WO2009081452A1 - Inhibiteur de corrosion et son procédé de production - Google Patents

Inhibiteur de corrosion et son procédé de production Download PDF

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Publication number
WO2009081452A1
WO2009081452A1 PCT/JP2007/001465 JP2007001465W WO2009081452A1 WO 2009081452 A1 WO2009081452 A1 WO 2009081452A1 JP 2007001465 W JP2007001465 W JP 2007001465W WO 2009081452 A1 WO2009081452 A1 WO 2009081452A1
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Prior art keywords
conductive material
powder
mass
anticorrosive
material powder
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PCT/JP2007/001465
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English (en)
Japanese (ja)
Inventor
Yasuhiro Sakakibara
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Restoration Environment Rebirth Co., Ltd.
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Application filed by Restoration Environment Rebirth Co., Ltd. filed Critical Restoration Environment Rebirth Co., Ltd.
Priority to PCT/JP2007/001465 priority Critical patent/WO2009081452A1/fr
Publication of WO2009081452A1 publication Critical patent/WO2009081452A1/fr

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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

Definitions

  • the present invention relates to a technique for preventing corrosion of a protected object including a metal member (a steel structure, a concrete structure including a reinforcing bar as a structural material), and more specifically, an anticorrosive agent that forms an anticorrosive coating on the protected object.
  • the present invention also relates to a method for producing the same and a method for anticorrosion treatment using the anticorrosive.
  • a corrosion prevention (rust prevention) method for metal parts such as steel materials
  • a coating method for covering the surface with a paint or other organic material to prevent contact with sulfides or halides etc.
  • a hot-dip galvanizing method in which zinc is deposited by immersing it in molten zinc, or by applying a sacrificial anodic reaction due to the potential difference between metals by melting zinc or aluminum with a gas flame or arc to adhere to the surface of the workpiece.
  • Rust metal spraying methods are known (Patent Documents 1 to 4).
  • the organic solvent-based paint is mainly used, so that the hardness tends to be insufficient. Therefore, the coating film may be damaged due to surface damage or wear and the rust prevention function may be impaired.
  • the hot dip galvanizing method requires a large plant for immersing an object to be processed in hot dip zinc, and is difficult to apply to thin steel plates and long steel materials due to problems of melting temperature and immersion pool. Moreover, since such immersion is required, it cannot be applied to maintenance of existing steel structures.
  • the metal spraying method is excellent in anticorrosion performance, the construction efficiency is generally low, the burden of carrying in and maintaining the apparatus is large, and it is difficult to apply to existing steel structures and narrow structural parts.
  • Patent Document 5 proposes a rust-preventing oil containing a silane coupling agent
  • Patent Document 6 proposes a resin composition for metal coating containing tetraalkoxysilane and / or its condensate. Rust prevention effect is not obtained.
  • Patent Document 7 proposes that an alloy layer of zinc and aluminum is provided on the metal surface, and a silicone layer is provided thereon, and Patent Documents 8 and 9 disclose that the coating film containing zinc, aluminum, and its alloy is applied. The provision of a silicone layer is described.
  • Patent Document 10 proposes a primary rust preventive paint comprising a mixture of a silicone compound-containing spreading agent and zinc
  • Patent Document 11 proposes a primary rust preventive paint comprising a silicone binder, zinc and ferric oxide. However, all of them are provided with a plurality of layers, and the workability is poor and the rust prevention characteristics are insufficient.
  • JP 2001-271152 A JP-A-9-125221 Japanese Patent Laid-Open No. 9-3614 JP-A-8-176781 Japanese Patent Laid-Open No. 3-164239 JP-A-6-329980 Japanese Patent Laid-Open No. 7-913 JP 2003-33719 A JP 2003-328151 A Japanese Unexamined Patent Publication No. 7-47328 JP-A-8-60038 JP 2005-232537 A Japanese Patent Laid-Open No. 10-245280 JP-A-6-2174
  • the present invention provides an anticorrosive agent for anticorrosion of an object to be protected having a metal member, which can be simply applied and can realize superior anticorrosive properties, and a method for producing the same. With the goal.
  • Another object of the present invention is to provide a method for easily and highly corrosion-protecting the above-mentioned protected object.
  • the anticorrosive manufacturing method includes a conductive material powder (described later) including flaky zinc powder and a treated flaky aluminum powder obtained by pre-treating aluminum powder formed into a flaky shape under reduced pressure.
  • Preparing the conductive material powder includes preparing an aluminum powder formed in a flaky shape, and performing the pretreatment (vacuum heat treatment) on the aluminum powder to obtain the treated flaky aluminum powder. Can be included.
  • the above production method is also represented by the following formula (1): (R 1 ) a Si (OR 2 ) 4-a (1); And preparing a binder component containing a silane compound and / or a partially hydrolyzed condensate thereof, and a metal alkoxide.
  • R 1 and R 2 in the above formula (1) are each selected from a methyl group and an ethyl group.
  • a is 1 or 2;
  • the manufacturing method also includes the conductive material powder and the binder component, and the total mass of the conductive material powder and the binder component is 100% by mass. Including blending at a ratio of mass%.
  • the silane compound represented by the above formula (1) and / or a partially hydrolyzed condensate thereof (B component in Examples described later.
  • curable silicone composition In other words, the alkoxy group (OR 2 ) possessed by the hydrolyzed and bonded to the hydroxyl group on the metal surface (typically by dehydration condensation), flaky zinc powder and flaky A film (cured film) in which the aluminum powder is firmly bonded (dissimilar metal bonding) in a laminated state can be formed.
