JP2009167246A - Paste for highly anticorrosive rust-preventive coating exhibiting excellent processability in service, highly anticorrosive rust-preventive coating, highly anticorrosive steel coated with the coating, and steel structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste for a highly anticorrosive rust-preventive coating that is excellent in anticorrosive properties and rust-preventive properties as well as excellent in processability in service such as weldability, fusibility and the like, and also to provide a highly anticorrosive rust-preventive coating, a highly anticorrosive steel material coated with the coating, and a steel structure. <P>SOLUTION: The paste for the highly anticorrosive rust-preventive coating exhibiting excellent processability in service comprises an organic solvent containing a dispersant and, dispersed as a pigment therein, a Zn alloy particle having an average particle size of 0.05-200 μm, where the Zn alloy particle contains 0.01-30 mass% of Mg and has a physically fractured face and/or a crack having a length of at least 0.01 μm or a crack having a depth of at least 0.01 μm on the surface thereof. The coating obtained by using the coating comprises the dispersant containing a saturated fatty acid amide and/or an unsaturated fatty acid amide in an amount of 0.01-10 mass% based on the organic solvent. The steel material coated with the coating and the steel structure are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a paste for high corrosion resistance rust preventive paint excellent in processability, high corrosion resistance rust preventive paint, high corrosion resistance rust preventive paint coated steel materials and steel structures, and in particular, paints mixed with a dispersant on the surface of various steel materials. Highly corrosion-resistant rust-proof paint paste, high corrosion-resistant rust-proof paint, steel material and steel structure that have both excellent sacrificial anti-corrosive action when applied to, and excellent workability such as weldability and fusing Related to things.

  As a countermeasure against corrosion of steel materials, zinc rich paint having a structure in which Zn metal particles containing inevitable impurities are used as a pigment, an organic material, and an inorganic material as a vehicle (liquid binder component) is frequently used. Zinc rich paint is mainly used for undercoating of heavy anticorrosion coating, and the feature of the anticorrosion mechanism is sacrificial anticorrosive action of Zn metal particles contained in the coating film. However, since the anticorrosive ability of the zinc rich paint coating depends strongly on the sacrificial anticorrosive action of the Zn metal particles as described above, the disappearance rate of zinc is large and the protective action against steel materials does not last long depending on the use environment. There is a case.

  Therefore, measures such as increasing the content of Zn metal particles in the coating film or increasing the film thickness have been taken. However, such as a decrease in adhesion to the steel surface, cracking or sagging of the coating film, etc. It is difficult to achieve both anticorrosion performance and physical properties and workability of the coating film.

  Under such circumstances, the development of a high-performance zinc rich paint that retains the advantages of the conventional zinc rich paint and exhibits sacrificial anticorrosive action for a long period of time is expected, and various proposals have been made so far. . For example, from Patent Document 1 to Patent Document 4, an invention related to an organic zinc rich paint containing Zn-Mg alloy particles or Zn-Mg-Al alloy particles in addition to Zn metal particles, and Patent Document 5, An invention related to an organic zinc rich paint containing Zn-Mg alloy particles and Mn metal particles in addition to Zn metal particles has been proposed.

  Under such circumstances, these organic paints deteriorate in a complex environment that is affected by ultraviolet rays, moisture, oxygen, etc., and inorganic paints that do not have the disadvantage of requiring maintenance in a relatively short period of time. Several proposals have been made so far for the purpose of improving the anticorrosion performance. For example, although the object is different from that of the present invention, Patent Document 6 proposes an invention relating to a coating composition containing a mixture of Zn metal particles and Mg or Mg alloy with the aim of suppressing coating deterioration during welding and fusing. .

JP 59-052645 A JP 59-167249 A Japanese Unexamined Patent Publication No. 1-311178 JP 2001-164194 A JP 59-198142 A Japanese Patent Laid-Open No. 61-213270

  However, Patent Documents 1 to 5 are organic paints, and it is said that maintenance is required in a relatively short time in consideration of deterioration in a complex environment that needs to consider the influence of ultraviolet rays, moisture, oxygen, and the like. A side problem remains. Further, Patent Document 6 has a problem that the fusing fume increases and the frequency of occurrence of blowholes is high, and there remains a problem that the work efficiency at the time of welding and fusing is lowered, and further improvement has been demanded.

  Therefore, the present invention is a mixture of a saturated fatty acid amide or an unsaturated fatty acid amide in a paste and combined with an inorganic or organic binder to exhibit excellent corrosion resistance and rust prevention, and further excellent weldability, The purpose is to provide a high corrosion resistance rust preventive paint paste having high processability such as fusing property, a high corrosion resistance rust preventive paint, and a steel material imparted with high corrosion resistance and rust resistance by applying the paint. .

