Classifications

• • 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
  • C08K3/28—Nitrogen-containing compounds
• • 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
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
  • C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
• • 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
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/04—Portland cements
• • 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
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/10—Copolymers of styrene with conjugated dienes
• • 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
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/14—Copolymers of styrene with unsaturated esters
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/26—Corrosion of reinforcement resistance
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

• the present invention relates to an anticorrosion coating composition used as an undercoat material on a steel surface, a method for producing the same, and a method for preventing corrosion of a steel material.
• Steel structures such as steel structures and steel bridges are premised on long-term use. For this reason, these steel structures have been conventionally surface-coated for the purpose of preventing corrosion and ensuring aesthetics.
• the coating consists of three layers: a base coat for the purpose of preventing rust, a top coat for the purpose of ensuring weather resistance and aesthetics, and an intermediate coat for improving the adhesion between the base coat and the top coat.
• the coating life is greatly influenced by the coating material and the use environment, but in a relatively severe environment, there are examples of 6 years for the modified epoxy paint and 10 years for the epoxy urethane paint. Accordingly, a plurality of repaints are required during the service period of the steel structure.
• iron rust prevention methods As one of iron rust prevention methods, a method is known in which the surface of iron is kept alkaline and passivated. In general, it is said that a passivating layer of Fe 2 O 3 is formed in a pH range of 9 to 12.5, and iron becomes stable.
• a technique for preventing rust by keeping the iron surface alkaline for example, in Patent Document 1, a compound in which carbon fiber is added to a main material composed of a mixture of white cement and ultrafine silica, and cationic styrene butadiene copolymer
• An invention of a surface coating agent comprising a water-soluble curing agent composed of a mixture of a coalesced polymer and a cyclohexyl methacrylate copolymer is disclosed.
• Patent Document 2 discloses an invention of a pollution-free rust-proof coating composition obtained by blending slag, mica, and aluminum phosphomolybdate containing an alkali group generated during a scouring process with respect to a resin solid content. Yes.
• Patent Document 3 a mortar formed by mixing a polymer cement, an aggregate, water, and a lithium nitrite solution is applied to a predetermined portion of a concrete structure through a mortar spray nozzle.
• the invention of the mortar spraying method characterized by spraying on the surface is disclosed.
• a passive film Fe 2 O 3
• an anion adsorbent is contained in the base conditioning material, so that a nest generated at the interface between the rust layer and the steel material (an anion is generated by the corrosion cell formed on the steel surface due to the corrosion of the steel).
• An invention of a base material adjustment material for steel that positively removes the anions in the portion is disclosed.
• JP-A-5-155649 Japanese Patent Laid-Open No. 2002-80786 JP 2007-177567 A JP 2004-299979 A
• the surface coating agent described in Patent Document 1 uses carbon fiber, which is a high-cost material.
• the coating thickness 700-800 ⁇ m
• the pollution-free rust-proof coating composition described in Patent Document 2 is said to be excellent in long-term rust-proof properties, but the passive film on the surface of a steel material formed by components such as slag containing an alkali group It is destroyed by a corrosive factor that enters from a flawed part caused by deterioration or external damage, rust progresses in a short time, and the lifetime is as short as about ten years.
• the present invention has been made in view of such circumstances, and is intended to reduce the surface treatment compared to the prior art, properly contain nitrite used as a rust inhibitor, reduce the diffusion speed of nitrite, and prevent rust prevention of steel materials. It aims at providing the anticorrosion coating composition which can maintain an effect over a long period of time, its manufacturing method, and the anticorrosion method of steel materials.
• An anticorrosive coating composition according to the present invention includes a compound containing cement, an inorganic powder material, and an expansion material, a polymer emulsion selected from a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion, Contains nitrite.
• a polymer emulsion selected from a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion Contains nitrite.
• nitrite ions NO 2 ⁇
• passivated film Fe 2 O 3
• a solid structure can be constructed by adjusting the mass ratio of the cement to the inorganic powder material to be 1.0 to 1.4.
• Styrene / butadiene copolymer and acrylic / styrene copolymer both have good adhesion to the substrate, have little dependence on temperature, and have excellent elasticity even at low temperatures and relatively high temperatures. . For this reason, the coating film excellent in water permeability and a weather resistance can be obtained.
• the synthetic resin of the cationic styrene butadiene copolymer system described in Patent Document 1 can be expected to have a rust prevention effect, but the deformation ability (elongation) of the coating film is 0.4%, and the bending axial force is applied to the steel material. If the elongation at the time of acting is 0.5% or more, there are problems such as cracks in the coating film.
• the epoxy-type synthetic resin described in Patent Document 4 has a smaller elongation than the synthetic resin of the cationic styrene butadiene copolymer system.
