛の酸化防止剤(いわゆる白錆抑制剤)として作用する。
モリブデン、モリブデン化合物の一方または双方を用いる場合、モリブデンおよびモリブデン化合物の含有量の合計は、亜鉛粉末(b)100質量部に対して、好ましくは0.05~5.0質量部、より好ましくは0.3~3.0質量部、さらに好ましくは0.5~2.0質量部である。含有量が前記範囲にある場合、充分な亜鉛の酸化防止作用が得られるとともに、亜鉛粉末(b)の防錆能力の活性の低下を防ぎ塗膜の防錆性を維持することができる。
本発明の組成物は、添加剤を含有してもよい。添加剤とは、塗料や塗膜の性能を向上させ、または保持するために用いられる材料である。添加剤としては、例えば、沈降防止剤、乾燥剤、流動性調整剤、消泡剤、分散剤、色分れ防止剤、皮張り防止剤、可塑剤、紫外線吸収剤が挙げられる。
添加剤は1種または2種以上用いることができる。
沈降防止剤の含有割合は、本発明の組成物が後述する2液型組成物の場合、顔料ペースト成分中において、通常は0.5~5.0質量%、好ましくは1.0~4.0質量%である。沈降防止剤の含有割合が前記範囲にあると、顔料成分の沈殿が少なく、顔料ペースト成分と主剤成分とを混合する際の作業性の点で好ましい。
本発明の組成物は、亜鉛粉末(b)の分散性が向上すること、また塗装工程において鋼板へのなじみ性が良く、鋼板との密着性に優れた塗膜が得られることから、有機溶剤を含有することが好ましい。
有機溶剤は1種または2種以上用いることができる。
本発明の一次防錆塗料組成物は、2液型組成物として通常用いられる。すなわち、前記塗料組成物は、通常、主剤成分(ビヒクル)と顔料ペースト成分とから構成される。使用前は主剤成分と顔料ペースト成分とを別容器に保存しておき、使用直前にこれらを充分に撹拌・混合して、一次防錆塗料を調製することが好ましい。
本発明の一次防錆塗膜付き基板は、鋼板などの基板と、前記基板表面に形成された、本発明の一次防錆塗料組成物からなる一次防錆塗膜とを有する。一次防錆塗膜の平均乾燥膜厚は、通常は30μm以下、好ましくは5~25μm、より好ましくは5~17μm、特に好ましくは5~10μmである。平均乾燥膜厚は、例えば、電磁式膜厚計を用いることによって測定することができる。
本発明の組成物は、船舶、海洋構造物、プラント、橋梁、陸上タンク等の大型鉄鋼構造物における鋼板加工工程で行われる鋼板の前処理での使用に適している。
エチルシリケート40(コルコート(株)製;SiO2換算分=40質量%)31.5g、工業用エタノール10.4g、脱イオン水5g、および35質量%塩酸0.1gを容器に仕込み、50℃で4時間40分攪拌した後、イソプロピルアルコール53gを加えて、アルキルシリケートの縮合物1を含有する溶液(SiO2換算分=12.6質量%)を調製した。
ゲルパーミエーションクロマトグラフィー(GPC)法で縮合物1の重量平均分子量(Mw)を測定したところMw=2,500であった。
なお、GPCの測定条件は、以下のとおりである。縮合物サンプルを少量取りテトラヒドロフランを加えて希釈し、さらにその溶液をメンブレムフィルターで濾過して、GPC測定サンプルを得た。
・装置:日本ウォーターズ社製 2695セパレ-ションモジュール
(Aliance GPC マルチシステム)
・カラム:東ソー社製 TSKgel Super H4000
TSKgel Super H2000
・溶離液:テトラヒドロフラン(THF)
・流速:0.6ml/min
・検出器:Shodex RI-104
・カラム恒温槽温度:40℃
・標準物質:ポリスチレン
沈降防止剤として1.0部のTIXOGEL MPZ(商品名;Rockwood Clay Additives GmbH製)と、(b)および(c)以外の無機粉末として18.3部のセラミックパウダーOF-T(商品名;キンセイマテック(株)製、カリ長石)と、0.7部のスーパーSS(商品名;丸尾カルシウム(株)製)と、(b)および(c)以外の導電性材料として1.0部の酸化亜鉛3種(商品名;ハクスイテック(株)製)と、有機溶剤として6.1部のキシレンと、5.7部の酢酸ブチルおよび8.4部のイソブチルアルコールとを、ポリエチレン製容器に仕込み、ガラスビーズを加えてペイントシェーカーにて3時間振とうした。次いで、亜鉛粉末(b)として3.4部のSTANDART Zinc Flake GTT(商品名;ECKART GmbH製)と、17.0部のF-2000(商品名;本荘ケミカル(株)製)とを加えて、さらに5分間振とうして、顔料成分を分散させた。その後、80メッシュの網を用いてガラスビーズを除去して顔料ペースト成分を調製した。
配合組成を表1に記載したとおりに変更したこと以外は調製例2-1と同様にして、顔料ペースト成分を調製した。なお、炭素系ナノ材料(c)は、有機溶剤を添加する際に添加した。
・STANDART Zinc Flake GTT:鱗片状亜鉛粉末、メディアン径(D50)=8.5μm、平均厚さ=0.4μm、アスペクト比(メディアン径/平均厚さ)=21)、ECKART GmbH製
・F-2000:球状亜鉛粉末、メディアン径(D50)=5μm、本荘ケミカル(株)製
・LFボウセイ PM-303W:リンモリブデン酸アルミニウム亜鉛系無機化合物、キクチカラー(株)製