  As a result of various studies, the present inventors have dispersed Zn alloy particles having an average particle size of 0.05 to 200 μm as a pigment in an organic solvent containing a dispersant, and as the dispersant, a saturated fatty acid amide and When one or both of the unsaturated fatty acid amides are contained in an amount of 0.01 to 10% by mass with respect to the organic solvent in the paste, in addition to excellent corrosion resistance and rust resistance, it also has excellent processability. A new headline has been reached, which has led to the construction of the basics of the present invention.

  Furthermore, the Zn alloy particles in the high corrosion resistance rust preventive paint having excellent utilization processability are examined in detail, and the Zn alloy particles are in mass%, Al: 0.01 to 10%, Si: 0.01 to 3%. It was found that further rust prevention and utilization processability were exhibited by containing one or two of the above.

  Furthermore, when the organic solvent containing one or both of saturated fatty acid amide and unsaturated fatty acid amide as a dispersant is toluene or xylene, it has been found that it has stable and excellent corrosion resistance, rust prevention property and processability. Is. Although the high corrosion resistance rust preventive paint containing the Zn alloy particles described above brings excellent corrosion resistance and rust preventive properties as they are, as a result of further studies, they are mixed with Zn metal particles that have been conventionally used as pigments. After the paint preparation, the one used for painting on the steel plate surface, etc. uses Zn metal particles alone, and has significantly superior corrosion resistance / rust prevention and superior utilization processing compared to those used for painting the steel plate surface etc. I found out that it also has sex.

  In general, with regard to coating thickness, corrosion resistance / rust prevention, and workability such as weldability and fusing properties are contradictory properties, and if coating thickness is increased in order to improve corrosion resistance and rust prevention properties, use processing Sex declines. On the other hand, when the coating thickness is reduced to improve the processability of use, the corrosion resistance and rust resistance are significantly reduced. In the present invention, it has been found that, while exhibiting excellent corrosion resistance and rust resistance in thin film coating having a coating thickness of 2 μm to 50 μm, it also exhibits excellent weldability and fusing properties.

The present invention has been brought about as a result of the above studies, and specific means for solving the problems are as follows.
(1) As a dispersant, 0.01% to 10% of one or both of a saturated fatty acid amide and an unsaturated fatty acid amide is contained by mass% with respect to the organic solvent, and the average particle size is 0 in the organic solvent. 0.05-200 μm Zn alloy particles are dispersed as a pigment, and the Zn alloy particles contain Mg: 0.01-30% by mass, the balance being Zn and inevitable impurities, and the Zn alloy particles High corrosion resistance prevention with excellent workability, characterized by having a physical fracture surface and / or a crack with a length of 0.01 μm or more or a crack with a depth of 0.01 μm or more on the alloy particle surface Rust paint paste.
(2) The paste for high corrosion resistance rust preventive paint excellent in utilization workability as described in (1) above, wherein the organic solvent is toluene and / or xylene.
(3) Furthermore, the Zn alloy particles contain 1% or 2 types of Al: 0.01 to 30% and Si: 0.01 to 3% by mass%. The paste for high corrosion resistance rust preventive paint according to (2).
(4) The high corrosion resistance rust prevention according to any one of (1) to (3), wherein the Zn alloy particles have a Mg solid solution phase and a Zn-Mg intermetallic compound on a physically crushed surface. Paint paste.
(5) In the above (4), the Zn—Mg intermetallic compound contains one or more of MgZn ₂ , Mg ₂ Zn ₁₁ , Mg ₂ Zn ₃ , MgZn, or Mg ₇ Zn _3. The paste for high-corrosion-resistant rust preventive paint as described.
(6) The high corrosion resistance rust preventive paint paste according to any one of (1) to (5), wherein the Zn alloy particles are non-spherical polyhedron and have two or more faces.
(7) A high corrosion resistance rust preventive paint using the paste for high corrosion resistance rust preventive paint according to any one of (1) to (6), wherein the Zn alloy particles are contained in mass% in terms of dry paint film. High corrosion resistance rust preventive paint characterized by containing 30% or more and 85% or less.
(8) A highly corrosion-resistant rust-preventing paint in which Zn metal particles composed of Zn having an average particle diameter of 0.05 to 50 μm and inevitable impurities are dispersed in addition to the Zn alloy particles, The high corrosion resistance rust preventive paint according to (7) above, wherein x is 300.0 or less when the value of the ratio of alloy particle amount: (Zn metal particle amount) is 1 / x.
(9) The above-mentioned (8), wherein the Mg content is 0.01% to less than 30% when the total of the mixed particles of the Zn alloy particles and the Zn metal particles is 100% by mass%. ) High corrosion resistance rust preventive paint described in).
(10) The high corrosion resistance rust preventive paint according to any one of (7) to (9), wherein the binder of the high corrosion resistance rust preventive paint is an inorganic binder or an organic binder.
(11) A steel material having the steel surface coated with the anticorrosive anticorrosion paint according to any one of (7) to (10), wherein the coating thickness is 2 to 50 μm, and the high corrosion resistance Steel material.
(12) A steel structure comprising the high corrosion resistance steel material according to (11) in part or in whole.