• the compound of the styrene / butadiene copolymer is changed (reduction in the amount of styrene), and further, the compound has a good compatibility with the emulsion (latex) whose composition is changed. In combination, the coating film with an elongation of 5% or more was successfully obtained.
• the stability of the coating film is taken into consideration, it is possible to sufficiently follow the deformation of the steel structure by setting the elongation percentage of the coating film formed by the anticorrosive coating composition according to the present invention to 5%.
• an acryl / styrene copolymer was employed as an anionic synthetic resin in order to promote the flow of nitrite ions (NO 2 ⁇ ) toward the anode.
• the amount of nitrite (solid content) used in the conventional polymer cement mortar described in Patent Document 3 is increased with respect to the total composition, abnormal setting of the cement occurs. Therefore, the upper limit of the amount of nitrite used is 5% by mass in the case of lithium nitrite and 1.25% by mass in the case of calcium nitrite. However, the amount of nitrite needs to be 2.5% by mass or more in order to maintain a long-term rust-preventing effect as the paint is made.
• the amount of nitrite is increased by setting the amount of styrene / butadiene copolymer to 5% by mass or more, or by setting the amount of acrylic / styrene copolymer to 6% by mass or more.
• the coating film was given an alkaline atmosphere with a pH of 11.5 to 12.5, thereby enabling the reduction of the ground treatment and the long-term corrosion prevention.
• the compound contains an inorganic powder material and an expansion material.
• the nitrite contained in the anticorrosion coating composition according to the present invention is preferably 2.5% by mass or more.
• the rust prevention effect is the same as that of an epoxy resin paint, and rust is generated at the crosscut portion in the salt spray test 3000 hours.
• the amount of nitrite in the present invention is 3% by mass, the amount of nitrite is about 2.5 times that of the conventional paint.
• the nitrite contained in the anticorrosion coating composition is preferably 7.5% by mass or less.
• the nitrite contained in the anticorrosion coating composition is preferably 9.0% by mass or less.
• nitrite exceeds 9.0% by mass, the amount of water when mixed with the acrylic / styrene copolymer increases, and voids in the cement hydrate increase. Along with this, moisture easily enters the voids, and the diffusion of nitrite in the cement hydrate is accelerated. As a result, a long-term rust prevention effect cannot be expected.
• the anticorrosion coating composition may contain 5 to 18% by mass of the styrene / butadiene copolymer.
• the styrene / butadiene copolymer is less than 5% by mass, the styrene / butadiene copolymer emulsion is less than 18 parts by mass with respect to 100 parts by mass of the cement, and the elongation and breaking strength of the coating film are not improved.
• the followability with respect to the deformation is reduced. For this reason, a coating-film crack is easy to generate
• the anticorrosion coating composition may contain 6 to 24% by mass of the acrylic / styrene copolymer.
• the acrylic / styrene copolymer is less than 6% by mass, the acrylic / styrene copolymer emulsion is less than 11 parts by mass with respect to 100 parts by mass of the cement, and the elongation and breaking strength of the coating film are not improved. The followability with respect to the deformation is reduced.
• the cement contained in the anticorrosion coating composition is 26 to 39% by mass
• the inorganic powder material is 20 to 28% by mass
• the expansion material is 0.5 to 1.5% by mass.
• the cement contained in the anticorrosion coating composition is preferably 26% by mass or more and 39% by mass or less.
• the cement is less than 26% by mass
• the water cement ratio exceeds 1.4 when the nitrite and the styrene / butadiene copolymer are properly mixed, and the required coating strength cannot be obtained.
• coating film peeling occurs due to insufficient adhesion strength, and cohesive failure occurs due to insufficient compression strength.
• the cement contained in the anticorrosion coating composition is preferably 26% by mass or more and 38% by mass or less.
• the cement is less than 26% by mass, the water cement ratio exceeds 1.0 when the nitrite and the acryl / styrene copolymer are properly mixed, and the required coating strength cannot be obtained. Specifically, coating film peeling occurs due to insufficient adhesion strength, and cohesive failure occurs due to insufficient compression strength.
• the cement exceeds 38% by mass, the required coating film strength can be expected, but the cement becomes excessive, the shrinkage amount increases, and cracks occur on the coating film surface.
• the coating film becomes cement-rich and the probability of occurrence of cracks during drying increases. In addition, the amount of water increases and the coating strength cannot be secured.
• the amount of the inorganic powder exceeds 28% by mass, the amount of aggregate powder is excessively increased, the viscosity of the cement hydrate is decreased, and the adhesive strength of the ground surface is decreased.
• the effect of the expansion material can be expected when the amount of cement used is appropriate.
• the expansion material is less than 0.5% by mass, when the amount of styrene / butadiene copolymer or acrylic / styrene copolymer is small, the coating film becomes brittle and cannot cope with shrinkage caused by cement.