  • the anticorrosive has a small content of metal powder (conductive material powder) compared to conventional general zinc rich paint, and contains a large amount of binder components having the above composition.
  • the anticorrosive is hard and dense due to curing of the anticorrosive.
  • a film can be formed.
  • Such a cured film is excellent in performance as a protective film that prevents corrosion-inducing factors such as water and oxygen from reaching the object to be protected.
  • the curable silicone composition constituting the binder component forms a cured product having excellent weather resistance, a coating film having high weather resistance (for example, resistance to acidic water such as acid rain) is formed according to the anticorrosive agent. Can be formed.
  • the mass of the nonvolatile content (film constituent component) contained in the paint is 100% by mass, and the ratio of the zinc powder is 80% by mass or more. Typically 90% by weight or more.
  • 93% by mass or more of the nonvolatile content is zinc powder, and the remaining 7% by mass is a binder component (alkyl silicate or the like).
  • the anticorrosive produced by the method disclosed herein contains the metal alkoxide (C component in the examples described later) and is preliminarily subjected to reduced-pressure heat treatment as flaky aluminum powder constituting the conductive material powder.
  • a cured product (anticorrosion coating) exhibiting sufficient conductivity to function as a sacrificial anode even though the proportion of the conductive material powder is relatively low, 50 to 80% by mass.
  • the surface of the aluminum powder formed into flakes is formed by the reaction between the chemical used in the production of the powder (for example, processing aids such as stearic acid and olein), aluminum and oxygen in the environment. Foreign matter such as an oxide film may be present.
  • Such foreign matter can be a factor that reduces the conductivity of the anticorrosion coating.
  • the treated flaky aluminum powder hereinafter sometimes referred to as aluminum flake
  • the conductivity is higher. Therefore, an anticorrosive agent capable of forming a film that can function more effectively as a sacrificial anode can be obtained.
  • the anticorrosive film formed from the anticorrosive agent excellent anticorrosive properties can be exhibited due to a combination of the function as the protective film (the function of preventing the contact of the corrosion inducing factor) and the function as the sacrificial anode.
  • This anticorrosion film is excellent in sustainability of the anticorrosion effect, and the film has high weather resistance, so that good anticorrosion properties can be reliably exhibited over a long period of time. Therefore, high weather resistance can be imparted to the protected object on which the anticorrosion coating is formed.
  • the anticorrosive manufacturing method disclosed here provides, as another aspect, an anticorrosive for forming an anticorrosive film on an object to be protected having a metal member.
  • the anticorrosive agent includes a conductive material powder containing flaky zinc powder and a processed flaky aluminum powder that has been formed into a flaky shape and subjected to a pretreatment that is heated under reduced pressure.
  • the anticorrosive also has the following formula (1): (R 1 ) a Si (OR 2 ) 4-a (1) (Wherein R 1 and R 2 are each selected from a methyl group and an ethyl group.
  • the binder component containing the silane compound represented by these and / or its partial hydrolysis-condensation product, and a metal alkoxide is included.
  • the anticorrosive agent comprises the conductive material powder and the binder component, and the total mass of the conductive material powder and the binder component is 100% by mass, and the proportion of the conductive material powder is 50 to 80% by mass. It mix
  • the anticorrosive agent having such a configuration it is possible to form an anticorrosive film that is hard and dense, excellent in weather resistance, and high in conductivity (and thus excellent in anticorrosive properties).
  • the anticorrosive can be preferably produced by applying any of the production methods disclosed herein, for example.
  • the pretreatment of the aluminum powder can remove at least a part of the foreign matter from the aluminum powder formed in a flaky shape (preferably, the foreign matter can be almost completely removed.
  • the foreign matter may be an oxide film (alumina coating) generated on the surface of the aluminum powder.
  • the pretreatment is preferably performed so that the oxide film can be removed.
  • the foreign matter may be an organic substance (typically a fatty acid such as stearic acid or oleic acid or other low molecular weight organic compound) attached to the surface of the aluminum powder. It is preferable to perform the pretreatment so that such organic substances can be removed.
  • the treated aluminum flakes obtained through the pretreatment are preferably kept in a non-oxidizing environment until the aluminum flakes are used (typically, until the aluminum flakes are blended with the binder component). . Thereby, it can prevent that the surface of this processed aluminum flakes oxidizes (an oxide film arises).
  • an anticorrosive film having higher conductivity (and thus exhibiting better anticorrosive properties) can be formed.
  • the conductive material powder includes a granular conductive material in a ratio of approximately 30% by mass or less, based on 100% by mass of the entire conductive material powder.
  • a granular conductive material in a ratio of approximately 30% by mass or less, based on 100% by mass of the entire conductive material powder.
  • the anticorrosion method (which can also be grasped as an anticorrosion processing method or an anticorrosion treatment method for an object to be protected) is any of the anticorrosive agents disclosed herein (the anticorrosive agent obtained by any of the methods disclosed herein). Including the provision of). Moreover, it includes providing the anticorrosive to the object to be protected (typically coating) to form an anticorrosive film. According to such a method, the object to be protected can be easily protected at a high level.
  • the method is preferably applied to corrosion prevention of existing steel structures and concrete structures (that is, maintenance of existing structures), and can exhibit good anticorrosion properties.
  • a pretreatment for applying a solution of a lithium compound (for example, lithium hydroxide aqueous solution) to the object to be protected is performed before applying the anticorrosive agent to the object to be protected.