  High corrosion resistance rust preventive paint paste, high corrosion resistance rust preventive paint, high corrosion resistance rust coated steel sheet, steel structure according to the present invention have conflicting properties such as corrosion resistance, rust resistance and weldability, and fusing ability. Because it is possible to have both, the industrial effect is immeasurable.

  In the Zn alloy particles used in the paste for high corrosion resistance rust preventive paint in the present invention, Mg: 0.01 to 30%, consisting of the balance Zn and inevitable impurities, a physically crushed surface and / or a length of 0. It has a crack of 0.01 μm or more or a crack of 0.01 μm or more in depth, and has an average particle size of 0.05 to 200 μm. The average value of the aspect ratio (maximum diameter / minimum diameter) of the maximum diameter and the minimum diameter is preferably 1 to 1.5.

  As a method for producing Zn alloy particles having an average particle diameter of 0.05 to 200 μm, a physically fractured surface and / or a crack having a length of 0.01 μm or more, or a crack having a depth of 0.01 μm or more, The Zn alloy particles produced by the gas atomization method or the mist method are added to toluene or xylene having a water content of 0.8% by mass or less to form a slurry. Can be manufactured. It can also be produced by a method in which the jet jet collides with a solid. By using this method, the average value of the aspect ratios of the maximum diameter and the minimum diameter can be set to 1 to 1.5.

  In the present invention, the Mg content in the Zn alloy particles needs to be Mg: 0.01 to 30%. Corrosion resistance compared to Zn alloy particles with the same amount of Mg added, even if less than 0.01% Mg, having a physically crushed surface and an average particle size of 0.05 to 200 μm. -Significant improvement in rust prevention is recognized, but the remarkable effect of improving corrosion resistance and rust prevention, which seems to be brought about by the combination with a physically fractured surface and / or crack, is not obtained remarkably. That is, the fundamental technology of the present invention is the remarkable effect of improving corrosion resistance and rust resistance due to the synergistic effect of the Zn alloy particles having a physically crushed surface and / or cracks and containing 0.01% or more of Mg. On the other hand, when Mg is added in excess of 30%, not only the above effects are saturated, but also economy and manufacturability are inhibited. Therefore, the amount of Mg added is set to 0.01% to 30%. The optimum value of the more preferable addition amount varies depending on the average particle diameter. In the case of an average particle diameter of 0.2 to 30 μm, which is generally considered optimal in spray coating, the lower limit is 0.1% and the upper limit is 20%. It is preferable from the viewpoint of improving the corrosion resistance and rust resistance and economical. Furthermore, if considering production stability, economy, and corrosion resistance, 0.2% to 15% is preferable. In addition, the physical crushing surface as used in the field of this invention points out the shape where a part of spherical particle was missing. When the Zn alloy particles have a physically crushed surface, the effect of improving corrosion resistance and rust resistance can be significantly obtained as described later.

  The crack in the present invention means a crack having a length of 0.01 μm or more existing on the particle surface or a depth of 0.01 μm or more from the surface. If the crack is less than 0.01 μm in length and depth, sufficient effects of improving corrosion resistance and rust resistance cannot be obtained, and a length or depth of 0.01 μm or more is required.

  The average particle size of the Zn alloy particles is set to 0.05 μm or more for ensuring adhesion during spray coating, and 200 μm or less for ensuring work stability during brush coating. In consideration of coating stability, 0.2 to 50 μm is preferable. Moreover, when considering the coating film adhesion, 0.2 to 30 μm is preferable.

  Furthermore, in this invention, the particle | grains of the said structure can contain 1 type or 2 types of Al: 0.01-30% and Si: 0.01-3%. By adding 0.01% or more of Al to particles having a physically crushed surface and / or cracks, the rust prevention property is further improved. When the Al content is about 0.01% or more, in addition to rust prevention, the corrosion resistance against self-corrosion of the particles is remarkably improved. Since it becomes difficult to form a physically crushed surface and / or a crack in the particles, the addition amount is set to 0.01 to 30%. Furthermore, 0.5 to 20% is preferable from the viewpoint of manufacturing stability and corrosion resistance. Furthermore, if considering the economy, 1.0 to 10% is preferable. Similarly, Si is further added to 0.01% or more of particles having a physically crushed surface and / or cracks, and the rust prevention property is further improved. However, the effect of the addition of Si exceeds 3%. Therefore, the addition amount was set to 0.01 to 3%. From the viewpoint of production stability and corrosion resistance, 0.5 to 3% is preferable. Furthermore, if considering the economy, 1.0 to 1.5% is preferable.