• the water content is preferably 13 to 42% by mass.
• the water is water in the styrene / butadiene copolymer emulsion and in the aqueous nitrous acid solution. If the water content is less than 13% by mass, 2.5% by mass of nitrite cannot be ensured, and if it exceeds 42% by mass, the nitrite exceeds 7.5% by mass, resulting in an excessive specification, resulting in an increase in cost.
• the water content is preferably 12 to 43% by mass.
• the water is water in the acrylic / styrene copolymer emulsion and in the aqueous nitrous acid solution. If the water content is less than 12% by mass, 2.5% by mass of nitrite cannot be ensured. If the water content exceeds 43% by mass, the nitrite exceeds 9.0% by mass, resulting in excessive specifications. Cost increases.
• the inorganic powder material is one selected from cinnabar powder, calcium carbonate, magnesium silicate, slag powder (steel slag powder, etc.), and clay powder. Or it is 2 or more types.
• cinnabar powder calcium carbonate, magnesium silicate, slag powder (steel slag powder, etc.), and clay powder.
• slag powder steel slag powder, etc.
• clay powder is 2 or more types.
• the use of clay powder makes it possible to ensure water retention, and the effect is further improved.
• the nitrite is preferably lithium nitrite.
• the cement is preferably blast furnace cement.
• the clinker produced in the cement manufacturing process is mainly composed of alite, belite, aluminate phase, and ferrite phase. The inventors have discovered that the aluminate phase in the clinker reacts with calcium nitrite, causing abnormal setting of the cement. Therefore, in order to prevent abnormal setting of the cement, it was decided to use lithium nitrite as the nitrite when the cement is ordinary Portland cement.
• blast furnace cement was used to reduce the aluminate phase and prevent abnormal cementation.
• a blast furnace cement and lithium nitrite are combined, since the setting time is extended, the paint drips during construction, and it becomes difficult to ensure the coating thickness.
• the anticorrosion coating film formed by the anticorrosion coating composition is selected from a compound containing cement, an inorganic powder material, and an expansion material, and a styrene / butadiene copolymer or an acrylic / styrene copolymer. It is an anticorrosion coating film containing a polymer and nitrite.
• One aspect of the anticorrosion coating film is an anticorrosion coating film containing a styrene / butadiene copolymer as the polymer, wherein 32.5 to 49% by mass of the cement (cement component) and 25 to 35% by mass of the anticorrosion coating film.
• An inorganic powder material 0.6 to 1.9% by mass of the expansion material, 6 to 23% by mass of the styrene / butadiene copolymer, 3.1 to 9.4% by mass of the nitrite, It contains 7 to 12% by mass of crystallization water, and the inorganic powder material is one or more selected from cinnabar powder, calcium carbonate, magnesium silicate, slag powder, and clay powder. .
• an anticorrosion coating film containing an acrylic / styrene copolymer as the polymer, wherein 32.5 to 47.5% by mass of the cement (cement component), 25 to 35 %
• cement cement component
• the inorganic powder material contains nitrite and further contains 7.8 to 12% by mass of crystallization water
• the inorganic powder material is one or two kinds selected from cinnabar powder, calcium carbonate, magnesium silicate, slag powder, and clay powder It is characterized by the above.
• the content of cement, expansion material, nitrite, etc. represents the content of each raw material component of the coating film, and the content of crystal water depends on the hydration reaction with cement, etc. Corresponds to the amount of water incorporated in the coating.
• the amount of water evaporated as the anticorrosion coating composition was cured was about 20% of the total mass of the anticorrosion coating composition from the experimental results. Therefore, the component ratio of the anticorrosion coating film is obtained by dividing the component ratio of the anticorrosion coating composition by 0.8.
• the method for producing an anticorrosive coating composition comprises adding the styrene / butadiene copolymer emulsion or the acrylic / styrene copolymer emulsion to the aqueous nitrite solution when producing the anticorrosive paint composition. And a second step of adding the compound containing the cement, the inorganic powder material, and the expansion material to the mixed solution that has been subjected to the constant temperature pretreatment. It is characterized by that.
• constant temperature pretreatment means a low-speed stirring for a predetermined time in a state in which a mixed solution obtained by adding a styrene / butadiene copolymer emulsion or an acryl / styrene copolymer emulsion to an aqueous nitrite solution while maintaining a predetermined temperature.
• the predetermined temperature is preferably 30 to 60 ° C., for example, around 40 ° C.
• the predetermined time is preferably 3 to 10 minutes, for example, about 5 minutes. It is more preferable to leave the premixed mixture at a constant temperature for 5 to 10 days, for example, about 7 days, and then add the compound to the mixture.