  • a pretreatment for applying a solution of a lithium compound for example, lithium hydroxide aqueous solution
  • a pretreatment for applying a solution of a lithium compound for example, lithium hydroxide aqueous solution
  • a solution of a lithium compound for example, lithium hydroxide aqueous solution
  • Such an embodiment can be preferably employed, for example, when the object to be protected is a concrete structure having a metallic member (typically a reinforcing bar) as a structural material.
  • the technique disclosed herein can be applied to corrosion protection of various objects that include a metal member (for example, the metal member as a structural material).
  • a metal member for example, the metal member as a structural material
  • it is useful for anticorrosion of an object to be protected provided with a metal member mainly composed of a metal material nobler than zinc (which may be a metal member substantially composed of the metal material).
  • a metal member mainly composed of a metal material nobler than zinc
  • it can be preferably applied to corrosion protection of an object to be protected including an iron member (referred to as a metal member in which the metal material is iron or an iron alloy (an alloy containing iron as a main component)).
  • the present invention relates to an anticorrosive agent for forming an anticorrosion coating (a coating capable of exhibiting an anticorrosion function) on an object to be protected provided with an iron (steel, cast iron, etc.) member, a method for producing the anticorrosive, and the anticorrosion A method for preventing corrosion of an object to be protected using an agent is provided.
  • the object to be protected may be in an aspect in which the metal member is exposed to the outside (that is, an aspect in which an anticorrosive agent can be directly applied to the metal member).
  • An object to be protected substantially composed of the metal member may be used.
  • the present invention provides, as another aspect, a steel structure corrosion prevention technique (a corrosion prevention agent for a steel structure and a method for producing the same, and a corrosion prevention method for a steel structure).
  • the technology disclosed herein can be particularly preferably applied to corrosion prevention of large structures such as elevateds, bridges, pipelines, factory facilities, and ships.
  • the object to be protected may also be in an aspect in which the metal member is hidden inside (typically, an aspect in which the metal member is embedded in another material).
  • a typical example of this type of protected object is a concrete structure (for example, a reinforced concrete structure) provided with a metal member such as an iron member as a structural material.
  • the present invention provides, as another aspect, an anticorrosion technique for a concrete structure (an anticorrosive agent for a concrete structure and a method for producing the same, and an anticorrosion method for a concrete structure).
  • the technology disclosed herein can be particularly preferably applied to corrosion prevention of large concrete structures such as buildings, roads, bridges, and factory facilities.
  • an anticorrosion method for protecting a concrete structure from deterioration for example, deterioration due to salt damage
  • an anode is installed on the surface of the concrete structure, and a metal structure material (typically a reinforcing bar) in the structure is used.
  • a cathode to supply a current (anti-corrosion current)
  • an anti-corrosion method is known that suppresses the corrosion reaction of the metal structural material.
  • Such an anticorrosion method is roughly classified into an external power source method and a flowing current anode method (also referred to as a sacrificial anode method).
  • a direct current power supply device is connected between the anode and the metal structural material to forcibly supply the anticorrosion current.
  • an anode made of a metal material having a higher standard electrode potential than the constituent metal materials of the metal structure material is electrically connected to the metal structure material, and the potential difference between these metal materials is used.
  • the anticorrosion current is supplied.
  • Patent Documents 13 and 14 are exemplified as conventional technical documents relating to the anticorrosion of concrete structures by the galvanic anode method.
  • the anode is installed on the surface of the concrete structure by attaching a sheet-like zinc plate to the surface of the structure, and zinc and aluminum are sprayed on the surface of the structure to form a zinc- There is a method of forming an aluminum sprayed coating.
  • any of these methods can be easily applied to existing concrete structures, and in particular, installation (construction) in complicated places tends to be difficult.
  • the anticorrosive disclosed herein is applied to an object to be protected having a metal member therein, and is cured on the object to be protected, so that an anode (generally flowing in an anticorrosion method using the galvanic anode method) is used.
  • An effective cured product can be formed as an electric anode (referred to as a galvanic anode or a sacrificial anode).
  • a galvanic anode typically used by electrically connecting the cured product and the metal member
  • corrosion of the metal member is suppressed (electrical protection). Effective).
  • a conventionally known general coating method can be appropriately employed.
  • the cured product can effectively function as a protective coating that prevents corrosion-inducing factors such as water and oxygen from entering the concrete structure from the outside.
  • the function as a galvanic anode (sacrificial anode) and the function as a protective film can be combined to effectively prevent deterioration of the concrete structure.
  • the phenomenon that the metal member inside the concrete rusts is highly suppressed, and deterioration of the concrete structure due to the rust (typically damage such as cracking and peeling) can be prevented.
  • the anticorrosive disclosed herein is preferably applied to a concrete structure that has already started to deteriorate, and can effectively suppress the progress of further deterioration.
  • flaky zinc powder formed by flaking zinc preferably zinc having a purity of 95% or more, typically 98% or more, for example, 99% or more
  • aluminum preferably a conductive material powder containing aluminum powder formed with flakes of 95% or more purity, typically 98% or more purity, for example, 99% purity aluminum or more
  • the conductive material powder comprises flaky zinc powder and flaky aluminum powder (hereinafter also referred to as “flaky metal powder”), approximately 50/50 to 99/1 (more preferably approximately 70/30 to 98). / 2, more preferably about 85/15 to 95/5).
  • the shape of the flaky metal powder has a size (maximum diagonal length or diameter) of 20 to 80 ⁇ m (more preferably 40 ⁇ m, as an average value when 10 points are measured with a microscope with a magnification of 2,000 times, for example. About 60 ⁇ m), and the thickness can be about 0.5-10 ⁇ m (more preferably 1-5 ⁇ m).