  Further, in the Zn alloy particles having a physically crushed surface and / or crack of the present invention, the Mg solid solution phase and the Zn-Mg intermetallic compound are present on the surface of the crushed portion and / or the particle including the crack. Furthermore, corrosion resistance and rust prevention can be improved. There are many unclear points about the reason why the corrosion resistance and rust prevention properties are improved by exposing the Mg solid solution phase and the Zn-Mg intermetallic compound to the surface, but one or more of these phases are crushing surfaces and / or, Co-existence with cracks has found that these properties can be obtained in a particularly stable manner, and the presence of the physical fracture surface and / or cracks makes the chemical nature of these phases more resistant to corrosion and It has been experimentally confirmed that the rust resistance is improved. Mg solid solution phase and Zn-Mg intermetallic compound are obtained by X-ray diffraction method or scanning electron microscope observation with an energy dispersive X-ray analyzer, and by analyzing the composition ratio of Mg and Zn on the physical fracture surface or crack surface. Can be identified.

Furthermore, in the present invention, the intermetallic compound phase contains one or more of MgZn ₂ , Mg ₂ Zn ₁₁ , Mg ₂ Zn ₃ , MgZn, or Mg ₇ Zn _3. Further improvement is possible. MgZn ₂ , Mg ₂ Zn ₁₁ , Mg ₂ Zn ₃ , MgZn, or Mg ₇ Zn ₃ is an Mg on the physical fracture surface or crack surface by X-ray diffraction or scanning electron microscope observation with an energy dispersive X-ray analyzer. And Zn composition ratio analysis.

  As described above, the Zn alloy particles having a physically fractured surface and / or crack of the present invention can control the chemical composition of the alloy particle simultaneously with the application of one or more physically fractured surfaces and / or cracks. However, it is possible to improve the corrosion resistance and rust prevention as never before, but the shape of the particles having the crushing surface is close to a non-flat spherical shape, one plane or curved surface surrounded by one closed ridgeline. By using a polyhedron (a crack is not included as a surface) and having a shape having two or more surfaces, it is possible to obtain more excellent corrosion resistance, rust prevention property and paintability at the same time. From the standpoint of improving corrosion resistance and rust prevention, the larger the number of physically crushed surfaces, the better. However, if the number of crushed surfaces is 1 or less, the reason is unknown at this time, but there is a large variation in the effect of improving the effect. Become. Furthermore, the above-mentioned shape range defines Zn alloy particles as a raw material, and absorbs moisture etc. in the air and actually agglomerates and binds these Zn alloy particles before being used in the paint. In addition, the shape of the Zn alloy particles such as the case where the particles are bonded to each other when cured on a steel material as a coating film is not specified.

  In the dispersant of the present invention, one or both of a saturated fatty acid amide such as stearic acid amide, palmitic acid amide, and behenic acid amide, or an unsaturated fatty acid amide such as oleic acid amide, erucic acid amide, and the like are added to an organic solvent. , 0.01 to 10% to add a high corrosion resistance rust preventive paint paste that exhibits the effect of preventing sedimentation and aggregation, and when a paint using this paste is applied to a steel material, the coating thickness is as described below Even if it is as thin as 2 to 50 μm, excellent corrosion resistance and rust resistance can be achieved, and an advantageous effect that has never been obtained can be obtained. That is, by this effect, utilization processability such as weldability and fusing property can be imparted as described later without sacrificing corrosion resistance and rust prevention. In addition to the saturated fatty acid amide or the unsaturated fatty acid amide, other dispersants such as silica may be used as the dispersant, but one or both of the saturated fatty acid amide and the unsaturated fatty acid amide are contained in the paste. The said advantageous effect is acquired by adding 0.01 to 10% with respect to the organic solvent of this. Although there remains an unclear point about this reason, the dispersant containing a predetermined amount of one or both of the saturated fatty acid amide and the unsaturated fatty acid amide has a network structure, and the precipitation of the Zn alloy particles used in the present invention. The Zn alloy particles that prevent agglomeration or adhere to the Zn alloy particles individually and prevent sedimentation and agglomeration, but the activity of the Zn alloy particles is improved by contact with these dispersants. It is presumed that the high corrosion resistance and rust prevention effect will be significantly amplified and the corrosion resistance and rust resistance will be improved. If the dispersant is less than 0.01%, the effect of preventing sedimentation / aggregation and the effect of improving corrosion resistance / rust resistance cannot be obtained. If the dispersant exceeds 10%, the corrosion resistance decreases. Even if it uses only 1 type of dispersing agent, or it mixes and uses 2 or more types, the said dispersing agent does not have a big influence on sedimentation prevention and corrosion resistance.