• the viscosity of the admixture is adjusted to a styrene / butadiene copolymer emulsion or acrylic by pretreating a mixture obtained by adding a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion to an aqueous nitrite solution.
• a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion to an aqueous nitrite solution / It becomes possible to reduce to about 1/40 of the viscosity of the styrene copolymer emulsion alone. As a result, significant improvement can be expected with respect to the kneading effect with the compound. In addition, it becomes a long-term stable admixture and can be stored for a long time.
• the steel material corrosion prevention method removes floating rust on the steel material surface, and then applies an undercoat material comprising the anticorrosive coating composition to the steel material surface to form an undercoat layer, and an elongation of 5% or more.
• An overcoating material for forming a coating film having a rate is applied on the undercoating layer to form an overcoating layer.
• the coating-film layer which concerns on this invention is formed from the undercoat layer which consists of the said anti-corrosion coating film, and the top-coat layer which consists of a coating film which has an elongation rate of 5% or more, It is characterized by the above-mentioned.
• the undercoat layer becomes alkaline (pH 11.5 or more) by the cement contained in the anticorrosion coating composition, a passive film (Fe 2 O 3 ) is formed on the steel material surface, and rusting is prevented. (Alkaline anti-corrosion function).
• the base material may be adjusted to about 3 types of keren to remove floating rust from the surface of the steel material.
• the passive film is damaged due to some external factor, nitrite is eluted to reconstruct the passive film (self-repair function).
• the undercoat layer is provided with flexibility by the styrene / butadiene copolymer or the acrylic / styrene copolymer, and an undercoat layer that can follow the deformation of the steel surface is formed.
• the elongation rate of the anticorrosive coating film according to the present invention is, as described above, because the elongation when the bending axial force is applied to the steel material is 0.5% or more, and the stability of the coating film is considered.
• the elongation percentage of the top coat film needs to be 5% or more.
• the overcoat layer may include at least one selected from an epoxy resin, a urethane resin, a polyurethane resin, an acrylic silicon resin, an acrylic urethane resin, a Halth hybrid resin, and the like, or may be composed of a coating film.
• the topcoat layer may be a single coating film or may be composed of two or more coating films.
• the total thickness of the overcoat layer is not particularly limited, but may be, for example, 60 to 130 ⁇ m.
• it may be composed of a first layer having a layer thickness of 60 to 80 ⁇ m and a second layer having a layer thickness of 20 to 40.
• it may be composed of a first layer having a layer thickness of 40 to 70 ⁇ m and a second layer having a layer thickness of 30 to 40 ⁇ m.
• the anticorrosion coating composition of the present invention comprises a compound containing cement, an inorganic powder material, and an expansion material, a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion, and a nitrite. It is a composition. In order to make the amount of nitrite 2.5% by mass or more, 5% by mass or more of styrene / butadiene copolymer or 6% by mass or more of acrylic / styrene copolymer emulsion is contained. In addition, the cement amount of the entire composition is set to 26% by mass or more.
• the coating film was given an alkaline atmosphere with a pH of 11.5 to 12.5, and the surface treatment was reduced and anticorrosion was possible for a long period of time.
• the cement paste after curing appropriately contains nitrite used as a rust preventive agent, the diffusion speed of nitrite is reduced, and the effect of nitrite can be maintained for a long time.
• the anticorrosion coating composition when the anticorrosion coating composition is produced, a mixed solution obtained by adding a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion to an aqueous nitrite solution in advance is subjected to a constant temperature pretreatment. Therefore, the viscosity of the mixed solution can be reduced to about 1/40 of the viscosity of the styrene / butadiene copolymer emulsion alone or the viscosity of the acrylic / styrene copolymer emulsion alone. As a result, significant improvement can be expected with respect to the kneading effect with the compound.
• the undercoat layer is alkaline, a passive film is formed on the steel surface, and rusting is prevented. This eliminates the need for advanced substrate adjustment on the steel surface. If the passive film is damaged by any external factor, nitrite will elute and reconstruct the passive film.
• the undercoat layer is provided with flexibility by the styrene / butadiene copolymer or the acrylic / styrene copolymer, and an undercoat layer that can follow the deformation of the steel surface is formed.
• the present invention is an anticorrosion coating composition used as a primer on the surface of a steel material.
• a mixed solution obtained by adding a styrene / butadiene copolymer emulsion or an acrylic / styrene copolymer emulsion to an aqueous nitrite solution and pre-isothermal treatment, It is produced by adding a compound containing cement, an inorganic powder material and an expansion material.
• the styrene / butadiene copolymer is preferably 5 to 18% by mass and the nitrite is preferably 2.5 to 7.5% by mass.
• the acrylic / styrene copolymer is 6 to 24% by mass and the nitrite is 2.5 to 9.0% by mass.
• the compounding ratio is more preferably 50 to 70% by mass based on the total composition.