  • the method for producing the flaky metal powder is not particularly limited. For example, zinc powder and aluminum powder formed into flakes using a stamping mill can be preferably used.
  • the standard electrode potential of iron is ⁇ 0.447V
  • the standard electrode potential of zinc is ⁇ 0.762V
  • the standard electrode potential of aluminum is ⁇ 1.662V.
  • the flaky aluminum powder is predetermined in advance (that is, prior to preparation of the anticorrosive, typically before being combined with the binder component). It is preferable to use treated aluminum flakes that have been pretreated.
  • the pretreatment is a treatment in which the aluminum powder formed in a flaky shape is heated under reduced pressure, and is performed so as to be able to remove foreign matters such as an oxide film and attached organic matter (for example, stearic acid) from the aluminum powder. Is preferred.
  • the processing conditions for performing such pretreatment can be set as appropriate so that the foreign matter can be appropriately removed.
  • the processing pressure is about 10 Pa to 10,000 Pa (preferably 100 Pa to 5,000 Pa, such as 500 Pa to 2,000 Pa), and the processing temperature is 200 ° C. or higher and below the melting point of aluminum (typically 300 ° C.
  • a temperature of about ⁇ 620 ° C., preferably about 400 ° C. to 600 ° C., for example, 500 ° C. to 550 ° C. can be employed.
  • the time for performing the reduced pressure heat treatment is not particularly limited, it is usually suitably 6 hours or less (preferably 5 hours or less) from the viewpoint of production cost and the like, for example, about 1.5 hours to 5 hours. be able to.
  • the time for performing the heat treatment under reduced pressure may be about 1.5 hours to 2 hours.
  • the treated aluminum flakes that have been subjected to the above pre-treatment are used until they are used (typically, the aluminum flakes and the binder component) in order to prevent the flakes from reacting with oxygen to form an oxide film on the surface. It is preferred to keep it in a non-oxidizing environment (until blended).
  • a non-oxidizing environment accommodates the treated aluminum flakes in a sealable container (in particular, a container excellent in performance for preventing the ingress of moisture and oxygen gas), and eliminates the gas in the container.
  • a non-oxidizing gas typically, an inert gas such as nitrogen gas or carbon dioxide gas.
  • an embodiment in which treated aluminum flakes are accommodated in a film bag body and the gas in the bag body is exhausted and sealed (the treated aluminum flakes are vacuum packed) can be preferably employed.
  • the flaky zinc powder may also be a flaky zinc powder obtained by subjecting the zinc powder to heat treatment under reduced pressure to remove foreign substances that may be present on the surface of the zinc powder.
  • the treatment temperature when the reduced-pressure heat treatment is performed on the zinc powder formed in the form of flakes is preferably about 200 ° C. or higher and below the melting point of zinc (typically 200 ° C. to 350 ° C.). According to the anticorrosive agent using the treated flaky zinc powder that has been subjected to such treatment, an anticorrosive film having better conductivity (and hence excellent anticorrosion properties) can be formed.
  • the conductive material powder used in the technology disclosed herein can be substantially composed of the flaky zinc powder and the flaky aluminum powder.
  • a conductive powder containing a granular conductive material in addition to these flaky metal powders may be used.
  • “granular” in the granular conductive material means that it is a particle (particle) gathered around the center of gravity, unlike a thinly spread shape like flakes, and is not limited to a strict spherical shape.
  • a metal powder, a carbon powder, or the like that includes a metal particle substantially composed of various conductive metals (for example, a metal particle formed by a known atomizing method). it can.
  • the metal powder may be a processed metal powder that has been previously subjected to a reduced pressure treatment for removing foreign matter.
  • a preferred example of the granular conductive material is granular zinc powder.
  • granular zinc powder having an average particle size of about 200 ⁇ m or less (typically 1 ⁇ m to 200 ⁇ m) can be preferably used, and the average particle size is about 3 ⁇ m to 150 ⁇ m (for example, 5 ⁇ m to 100 ⁇ m). ) Is more preferable.
  • zinc powder manufactured by a known atomizing method can be preferably used as the granular conductive material.
  • granular conductive material examples include carbon powder.
  • granular zinc powder having an average particle size of about 100 nm or less (typically 0.5 nm to 100 nm) can be preferably used, and the average particle size is about 0.7 nm to 50 nm ( For example, 0.7 nm to 5 nm) may be used.
  • carbon particles having an average particle size of about 1 nm or less typically 0.7 nm to 1 nm
  • the amount of such a granular conductive material used can be appropriately set in consideration of the effect of adding the conductive material (effect of improving conductivity), the influence on the physical properties of the film, the material cost, and the like.
  • the granular conductive material can be used at a rate of about 50% by mass or less based on 100% by mass of the entire conductive material powder, and usually at a rate of about 30% by mass or less of the entire conductive material powder.
  • a conductive material is preferable to use a conductive material.
  • the ratio is preferably about 30% by mass or less (typically about 0.01 to 30% by mass, eg about 5 to 30% by mass).
  • carbon powder is used as the granular conductive material, the ratio is set to about 5% by mass or less (typically about 0.001 to 5% by mass, for example about 0.01 to 1% by mass). preferable.
  • the curable silicone composition has the following formula (1): (R 1 ) a Si (OR 2 ) 4-a (1); Or a partial hydrolysis condensate thereof.
  • R 1 and R 2 in the above formula (1) are each selected from a methyl group and an ethyl group. a is 1 or 2;
  • a is 1 or 2;
  • the silane compound and / or its partial hydrolysis-condensation product have several R ⁇ 1 > in 1 molecule, those R ⁇ 1 > may be the same and may differ. The same applies to R 2 .