  Furthermore, although it is the organic solvent of this invention, the further superior sacrificial anticorrosive effect and long-term rust preventive effect can be acquired by using toluene and / or xylene. Although the reason remains unclear, it is estimated that the moisture contained in a trace amount in toluene and xylene is uniformly dispersed in the paint. Other than toluene and / or xylene, one or two of alkane hydrocarbons such as octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, and hexadecane contained in gasoline, kerosene and light oil, or paraffins The same effect can be obtained with the above mixture.

  The Zn alloy particles having the above-described crushed surface and / or crack in the present invention are required to be contained in the coating film by 30% or more when used. If it is less than 30% by mass, effects such as corrosion resistance cannot be obtained. The upper limit is not particularly specified, but if it exceeds 85%, the binder component becomes too small and defects are likely to occur in the coating film. In addition, as a binder component in a coating film, in order to ensure film forming property, it is preferable to set it as at least 15%. Furthermore, as long as it contains 30% or more of the Zn alloy particles, other powder particles may be added. For example, metal powders such as Al and stainless steel (for the purpose of design), titanium oxide, and zinc oxide It may contain an extender pigment such as oxide powder such as talc and stone powder.

  Furthermore, the above-described fractured surface and / or cracked Zn alloy particles in the present invention contain Zn metal particles having an average particle size of 0.05 to 50 μm when used, and in mass%, When the ratio value of the amount of Zn metal particles is 1 / x, x can be mixed and used at 300 or less. The term “Zn metal particles” as used herein means particles composed of Zn and inevitable impurities, and the Zn metal particles are mixed with the above-described fractured surface and / or Zn alloy particles having cracks to be used for paint pigments. Thus, the corrosion resistance and rust preventive property are remarkably improved as compared with the conventional pigments using Zn metal particles alone, but the ratio of Zn alloy particle amount: mass% of Zn metal particle amount is 1 / x. When x is more than 300.0, the effect of the Zn alloy particles on the improvement of the corrosion resistance and rust resistance is not sufficiently exhibited. Therefore, the x value is set to 300.0 or less. Furthermore, in consideration of corrosion resistance and economy, the x value is preferably 1 to 120. Further, considering the mixing stability, the x value is preferably 1-30. Moreover, in this invention, the average particle diameter of Zn metal particle used for mixing shall be 0.05-50 micrometers. The effect of improving the corrosion resistance and rust prevention in the present invention is recognized when the average particle diameter of the Zn metal particles to be mixed is in the range of 0.05 to 300 μm. Because of the diameter, the average particle diameter of the Zn metal particles was set to 0.05 to 50 μm.

  On the other hand, the mixing effect of the above-described fracture surface and / or cracked Zn alloy particles and Zn metal particles of the present invention can be roughly arranged by the content of Mg contained in the entire antirust pigment. When the total of the Zn alloy particles having a physically crushed surface and / or crack of the present invention and the Zn metal particles is 100% by mass%, the Mg content is 0.01-30. % Can be used. In addition, the effect of improving the corrosion resistance and rust prevention is to be 0.1 to 20%, which is the most remarkable range of the mixing effect of the fractured surface and / or cracked Zn alloy particles and Zn metal particles. From the viewpoint of economy, in addition, considering economic efficiency, it is more preferably 0.5 to 15%, but it can be appropriately applied depending on the purpose.

  In any case, the ratio of the Zn alloy particles or the mixed particles of the Zn alloy particles and the Zn metal particles in the paste is often adjusted to 60 to 95% by mass% from the viewpoint of easy handling. However, in order to produce a paint using these pastes, Zn alloy particles or mixed particles of Zn alloy particles and Zn metal particles are sequentially discharged every time the paint is produced. The ratio of the Zn alloy particles or the mixed particles of Zn alloy particles and Zn metal particles naturally decreases to 0%. Accordingly, there is no particular significance for the range of the ratio of Zn alloy particles or Zn alloy particles and Zn metal particles in the paste.