• an acrylic / styrene copolymer it is more preferably 50-60% by mass of the total composition.
• the inorganic powder material is made 20 to 28% by mass, and in order to suppress the SO 3 (sulfur trioxide) amount of the coating film, the expansion material is made 0.5 to 1% by mass. More preferably.
• Nitrite is a substance that imparts a rust prevention effect. Lithium nitrite, sodium nitrite, potassium nitrite, calcium nitrite, magnesium nitrite, barium nitrite and the like can be used, but lithium nitrite and calcium nitrite have good compatibility with cement.
• Cement keeps the coating film alkaline and has a function as a binder.
• Cement is not particularly limited, and various portland cements, various mixed cements, blast furnace cement, fly ash cement, etc. can be used. When calcium nitrite is used as the nitrite, use blast furnace cement to improve fluidity. Is preferred.
• the inorganic powder material enhances the dispersibility and adhesion of the compound.
• cinnabar powder such as natural cinnabar and regenerated cinnabar, clay powder or calcium carbonate or slag powder can be used, among which calcium carbonate, magnesium silicate, slag powder and clay powder are selected. It is preferable to use two or more species.
• the coating thickness cannot be secured, and the coating contracts as the cement hardens. For these reasons, it is necessary to add an inorganic powder material to the anticorrosive coating composition. In this case, a stable coating film cannot be obtained unless the particle size of the inorganic powder material is reduced to about 1/3 of the minimum coating film thickness. Therefore, the particle size distribution of the inorganic powder material is such that the minimum coating thickness is 200 ⁇ m and the ratio of the inorganic powder material of 74 ⁇ m or less is 80% or more.
• ⁇ Expansion material is used to prevent dry shrinkage of the compound.
• a commercially available material such as anhydrous gypsum can be used as the expansion material.
• a water reducing agent for reducing moisture and increasing fluidity, a thickening agent for increasing viscosity, and the like may be added as an admixture.
• the amount of the admixture is preferably 0.4 to 0.8% by mass, and more preferably 0.6% by mass.
• the amount of the admixture is preferably 0.3 to 0.6% by mass, and more preferably 0.4% by mass.
• the expected life of each coating is 30 years, 7 years, 8 years, 10 years, material costs and temporary construction
• the total cost such as costs, assuming that the total cost when using the anticorrosive coating composition according to the present invention is 1, it is 5.0 for epoxy resin coating, 4.1 for alkali coating, and 5 for heavy anticorrosion coating. 0.0. This also shows that the life cycle cost of a steel structure can be significantly reduced by using the anticorrosion coating composition according to the present invention.
• the coating film formed on the undercoat layer made of the anticorrosive coating composition is required to have a substrate follow-up property, nitrite elution prevention, and excellent weather resistance.
• a coating material having high weather resistance will be described here.
• a topcoat material used for a topcoat layer formed directly on the undercoat layer a two-component mixed paint in which a solution obtained by dissolving an acrylic silicon resin in a terpene-based weak solvent is used as a main agent and an isocyanate is hardened. Can be used.
• the mixing ratio of the main agent and the curing agent is preferably 2 to 15 parts by mass of the main agent with respect to 1 part by mass of the curing agent.
• an acrylic silicon resin having excellent weather resistance is used as the main component of the main agent, and by mixing isocyanate as a curing agent, the OH group of the main agent and the isocyanate group of the curing agent are combined to form a coating film. Urethane crosslinks are formed in the molecular structure. Thereby, the molecular structure of a coating film becomes a three-dimensional network structure, and the sealing property of a coating film improves. That is, it is possible to prevent nitrite contained in the undercoat layer from eluting into the topcoat layer.
• bridge crosslinking
• crosslinking density ratio of the number of the crosslinking points with respect to the whole structural unit
• softening a pencil hardness is about H
• the overcoat layer is required to have excellent weather resistance that can maintain gloss over a long period of time. Therefore, as another example of the topcoat material used for forming the topcoat layer, a two-component mixed paint using a solution obtained by dissolving a Hals hybrid resin in a strong solvent such as toluene or xylene as a main agent and an isocyanate as a curing agent is used. Can be used.
• the mixing ratio of the main agent and the curing agent is preferably 2 to 15 parts by mass of the main agent with respect to 1 part by mass of the curing agent, as in the case of the top coating material.
• the Hals hybrid resin which is the main component of the main agent, is an acrylic polyol resin obtained by copolymerizing a hindered amine light stabilizer (Hindered Amine Light Stabilizer) and cyclohexyl methacrylate.
• the hindered amine light stabilizer (hereinafter referred to as “HALS”) captures radicals generated by ultraviolet rays and reacts with the oxygen in the air when the radicals are generated. The phenomenon of radical generation and deterioration of the coating).