  • silane compound represented by the above formula (1) that is, alkyltrialkoxysilane or dialkyldialkoxysilane
  • partial hydrolysis condensates thereof include methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxy.
  • Hydrolysis condensate single hydrolysis condensate of any one silane compound selected from these silane compounds, these silanes Mention may be made of cohydrolyzed condensates of two or more silane compounds selected from compounds.
  • the concept of “hydrolysis condensate” includes a single hydrolytic condensate of one silane compound and a cohydrolysis condensate of two or more silane compounds. .
  • the curable silicone composition is represented by one or more (typically one) partial hydrolysis condensate of the silane compound represented by the above formula (1) and the above formula (1).
  • One or two or more (typically one) silane compounds can be used in combination.
  • a curable silicone composition substantially composed of the partial hydrolysis condensate which may contain a plurality of partial hydrolysis condensates having different average polymerization degrees as described later
  • the silane compound is preferable.
  • a curable silicone composition containing any one silane compound represented by the above formula (1) and a partially hydrolyzed condensate of the same silane compound as the silane compound may be used.
  • the proportion of the silane compound represented by the formula (1) is 30 to 50% by mass.
  • a curable silicone composition having a certain composition typically the balance is a partial hydrolysis-condensation product of the silane compound represented by the formula (1)) is preferable.
  • the partially hydrolyzed condensate is A curable silicone composition which is a partially hydrolyzed condensate of dialkoxysilane or trialkoxysilane (for example, methyltrimethoxysilane) in which R 1 and R 2 are both methyl groups can be preferably used.
  • the partial hydrolysis condensate contained in the curable silicone composition is a condensate having an average degree of polymerization of 3 to 5 of the silane compound represented by the formula (1) (that is, an average of 3 to 5 mer, hereinafter “A low molecular weight condensate) and a condensate of the silane compound having an average degree of polymerization of 12 to 18 (hereinafter also referred to as a “high molecular weight condensate”.
  • the term “molecular weight” may include a higher molecular weight compared to the above-mentioned condensates having an average degree of polymerization of 3 to 5.
  • the partial hydrolysis condensate may be substantially composed of the low molecular weight condensate and the high molecular weight condensate.
  • An anticorrosive agent prepared by preparing two kinds of condensates having such an average degree of polymerization and blending them is preferable.
  • the blending ratio of the low molecular weight condensate and the high molecular weight condensate is, for example, about 15 to 35 parts by mass (preferably 20 to 30 parts by mass) of the high molecular weight condensate with respect to 45 parts by mass of the low molecular weight condensate. It is appropriate to do.
  • the anticorrosive agent according to the present invention may contain, for example, 40 to 50 parts by mass of the low molecular weight condensate with respect to 45 parts by mass of the silane compound represented by the formula (1).
  • the high molecular weight condensate may be contained, for example, in a proportion of 15 to 35 parts by mass (preferably 20 to 30 parts by mass) with respect to 45 parts by mass of the silane compound.
  • the metal alkoxide used in the anticorrosive agent disclosed herein is a component that functions to enhance the conductivity of the cured product while assisting the curing of the curable silicone composition.
  • the anticorrosive agent of the present invention containing such a metal alkoxide has good conductivity (that is, it can function well as a sacrificial anode) despite the relatively high content of the binder component as described above.
  • the cured product shown can be formed. According to the anticorrosive having such a composition, a cured product having both a function as a sacrificial anode and a function as a protective film can be formed.
  • metal alkoxides such as aluminum (Al), titanium (Ti), tin (Sn), zirconium (Zr), zinc (Zn) and iron (Fe) can be used. Only one type of metal alkoxide may be used, or two or more types of metal alkoxide may be used in combination. Usually, a metal alkoxide having a structure in which two or more alkoxy groups are bonded to one metal atom can be preferably used.
  • aluminum alkoxide typically aluminum trialkoxide
  • the alkoxy group is preferably one having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, hexyloxy group, phenoxy group, etc.
  • a metal alkoxide having a structure in which one or two or more alkoxy groups are bonded to a metal can be preferably used. From the viewpoint of ease of handling, metal alkoxides in which at least one (preferably all) of the alkoxy groups are isopropoxy groups are particularly preferable.
  • aluminum triisopropoxide can be preferably used as the metal alkoxide in the present invention.
  • a metal having a structure in which at least one organic group having an acylate group and at least one (preferably two or more) alkoxy groups are bonded to the metal such as di-n-butoxy (ethylacetoacetate) aluminum.
  • Alkoxides preferably aluminum alkoxides
  • the anticorrosive has a total mass of the curable silicone composition and the metal alkoxide of 100% by mass, and the metal alkoxide is, for example, 5 to 20% by mass (preferably Is contained in the range of 8 to 15% by mass.
  • the conductivity of the resulting cured product performance as a sacrificial anode
  • the handleability of the anticorrosive agent for example, ease of application to the protected material
  • the anticorrosive agent of the present invention can be produced by mixing the above-described materials at a predetermined ratio.
  • the total weight of the conductive material powder, the curable silicone composition, and the metal alkoxide is 100% by mass, and these materials are mixed at a ratio of 50-80% by mass of the conductive material powder. Is appropriate.
  • the total mass of the flaky metal powder, the curable silicone composition, and the metal alkoxide is 100% by mass, and these materials are used at a ratio of 50 to 80% by mass. It is appropriate to mix.
  • a curable silicone composition and a metal alkoxide are mixed to prepare a binder composition (binder component), and then a conductive material powder is added and mixed thereto. It is done.