  However, the proportion of the Zn alloy particles or the mixed particles of Zn alloy particles and Zn metal particles in the paste is required to be 1% or more from the viewpoint of economy, and the upper limit is from the necessity of dispersion of the particles. 99% is desirable. Furthermore, when importance is attached to economy or handleability, the range of 5% or more and 95% or less is desirable. In addition, even if the ratio of the Zn alloy particles or the Zn alloy particles and the Zn metal particles in the paste is changed within the range of more than 0% to 99%, the change of the paint produced using the paste, The ability to impart corrosion resistance and rust resistance to steel materials is hardly affected.

  Next, in the present invention, the kind of the binder of the paint is not particularly defined, and any inorganic or organic binder (resin) can be used. The scope of the present invention is not limited, but examples include inorganic silicates, alkyl silicates, etc., organic epoxies, modified epoxy resins, acrylic resins, urethane resins, polyester resins. Etc. can be applied as appropriate. Moreover, the compounding type of a hardening | curing agent can apply suitably the hardening type by multiple liquids, such as 1 liquid hardening type and 2 liquid hardening type, according to the objective. Further, as a curing method, room temperature curing, heat curing, UV curing, electron beam curing, underwater curing, and the like can be appropriately applied according to each purpose.

  The steel material and the steel structure targeted by the high corrosion resistance rust preventive paint of the present invention are not particularly specified, but the coating thickness is 2 to 50 μm in consideration of the corrosion resistance / rust preventive property and utilization processability of the present invention example. Stipulated. In order to obtain the corrosion resistance and rust resistance by applying the coating material of the present invention to the surfaces of steel materials and steel structures, it is necessary to make the coating thickness 2 μm or more. On the other hand, if the coating thickness exceeds 50 μm, when welding steel with the coating film on the surface, the thick coating causes blowholes and damages the soundness of the weld. In the case of fusing, a thick coating film causes the generation of fume, which deteriorates the working environment and deteriorates the fusing property. Therefore, in order to ensure utilization processability such as weldability or fusing property, the coating thickness is set to 50 μm or less.

  In addition, the steel material and steel structure targeted by the present invention are those in which the high corrosion resistance and rust preventive paint of the present invention is applied in a thickness of 2 μm or more and 50 μm or less, and the steel material chemical composition, shape or structure, or Including those having a surface on which other anticorrosion means are used in combination, any selection does not depart from the scope of the present invention. In consideration of coating workability, the thickness of the highly corrosion-resistant and anticorrosive paint of the present invention is preferably 5 to 30 μm. Furthermore, 7-20 micrometers is preferable from a viewpoint of economical efficiency and utilization processability. Although it does not prescribe the technical scope of the present invention, enumerated examples of coating objects include cast iron, carbon steel, special steel, stainless steel, corrosion-resistant steel, welded joints, etc. , Steel bars, etc., and the shapes obtained by processing these include (1) high-temperature and wet corrosive environments such as internal combustion engine exhaust systems such as automobiles and ships, boiler exhaust systems, low-temperature heat exchangers, incinerator floors, (2) Bridges, struts, interior / exterior materials for buildings, roofing materials, joinery, kitchen members, various handrails, guardrails, various hooks, roof drains, railcars, etc., (3) various storage tanks, struts, piles, Soil corrosive environments such as sheet piles, (4) Condensed corrosive environments (including corrosive environments where freezing, wetting and drying are combined) such as can containers, various containers, low-temperature heat exchangers, bathroom members, automobile structural members, (5) water storage Tank, water supply pipe, hot water supply pipe Canned containers, various containers, tableware, cooking equipment, bathtubs, pools, vanity tables and other tap water corrosive environments, (6) Various containers, tableware, cooking equipment corrosive drinking water environments, (7) Various reinforcing bar structures, Concrete corrosive environments such as struts, (8) seawater corrosive environments such as ships, bridges, piles, sheet piles, offshore structures, and the like, and other anticorrosive means that can be used in combination include plating, painting, and cathodic protection.

  Hereinafter, the present invention will be described using examples.

  The paste for coating materials was produced on the conditions shown in the column of the content of each paste of Tables 1-11. The Zn alloy particles, except for Comparative Examples 5 to 8 in Table 1, were prepared by adding Zn alloy particles produced by a gas atomizing method to toluene or xylene having a water content of 0.8% by mass or less to form a slurry. Zn jet particles having a physically crushed surface and / or a crack with a length of 0.01 μm or more or a crack with a depth of 0.01 μm or more produced on a surface by pulverizing by a method of making jet jets that collide with each other ,used. Here, in determining the average particle diameter of the Zn alloy particles and the Zn metal particles described later, a measurement method by a laser diffraction scattering method was employed. Therefore, the average particle diameter is evaluated as a sphere equivalent diameter. About the Zn alloy particle | grains of Comparative Examples 5-8 of Table 1, it manufactured by the gas atomizing method or the mist method.