・Genable 1031:グラフェンのキシレン/樹脂分散液、グラフェン固形分10質量%、メディアン径(D50)=1~3μm、Applied Graphene Materials plc製
・Genable 1231:グラフェンのキシレン/樹脂分散液、グラフェン固形分1質量%、メディアン径(D50)=5~6μm、Applied Graphene Materials plc製
・Graphene Dispersion in NMP:グラフェン4質量%(N-メチル-2-ピロリドン 94.9質量%)、粒子径0.5~5μm(長さ方向)、ACS Material社製
・Carbon Nanotube Single-walled (>85%) below 3nm(Average diam.), over 5μm(Average length):単層カーボンナノチューブ、平均直径3nm以下、平均繊維長5μm以上、東京化成工業(株)製
・Fullerene C60:C60フラーレン、純度99.0%以上、東京化成工業(株)製
・土状黒鉛:グラファイト、西村黒鉛(株)製
調製例1で得られた、アルキルシリケートの縮合物1を含有する溶液と、表1記載の配合割合で調製された顔料ペースト成分とを、各々の含有成分の比率が表1記載の割合(質量基準)にて混合し、一次防錆塗料を調製した。
塗膜の平均乾燥膜厚が8μmとなるようにライン塗装機(装置名:SP用コンベア塗装機、竹内工作所(株)製)のライン条件(ライン速度:10m/min、塗装圧力:0.2MPa)を調整した。このライン条件で、実施例および比較例で得られた一次防錆塗料を用いて、以下のようにして試験板を作成し、評価を行った。
サンドブラスト処理板(JIS G3101、SS400、寸法:150mm×70mm×2.3mm)のブラスト処理面に、ライン塗装機を用いて一次防錆塗料を塗装した。次いで、JIS K5600 1-6の規格に従い、温度23℃、相対湿度50%の恒温室内で1週間乾燥させて、平均乾燥膜厚8μmの一次防錆塗膜と前記処理板とからなる試験板を作成した。平均乾燥膜厚は、電磁式膜厚計「LE-370」(商品名;(株)ケット科学研究所製)を用いて測定した。
10:発錆を認めない、または発錆の面積比率は0.01%以下
9:極僅かな発錆、または発錆の面積比率は0.01%を超え0.03%以下
8:僅かな発錆、または発錆の面積比率は0.03%を超え0.1%以下
7:発錆の面積比率は0.1%を超え0.3%以下
6:明瞭な点錆、または発錆の面積比率は0.3%を超え1%以下
5:発錆の面積比率は1%を超え3%以下
4:発錆の面積比率は3%を超え10%以下
3:発錆の面積比率は10%を超え1/6(16%)以下
2:発錆の面積比率は1/6(16%)を超え1/3(33%)以下
1:発錆の面積比率は1/3(33%)を超え1/2(50%)以下
0:発錆の面積比率はほぼ1/2(50%)を超え100%まで
10:白錆を認めない、または白錆の面積比率は0.01%以下
9:極僅かな白錆、または白錆の面積比率は0.01%を超え0.03%以下
8:僅かな白錆、または白錆の面積比率は0.03%を超え0.1%以下
7:白錆の面積比率は0.1%を超え0.3%以下
6:明瞭な白錆の点、または白錆の面積比率は0.3%を超え1%以下
5:白錆の面積比率は1%を超え3%以下
4:白錆の面積比率は3%を超え10%以下
3:白錆の面積比率は10%を超え1/6(16%)以下
2:白錆の面積比率は1/6(16%)を超え1/3(33%)以下
1:白錆の面積比率は1/3(33%)を超え1/2(50%)以下
0:白錆の面積比率はほぼ1/2(50%)を超え100%まで
Claims (6)
- アルキルシリケートおよびアルキルトリアルコキシシランから選択される少なくとも1種の化合物の縮合物であるシロキサン系結合剤(a)と、
亜鉛粉末(b)と、
グラフェン、フラーレンおよびカーボンナノチューブから選択される少なくとも1種の炭素系ナノ材料(c)とを含有する一次防錆塗料組成物。 - 亜鉛粉末(b)が、鱗片状亜鉛粉末および球状亜鉛粉末から選択される少なくとも1種の亜鉛粉末である請求項1に記載の一次防錆塗料組成物。
- 亜鉛粉末(b)100質量部に対する炭素系ナノ材料(c)の含有量が、0.0001~0.7質量部である請求項1または2に記載の一次防錆塗料組成物。
- 炭素系ナノ材料(c)が、グラフェンを含む請求項1~3のいずれか1項に記載の一次防錆塗料組成物。
- 基板と、
前記基板表面に形成された、請求項1~4のいずれか1項に記載の一次防錆塗料組成物からなる一次防錆塗膜とを有する一次防錆塗膜付き基板。 - 基板表面に、請求項1~4のいずれか1項に記載の一次防錆塗料組成物を塗装する工程、および塗装された前記一次防錆塗料組成物を硬化させて一次防錆塗膜を形成する工程を有する、一次防錆塗膜付き基板の製造方法。
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EP3991857A4 (en) | 2023-06-28 |
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