  • a conductive material powder flaky aluminum powder, and granular conductive material used as a suitable optional component
  • a mixed powder obtained by mixing a part or all of these binders. It may be mixed with the composition, or each component may be added to the binder composition and mixed.
  • the viscosity (kinematic viscosity) at 0 ° C. is, for example, preferably in the range of about 1 to 200 mm 2 / S, more preferably in the range of about 5 to 50 mm 2 / S, as measured by JIS K 2283. More preferably, it is in the range of 10 to 30 mm 2 / S.
  • the viscosity of the binder composition is set to the above range, whereby the concrete It can be set as the anti-corrosion agent which permeates the inside of a structure well and exhibits a high anti-corrosion effect (deterioration prevention effect).
  • the anticorrosive agent according to the present invention can further contain components other than the above-mentioned materials as long as the effects of the present invention are not significantly impaired.
  • What can be selected as such an optional component may include general curing catalysts (typically moisture curing catalysts) other than metal alkoxides, alcohols (for example, monovalent lower alcohols), and the like.
  • general curing catalysts typically moisture curing catalysts
  • alcohols for example, monovalent lower alcohols
  • Other additives used in general curable silicone compositions colorants such as dyes and pigments, fillers, adhesion improvers, leveling improvers, inorganic and organic UV absorbers, storage stability
  • An improving agent, a plasticizer, an antiaging agent, etc. may be contained.
  • the blending amount of the curing catalyst varies depending on the content of the curable silicone composition to be used, the type of the curing catalyst, and the desired curing speed, but if it is too little or too much, the curability, workability, storage stability, Since there is a risk that the coating film characteristics and the like tend to be reduced, it is generally appropriate that the range is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable silicone composition. A range of 0.5 to 10 parts by mass is preferred.
  • the anticorrosive agent of the present invention is typically a fluid property (liquid) at 25 ° C.
  • an anticorrosive having a viscosity at 25 ° C. in the range of about 20 to 400 mPa ⁇ S (more preferably about 50 to 200 mPa ⁇ S) is preferable.
  • the viscosity here is a value measured with a digital rotary viscometer Visco Basic Plus (manufactured by Viscotec Corporation).
  • the anticorrosive agent can contain a small amount of a solvent (typically an organic solvent such as a lower alcohol) for viscosity adjustment or the like.
  • the mass of the anticorrosive is 100% by mass and the content of the solvent is about 10% by mass or less. More preferably, the content is about 5% by mass or less.
  • the anticorrosive agent is a liquid composition that does not substantially contain a solvent (that is, a solvent-free type).
  • the anticorrosive disclosed herein is applied to the surface of various objects to be protected as described above, and corrosion of metal members constituting the objects to be protected (and thus deterioration of objects to be protected including the metal members). ) Can be prevented.
  • a general coating method (which may be on-site coating) such as roller coating, spray coating, brush coating, or dipping can be appropriately employed.
  • the preferred coating amount varies depending on the length of the anticorrosive effect provided by the anticorrosive agent (lifetime), the composition of the anticorrosive agent (for example, the type of metal powder and its content), and the thickness of the cured product, for example. Is suitably in the range of about 30 to 120 ⁇ m, and usually in the range of about 50 to 70 ⁇ m in thickness.
  • the range to which the anticorrosive agent is applied may be the entire range of the surface of the object to be protected, or may be a partial range.
  • the anticorrosive disclosed herein is applied to a protected object in which the metal member is exposed to the outside, the anticorrosive film is formed so as to form a substantially entire range of the exposed metal member. It is preferable to provide an anticorrosive.
  • the anticorrosive disclosed herein is used for, for example, anticorrosion (electrical anticorrosion) of a concrete structure, the anticorrosive is provided so as to obtain an anticorrosion current sufficient to exhibit the target anticorrosion performance. Area (in other words, the installation area of the cured product) can be adjusted.
  • a pattern such as a planar shape, a stripe shape, a lattice shape, or a dot shape may be used as appropriate, and these patterns may be combined.
  • an anticorrosive agent in a plane shape over a relatively wide range (in other words, to form a cured anticorrosive agent).
  • the anticorrosive provided by the present invention can typically be cured by moisture in the air at room temperature to form a cured anticorrosive (anticorrosion coating) (ie, room temperature curable). Therefore, for example, the anticorrosive agent is applied to an object to be protected and allowed to stand for several hours or more (preferably several days or more), thereby exhibiting a good anticorrosive effect (typically good as a sacrificial anode and a protective film).
  • the anti-corrosion coating can be appropriately formed.
  • thermal damage thermal brittleness
  • the anticorrosive agent according to the present invention can be applied to the protected object and cured at room temperature. This thermal damage is avoided.
  • the anticorrosive agent of the present invention When the anticorrosive agent of the present invention is cured, a chemical bond (mainly between the hydroxyl group on the metal surface and the alkoxy group of the curable silicone composition) between the flaky metal powder contained in the anticorrosive agent and the binder component. By hydrolytic condensation reaction). By this, the anticorrosive hardened
  • the cured product typically constitutes a laminated film in which flaky zinc powder and aluminum powder are stacked in the thickness direction. The cured product thus configured can effectively exhibit the function as a sacrificial anode and the function as a protective film.
  • the anticorrosive according to the present invention contains a large amount of a predetermined binder component, a hard and dense film can be formed by curing of the anticorrosive. Therefore, desired anticorrosion characteristics can be exhibited without requiring a troublesome additional process such as a sealing process. Moreover, the anticorrosion film formed by hardening of this anticorrosive agent can exhibit a desired anticorrosion characteristic, without requiring the topcoat layer which covers this film. However, it is not excluded to provide an additional layer on the anticorrosion coating.