  In addition, the shape of 50 to 100 Zn alloy particles extracted at random was observed with an electron emission electron gun type scanning electron microscope, and a physical crushing surface or a length of 0. It was confirmed to have a crack of 01 μm or more or a crack of 0.01 μm or more in depth. Some of the Zn alloy particles had a physically fractured surface and a crack having a length of 0.01 μm or more or a crack having a depth of 0.01 μm or more on the surface. In the table, “crushed surface, presence / absence of crack” means that crushed surface and / or cracked, and × means fractured surface and no crack.

  The number of faces of the Zn alloy particles was determined by observation with the scanning electron microscope. In this observation, only one side of each particle is seen, but the number of faces is judged on the assumption that the same shape exists continuously and symmetrically on the opposite side of the shadow. The average value was expressed by one significant digit.

In the present invention example, before the Zn alloy particles used in each paste collide with each other as a jet jet and are refined, the solid solution or the type of intermetallic compound contained in the Zn alloy particles is analyzed by powder X-ray diffraction analysis. Next, after finely pulverizing the particles, a physical crushing surface of particles that are easy to observe in the field of view by scanning electron microscope observation with an energy dispersive X-ray analyzer, or a length of 0.01 μm or more The crack surface of the crack or the crack surface with a depth of 0.01 μm or more is selected and analyzed. From the result of the composition ratio analysis of Mg and Zn and the measurement result by the above-mentioned powder X diffraction method, the solid solution on each surface The presence or absence of intermetallic compounds and the types of intermetallic compounds were identified. If the presence of a solid solution and an intermetallic compound was observed even at one of the 10 surfaces investigated, the solid solution and the intermetallic compound were judged as “present”; As for the type of intermetallic compound, the presence of one or more kinds of Zn—Mg intermetallic compounds among MgZn ₂ , Mg ₂ Zn ₁₁ , Mg ₂ Zn ₃ , MgZn, or Mg ₇ Zn ₃ by X-ray diffraction. And the atomic composition ratio of one or more of Mg and Zn among the intermetallic compounds confirmed by X-ray diffraction is a physically fractured surface by a scanning electron microscope with an energy dispersive X-ray analyzer, or Also in the analysis of the crack surface, if the component error can be confirmed within 10% even at one place, it is considered that the presence of the Zn-Mg intermetallic compound is confirmed, and it is determined as “Yes”, otherwise “No”. It was.

  In Tables 1 and 7 to 11, a mixture of Zn metal particles in addition to the Zn alloy particles was used.

  As the organic solvent, toluene, xylene, a mixture of toluene and xylene in a mass ratio of 1: 1 was used, and organic solvents were prepared by adding a dispersant at various concentrations. As the dispersant, those listed in each table were used.

  The paste for high corrosion resistance rust preventive paint prepared by the above method was prepared. In addition, paint preparation was implemented by the general method, and the binder used the inorganic binder of the commercially available alkali silicate or the alkyl silicate resin, or the commercially available four types of organic binder. The paint prepared on the steel sheet was applied by brush painting or spray painting.

  In the evaluation test, a corrosion evaluation test and a use workability evaluation were performed.

  For the corrosion test evaluation, a salt spray test (5% NaCl spray, 35 degrees) based on JIS K 5600 was performed. A test piece having a size of 150 × 70 × 3.2 mm was used as a coating test piece, and an X cut was inserted into the lower part of the test piece with a cutter. The corrosion test was evaluated based on the red rust generation time from the surface of the test piece. When red rust was generated for less than 900 hours, the corrosion resistance was evaluated as poor and indicated by x in the table. Moreover, when the red rust generation time was between 900 and less than 1400 hours, the corrosion resistance was evaluated as slightly poor and indicated by Δ in the table. Moreover, when red rust generation | occurrence | production time was between 1400 hours and less than 2000 hours, it evaluated that corrosion resistance was favorable and displayed by (circle) in the table | surface. Moreover, when the red rust generation time was 2000 hours or more, it was evaluated that the corrosion resistance was very good, and indicated by “◎” in the table.

  In addition, in the useability evaluation test, pit / blowhole resistance during welding and fume resistance during fusing were performed.