• cyclohexyl methacrylate has high hydrophobicity in addition to not having a benzene skeleton that easily absorbs sunlight and generates radicals.
• Hals Hybrid resin chemically binds HALS into the resin to prevent bleed out of HALS, suppresses the auto-oxidative degradation reaction of the coating film for a long time, and the high hydrophobicity of cyclohexyl methacrylate makes the coating film Long life has been achieved.
• the OH group of the main agent and the isocyanate group of the curing agent are combined to form a urethane bridge in the molecular structure, so the molecular structure of the coating film is a three-dimensional network structure.
• the sealing property of the coating film is improved.
• An undercoat layer made of the above-described anticorrosion coating composition is applied to the surface of the steel material that has been prepared to form an undercoat layer.
• the thickness of the undercoat layer is set to 200 ⁇ m to 650 ⁇ m.
• the standard drying time is about one day, but it varies depending on environmental conditions such as humidity.
• a first overcoat layer is formed by applying a solution obtained by dissolving an acrylic silicon resin in a weak solvent and an isocyanate and mixing and stirring on the undercoat layer. At this time, the thickness of the first overcoat layer is set to 60 ⁇ m to 80 ⁇ m. The standard drying time is about one day, but it varies depending on environmental conditions such as humidity.
• a second topcoat layer is formed by applying a solution obtained by dissolving a Hals hybrid resin in a strong solvent and an isocyanate and mixing the stirred topcoat onto the first topcoat layer. At this time, the thickness of the second overcoat layer is set to 20 ⁇ m to 40 ⁇ m. The standard drying time is about one day, but it varies depending on environmental conditions such as humidity.
• coating method of undercoat and 1st and 2nd topcoat may be any of brush coating, roller coating, and spray coating. When it rains after application, the next coating is performed after about 3 days.
• the reference example uses an anti-corrosion coating composition according to the present invention as an undercoat material and an overcoat material having a coating film elongation of less than 5%.
• an anti-corrosion coating composition according to the present invention as an undercoat material and an overcoat material having a coating film elongation of less than 5%.
• two test pieces were used, and each test piece was coated with a top coat material, and then a ruler was applied to the surface of the test piece and a cross cut was made with a cutter knife.
• Examples A1 to A6 used lithium nitrite as the nitrite contained in the primer, and Examples A7 to A11 used calcium nitrite.
• Examples A1 to A6 ordinary Portland cement was used, and in Examples A7 to A11, blast furnace cement was used.
• a combination of calcium carbonate and magnesium silicate and clay powder in Examples A1, A3 to A5, a combination of dredged sand powder and clay powder in Example A8, and a slag in Example A11 A combination of powder (iron slag powder) and clay powder, slag powder in Example 2, calcium carbonate and magnesium silicate in Examples A6 and 9, cinnabar powder in Example A7, and clay powder in Example A10 did.
• the overcoat layer has a two-layer structure composed of two types of topcoat materials different for each example, and the total thickness is set to 80 ⁇ m or 100 ⁇ m.
• the crosslink density of the topcoat material is a comparative evaluation of the crosslink densities of Examples A1 to A11 with respect to the average value of the first topcoat layer and the second topcoat layer.
• the elongation percentage of the top coat material is an average value of the first top coat layer and the second top coat layer.
• Reference Examples A1 to A4 lithium nitrite was used as the nitrite contained in the primer and the cement was ordinary Portland cement.
• Reference Example A5 calcium nitrite was used as the nitrite contained in the primer, and the cement was blast furnace cement.
• Reference Examples A1, A4 and A5 are calcium carbonate and magnesium silicate
• Reference Example A2 is a combination of slag powder and clay powder
• Reference Example A3 is calcium carbonate and magnesium silicate and clay powder. Each combination was used.
• reference examples A1 and A2 used epoxy resins
• reference example A3 used weak solvent silicone epoxy resins
• reference examples A4 and A5 used modified silicone epoxy resins.
• Comparative Examples A1 to A3 Mighty CF manufactured by Mighty Chemical Co., Ltd., mainly composed of white cement and ultrafine silica was used.
• the undercoat material of Comparative Examples A6 and A7 was an alkali paint
• the undercoat material of Comparative Example A8 was a zinc rich paint
• the undercoat material of Comparative Example A9 was an epoxy resin paint.
• Comparative Examples A10 to A12 are paints comprising the same components as in the present invention, but the blending ratio is outside the scope of the present invention.
• On the other hand, as for the overcoat material of Comparative Examples A1 to A12 only Comparative Example A7 used a chlorinated olefin-based paint, and other Comparative Examples used epoxy resin.
• Comparative Examples A13, A14, A17 to A21, A23, A24, A29, and A30 lithium nitrite was used as the nitrite contained in the primer, and ordinary Portland cement was used as the cement.