  • the technique disclosed here is one or two or more layers (for example, the purpose of decoration etc.) covering a partial area or the entire area of the coating film on the corrosion protection film formed by using the corrosion inhibitor according to the present invention.
  • the resin-based paint layer provided in (1) may be implemented.
  • an embodiment in which a pretreatment for applying a solution of a lithium compound before applying the anticorrosive to the object to be protected is preferable.
  • the object to be protected is a concrete structure, it is particularly effective to perform such pretreatment.
  • lithium ions can be supplied to an object to be protected (more specifically, for example, inside a microcrack existing in an existing concrete structure).
  • the electron movement in this to-be-protected object is accelerated
  • the lithium compound solution it is preferable to use a solution in which a lithium compound is dissolved in an aqueous solvent (water or a mixed solvent containing water as a main component, typically water) from the viewpoints of environmental load and workability.
  • aqueous solvent water or a mixed solvent containing water as a main component, typically water
  • lithium hydroxide LiOH
  • concentration of the said lithium compound solution is not specifically limited, For example, the solution of about 1M (1 mol / l) can be used preferably.
  • the anticorrosive agent was manufactured using the following materials.
  • A1 Flaked zinc powder (size: 40 ⁇ m to 60 ⁇ m, thickness: 1 ⁇ m to 5 ⁇ m, purity: 98%)
  • A2 Flaky aluminum powder subjected to heat treatment under reduced pressure (flaky aluminum powder having a size of 40 ⁇ m to 60 ⁇ m, a thickness of 1 ⁇ m to 5 ⁇ m and a purity of 98%, treated at 7.5 Torr (about 1000 Pa) at 530 ° C. for 3 hours And then immediately vacuum-packed and saved).
  • A3 Granular zinc powder produced by the atomizing method (average particle size 10 ⁇ m).
  • B1 Partially hydrolyzed condensate of methyltrimethoxysilane (average polymerization degree 4, kinematic viscosity 4 mm 2 / S).
  • B2 Partial hydrolysis-condensation product of methyltrimethoxysilane (average polymerization degree 15, kinematic viscosity 60 mm 2 / S).
  • B3 Dimethyltrimethoxysilane.
  • C1 Aluminum triisopropoxide.
  • C2 Di-n-butoxy (ethyl acetoacetate) aluminum (product of Hope Pharmaceutical Co., Ltd., trade name “Kerope ACS”).
  • an anticorrosive was produced according to the following procedure. That is, in a nitrogen atmosphere at room temperature, 45 parts by mass of B1 (low molecular weight condensate of methyltrimethoxysilane), 25 parts by mass of B2 (high molecular weight condensate of methyltrimethoxysilane), and 45 parts by mass of B3 (Dimethyldimethoxysilane) was mixed with stirring. To 115 parts by mass of the mixture, 15 parts by mass of C1 (aluminum triisopropoxide) and 12 parts by mass of C2 (di-n-butoxy (ethylacetoacetate) aluminum) were added and further stirred. Thus, the binder composition (binder component) which does not contain an organic solvent substantially was prepared.
  • A1 flaky zinc powder
  • A2 treated flaky aluminum powder
  • A3 granular zinc powder
  • the 55 parts by mass of the mixed powder and 45 parts by mass of the binder composition were mixed in a nitrogen atmosphere. This mixing was performed while cooling the system from the outside so that the temperature of the system did not exceed 35 ° C. In this way, an anticorrosive having a viscosity at 25 ° C. of about 100 mPa ⁇ S was obtained.
  • ⁇ Rust prevention test (Cass test)> A steel plate (material SS400, 3 mm ⁇ 70 mm ⁇ 150 mm) is surface-treated with sand blasting, and the anticorrosive agent is applied by a spraying method so that the film thickness after curing is 50 ⁇ m, and then the atmosphere is 25 ° C. and 65% relative humidity It was left for 5 days to cure. In this way, a test piece according to Example 1 was produced. Further, a test piece (Comparative Example 1) was prepared by spraying zinc on the same steel plate as described above to a thickness of 100 ⁇ m to form a zinc spray coating and applying a butyral resin sealing agent to the coating.
  • test piece (Comparative Example 2) in which a 100 ⁇ m zinc-aluminum composite metal sprayed coating was formed on the same steel plate as described above and a butyral resin sealing agent was applied to the coating was prepared.
  • These test pieces were immersed in a test solution according to JIS H8502, and the presence or absence of rust and the degree thereof were observed every day.
  • the test piece of Comparative Example 1 was rusted red after 7 days and the test piece of Comparative Example 2 was rusted after 12 days, whereas the test piece of Example 1 was rusted after 45 days. Not observed.
  • a vinyl chloride resin plate having a width of 100 mm, a length of 300 mm, and a thickness of 3 mm was prepared.
  • the anticorrosive produced above was applied to the entire surface of the resin plate.
  • the coating thickness of the anticorrosive was adjusted so that the thickness of the film formed by curing was about 50 ⁇ m.
  • the resin plate coated with the anticorrosive was allowed to stand for 5 days in an atmosphere of a temperature of 24 ° C. and a relative humidity of 65% to cure the anticorrosive.
  • the cured product (anticorrosion coating) thus obtained was hard and dense.
  • the voltmeter connected between them was about 0.9V. Indicated.
  • the anticorrosion film is formed on the surface of a concrete structure having an iron structure material (typically, a reinforcing bar), the anticorrosion film and the iron structure material in the concrete structure are formed. It shows that a potential difference of about 0.9V can occur.