• Comparative Examples A15, A16, A22, A25 to A28, and A31 to 34 used calcium nitrite as the nitrite contained in the primer and blast furnace cement as the cement.
• an inorganic type powder material in Comparative Examples A13, A14, A16, A25, and A26, a combination of calcium carbonate and magnesium silicate and clay powder is used, and in Comparative Example A27, a combination of cinnabar powder and clay powder.
• Comparative Examples A30 and A31 a combination of slag powder and clay powder is used.
• Comparative Examples A15, A19, A20, and A32 to A34 calcium carbonate and magnesium silicate are used, and Comparative Examples A17 and A18 are used.
• the overcoat material of Comparative Examples A13 to A34 was a weak solvent acrylic urethane resin, and the thickness was all 180 ⁇ m.
• each coating-film thickness of Table 2, Table 5, and Table 7 is a measured value with a film thickness meter.
• a cass spray test was carried out at 35 ° C. for 4 hours, then dried at 60 ° C. and a humidity of 50% for 2 hours, and further a moisture resistance test at a temperature of 50 ° C. and a humidity of 95%.
• the test for a total of 8 hours that is performed for 2 hours is defined as one cycle, and a plurality of cycles are performed.
• the cast spray test is a test in which the test solution is changed from salt water to a cast solution in the salt spray test method according to JIS Z 2371.
• the cast solution is an aqueous solution containing 40 g / L of sodium chloride and 0.205 g / L of cupric chloride and adjusted to pH 3.0 with acetic acid.
• the moisture resistance test was performed in accordance with JIS K 5600-7-3 moisture resistance (discontinuous condensation method).
• the combined cycle test was conducted 200 times.
• the rust generation state (rust prevention effect) on the surface of the two test pieces was evaluated based on the criteria shown in Table 9, with a maximum of 10 points. The average of the evaluation points was obtained.
• the comprehensive evaluation in Table 4, Table 6, and Table 8 is the result of comprehensively evaluating the rust prevention effect, the workability, the ground followability, and the weather resistance.
• Example adhesion strength test This test determines the degree of adhesion between the base material and the coating film. This time, it was carried out according to the provisions of JIS A 6203 “Polymer dispersion for cement admixture and re-emulsified powder resin”. Table 12 shows the composition of the anticorrosion coating composition of Example A13.
• Example adhesion strength of A13 is 1.1 N / mm 2, bond strength of 1.0N JIS A bond strength of 6916 to a defined thin intermediate coating material 0.5 N / mm 2 and a thickness intermediate coating material / Mm 2 is satisfied.
• [Composite cycle test] A composite cycle test was performed on a test piece in which an undercoat material and an overcoat material were applied to a strip-shaped steel plate that had been subjected to a surface base treatment.
• Tables 13, 14, and 15 show the material configurations and properties of the topcoat materials of Examples and Reference Examples in which combined cycle tests were performed, and Table 16 shows the test results.
• Table 17, Table 18, Table 19, and Table 20 show the material configurations and test results of the comparative examples.
• the reference example uses an anti-corrosion coating composition according to the present invention as an undercoat material and an overcoat material having a coating film elongation of less than 5%.
• two test pieces were used, and each test piece was coated with a top coat material, and then a ruler was applied to the surface of the test piece and a cross cut was made with a cutter knife.
• Examples B1 to B6 used lithium nitrite as the nitrite contained in the primer, and Examples B7 to B11 used calcium nitrite.
• Examples B1 to B6 ordinary Portland cement was used, and in Examples B7 to B11, blast furnace cement was used.
• inorganic powder materials in Examples B1 and B3 to B5, a combination of calcium carbonate and magnesium silicate and clay powder, in Example B8, a combination of dredged sand powder and clay powder, in Example B11, slag A combination of powder (steel slag powder) and clay powder, slag powder in Example B2, calcium carbonate and magnesium silicate in Examples B6 and B9, cinnabar powder in Example B7, and clay powder in Example B10 did.
• the overcoat layer has a two-layer structure composed of two types of topcoat materials different for each example, and the total thickness is set to 80 ⁇ m or 100 ⁇ m.
• the crosslink density of the topcoat material is an average value of the first topcoat layer and the second topcoat layer, and is a comparative evaluation of the crosslink densities of Examples B1 to B11.
• the elongation percentage of the top coat material is an average value of the first top coat layer and the second top coat layer.
• Reference Examples B1 to B4 lithium nitrite was used as the nitrite contained in the primer, and the cement was ordinary Portland cement.
• Reference Example B5 calcium nitrite was used as the nitrite contained in the primer, and the cement was blast furnace cement.