  • the anticorrosion coating is galvanic. It shows that it can function properly as an anode (sacrificial anode).
  • the composition prepared by the same operation as the production of the anticorrosive is applied to one side of the vinyl chloride resin plate in the same manner as described above except that the C component (C1, C2) is not used. Cured.
  • the cured product-attached resin plate and the iron plate were immersed in a 0.3% strength NaCl aqueous solution in the same manner as described above and a voltmeter was connected between them, no voltage was measured. This result shows that the cured product formed from the above composition not containing C1 and C2 has low conductivity and is not suitable for use as a flowing anode.
  • the resin plate with cured product and the iron plate were immersed in a 0.3% NaCl aqueous solution in the same manner as described above, and a voltmeter was connected between the two. Not measured.
  • This result shows that since the content ratio of the mixed powder is too small in such a composition, the cured product formed from the cured product has low conductivity and is not suitable for use as a galvanic anode.
  • the resulting cured film When applied to one side of the resin plate and cured, the resulting cured film was porous and poor in performance to prevent the permeation of water and oxygen.

Abstract

Cette invention concerne un inhibiteur de corrosion empêchant la corrosion d'un objet contenant un élément métallique. Cet inhibiteur est facile à appliquer et peut présenter de meilleures propriétés anticorrosives. L'invention concerne aussi un procédé de production de l'inhibiteur de corrosion. Une poudre conductrice est préparée et comprend une poudre lamellaire de zinc et une poudre lamellaire d'aluminium traitée et obtenue par un traitement préalable dans lequel une poudre constituée de flocons d'aluminium est chauffée à une pression réduite. Un liant est préparé et comprend : un composé silane de formule (R1)aSi(OR2)4-a et/ou un produit d'hydrolyse partielle et de condensation du composé ; et un alcoxyde métallique. Dans la formule, R1 et R2 sont chacun un méthyle ou un éthyle et a vaut 1 ou 2. La poudre conductrice est mélangée avec le liant en une proportion telle que la quantité de la poudre représente 50 à 80 % en masse de la somme poudre et liant.
PCT/JP2007/001465 2007-12-25 2007-12-25 Inhibiteur de corrosion et son procédé de production WO2009081452A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014501846A (ja) * 2010-11-08 2014-01-23 グラス，ガレス アノードアッセンブリ及びその方法
EP2876144A4 (fr) * 2012-07-20 2016-03-09 Chugoku Marine Paints Composition de revêtement primaire antirouille et son utilisation
EP2998366A1 (fr) * 2014-09-16 2016-03-23 China Steel Corporation Plaque en acier revêtu résistant à l'oxydation à haute température et son procédé d'estampage à chaud

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JPS6383172A (ja) * 1986-09-29 1988-04-13 Kansai Paint Co Ltd 溶接可能な防錆潤滑性被覆形成性組成物及びこれを用いた表面処理鋼板の製造方法
JPH07150374A (ja) * 1993-08-31 1995-06-13 Basf Corp 徐放性腐食防止化合物で処理したアルミニウムフレーク顔料およびそれを含有する塗料
JPH1060662A (ja) * 1996-08-19 1998-03-03 Ebara Yuujiraito Kk 塗装前処理方法
JPH10237579A (ja) * 1997-02-21 1998-09-08 Sumitomo Metal Ind Ltd 低熱膨張・高熱伝導熱放散材料とその製造方法
JP2004218072A (ja) * 2002-12-24 2004-08-05 Nippon Paint Co Ltd 塗装前処理方法
JP2005232537A (ja) * 2004-02-19 2005-09-02 Kinzoku Kagaku Kenkyusho:Kk 防錆剤及び塗装物品
JP2006240157A (ja) * 2005-03-04 2006-09-14 Sumitomo Metal Ind Ltd 潤滑処理鋼板および潤滑皮膜形成用処理液

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JPS6383172A (ja) * 1986-09-29 1988-04-13 Kansai Paint Co Ltd 溶接可能な防錆潤滑性被覆形成性組成物及びこれを用いた表面処理鋼板の製造方法
JPH07150374A (ja) * 1993-08-31 1995-06-13 Basf Corp 徐放性腐食防止化合物で処理したアルミニウムフレーク顔料およびそれを含有する塗料
JPH1060662A (ja) * 1996-08-19 1998-03-03 Ebara Yuujiraito Kk 塗装前処理方法
JPH10237579A (ja) * 1997-02-21 1998-09-08 Sumitomo Metal Ind Ltd 低熱膨張・高熱伝導熱放散材料とその製造方法
JP2004218072A (ja) * 2002-12-24 2004-08-05 Nippon Paint Co Ltd 塗装前処理方法
JP2005232537A (ja) * 2004-02-19 2005-09-02 Kinzoku Kagaku Kenkyusho:Kk 防錆剤及び塗装物品
JP2006240157A (ja) * 2005-03-04 2006-09-14 Sumitomo Metal Ind Ltd 潤滑処理鋼板および潤滑皮膜形成用処理液

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014501846A (ja) * 2010-11-08 2014-01-23 グラス，ガレス アノードアッセンブリ及びその方法
EP2876144A4 (fr) * 2012-07-20 2016-03-09 Chugoku Marine Paints Composition de revêtement primaire antirouille et son utilisation
EP2998366A1 (fr) * 2014-09-16 2016-03-23 China Steel Corporation Plaque en acier revêtu résistant à l'oxydation à haute température et son procédé d'estampage à chaud

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