• Reference Examples B1, B4, and B5 are calcium carbonate and magnesium silicate
• Reference Example B2 is a combination of slag powder and clay powder
• Reference Example B3 is calcium carbonate and magnesium silicate and clay powder. Each combination was used.
• Reference Examples B1 and B2 used epoxy resins
• Reference Example B3 used weak solvent silicone epoxy resins
• Reference Examples B4 and B5 used modified silicone epoxy resins.
• Comparative Examples B1 to B3 For the undercoat material of Comparative Examples B1 to B3, Mighty CF manufactured by Mighty Chemical Co., Ltd., mainly composed of white cement and ultrafine silica was used.
• the undercoat material of Comparative Examples B6 and B7 was an alkali paint
• the undercoat material of Comparative Example 8 was a zinc rich paint
• the undercoat material of Comparative Example B9 was an epoxy resin paint.
• Comparative Examples B10 to B12 are paints comprising the same components as in the present invention but having a blending ratio outside the scope of the present invention.
• On the other hand, for the overcoat materials of Comparative Examples B1 to B12 only Comparative Example B7 used a chlorinated olefin-based paint, and the other Comparative Examples used epoxy resins.
• Comparative Examples B13, B14, B17 to B21, B23, B24, B29, and B30 lithium nitrite was used as the nitrite contained in the primer, and ordinary Portland cement was used as the cement.
• Comparative Examples B15, B16, B22, B25 to B28, and B31 to B34 calcium nitrite was used as the nitrite contained in the primer and blast furnace cement was used as the cement.
• inorganic powder materials in Comparative Examples B13, B14, B16, B25, and B26, a combination of calcium carbonate and magnesium silicate and clay powder is used, and in Comparative Example B27, a combination of cinnabar powder and clay powder is used.
• Comparative Examples B30 and B31 a combination of slag powder and clay powder is used.
• Comparative Examples B15, B19, B20, and B32 to B34 calcium carbonate and magnesium silicate are used, and Comparative Examples B17 and B18 are used.
• B28 used cinnabar powder
• Comparative Examples B21, B22 and B29 used slag powder
• Comparative Examples B23 and B24 used clay powder.
• the overcoat material of Comparative Examples B13 to B34 was a weak solvent acrylic urethane resin, and the thickness was all 180 ⁇ m.
• each coating-film thickness of Table 13, Table 17, and Table 19 is a measured value with a film thickness meter.
• a cass spray test was carried out at 35 ° C. for 4 hours, then dried at 60 ° C. and a humidity of 50% for 2 hours, and further a moisture resistance test at a temperature of 50 ° C. and a humidity of 95%.
• the test for a total of 8 hours that is performed for 2 hours is defined as one cycle, and a plurality of cycles are performed.
• the above-mentioned cast spray test is a test in which the test solution is changed from salt water to a cast solution in the salt spray test method according to JIS Z 2371.
• the cast solution is an aqueous solution containing 40 g / L of sodium chloride and 0.205 g / L of cupric chloride and adjusted to pH 3.0 with acetic acid.
• the moisture resistance test was performed in accordance with JIS K 5600-7-3 moisture resistance (discontinuous condensation method).
• the combined cycle test was conducted 200 times.
• the rust generation state (rust prevention effect) on the surface of the two test pieces was evaluated based on the criteria shown in Table 21, with a maximum of 10 points. The average of the evaluation points was obtained.
• the comprehensive evaluation in Table 16, Table 18, and Table 20 is the result of comprehensively evaluating the rust prevention effect, the workability, the ground followability, and the weather resistance.
• Adhesion strength test This test determines the degree of adhesion between the base material and the coating film. This time, it was carried out according to the provisions of JIS A 6203 “Polymer dispersion for cement admixture and re-emulsified powder resin”. Table 24 shows the composition of the anticorrosion coating composition of Example B13.
• Implementation adhesion strength of Example B13 is 1.1 N / mm 2, bond strength of 1.0N JIS A bond strength of 6916 to a defined thin intermediate coating material 0.5 N / mm 2 and a thickness intermediate coating material / Mm 2 is satisfied.
• the coating film formed on the steel material surface using the anticorrosion coating composition of the present invention has an alkaline atmosphere with a pH of 11.5 to 12.5. If a coating film layer having such a coating film as an undercoat layer is formed, a passive film is formed on the steel material surface, and rusting is prevented. Moreover, since the nitrite is appropriately held by the cement paste, the rust preventive effect by the nitrite can be maintained for a long time. Further, the polymer made of styrene / butadiene copolymer or acrylic / styrene copolymer imparts flexibility to the undercoat layer and can follow the deformation of the steel surface. These effects eliminate the need for advanced substrate preparation on the steel surface and enable long-term corrosion protection.

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• 2011
  • 2011-02-25 WO PCT/JP2011/054237 patent/WO2011105529A1/ja active Application Filing
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