  In the pit / blowhole test, a t15w100-L500 mm steel plate coated with the above-mentioned requirements was prepared, and T-type welding was performed. The welding conditions were horizontal fillet automatic carbon dioxide welding. As a welding material, a wire SM-1Fφ 1.2 mm manufactured by Nippon Steel & Sumikin Welding Co., Ltd. was used. One pass was performed at a current of 250 A, a voltage of 30 V, a welding speed of 800 mm / min, a wire protrusion of 25 mm, and a torch angle of 45 °. The evaluation was performed based on the presence or absence of pit generation by visual observation of the surface of the weld metal after welding, and the blow hole occurrence rate of the fracture surface after breaking with a hammer and a V notch. Here, the blowhole occurrence rate is the blowhole area in the fractured surface obtained by observing the field of view of the weld metal part 10 times by 10 times and analyzing with an image analyzer from a direction substantially perpendicular to the fractured surface. Rate. The blowhole was recognized as a blowhole having a substantially circular cross section with a diameter of 0.3 mm or more, and the area ratio is taken as the blowhole occurrence rate.

  For both pits and blowholes, 50 mm on both ends of the total length of the test specimen for welding of 500 mm was excluded from the evaluation. Both the presence / absence of pit generation and the blowhole generation rate were obtained by preparing three test pieces for welding each having a total length of 500 mm.

  As an evaluation standard, in the case of weldability, when pits occurred on the surface of the weld metal after welding, it was evaluated as x. Moreover, there was no pit generation, and the blow hole generation rate was 8% or less ◎, 8 to 10% ○, 10% or more was rated as x. This is because when the pits are generated or the blowhole generation rate is 10% or more, the mechanical soundness as a welded portion cannot be guaranteed.

  Also, the fume resistance is downward automatic carbon dioxide welding, wire SM-1F φ1.2 mm, manufactured by Nippon Steel & Sumikin Welding Industries, current 250A, voltage 29V, welding speed 40 cm / min, welding time 30 sec (fume suction time +30 sec, total 60 sec) Welding was carried out, fume was captured by the method described in JIS Z 3930, and the total amount of fume captured was evaluated as the amount of generated fume. This method determines the amount of fumes generated by welding, but it can evaluate not only welding but also the small amount of fumes generated at the time of fusing, that is, the resistance to fumes. As the fusing property, the evaluation of fume resistance was ◎ for a fume generation amount of 400 mg or less, ◯ for 400 to 450 mg, and x for 450 mg or more. This is because the working environment is clearly deteriorated at a fume generation amount of 450 mg or more, and a local exhaust device is required.

  In the examples shown in Tables 3, 4, 6, 8, 9, and 11, the case of containing Al and Si as Zn alloy particles was shown. Except for containing Al and Si, the same production method as in the examples not containing these is used.

In the examples shown in Tables 4 to 6 and 9 to ₁₁ , the presence or absence of the Mg solid solution layer and the Zn—Mg intermetallic compound layer on the surface of the Zn alloy particles was evaluated, and MgZn ₂ , Mg ₂ Zn ₁₁ , Mg ₂ Zn ₃ The presence or absence of any one of MgZn or Mg ₇ Zn ₃ was evaluated. In the example having the Mg solid solution layer and the Zn—Mg intermetallic compound layer, the effect of improving the corrosion resistance was observed. In the examples shown in the other tables, the presence or absence of the Mg solid solution layer and the intermetallic compound layer was not evaluated.

  In the examples shown in Tables 5, 6, 10, and 11, the number of faces of the Zn alloy particles was evaluated. There was a tendency to improve performance as the number of faces increased. In the examples shown in the other tables, the number of faces of the Zn alloy particles was not evaluated.

  From Tables 2 to 6, it can be seen that the Zn alloy particles exhibit excellent corrosion resistance, rust resistance, blowhole resistance, and fume resistance. Further, in Tables 7 to 11, when the ratio of (Zn alloy particle amount%) :( Zn metal particle amount%) is 1: x in terms of mass% in terms of a dry coating film prepared with Zn alloy particles and Zn metal particles When x is 300.0 or less, it can be seen that excellent corrosion resistance and rust resistance are exhibited.

  The total ratio of Zn alloy particles and Zn metal particles in the paste was initially adjusted to 60 to 95% by mass%, but in order to produce a paint using these pastes, Zn was used. Since the alloy particles or the mixed particles of Zn alloy particles and Zn metal particles were sequentially dispensed every time the paint was prepared, the Zn alloy particles in the paste or the mixed particles of Zn alloy particles and Zn metal particles in the paste were finally obtained. The percentage decreased from over 0% to 30%. However, even if the ratio of Zn alloy particles or Zn alloy particles and Zn metal particles in the paste changes each time the Zn alloy particles or Zn alloy particles and Zn metal particles are dispensed, It was not found that the ability of imparting corrosion resistance and rust resistance to the steel material of the coating material produced by using the coating material fluctuated, and the influence could be ignored.

  Table 1 shows a comparative example. In Comparative Examples 1 to 4, the Mg concentration of the Zn alloy particles deviated from the scope of the present invention. In Comparative Examples 5 to 8, the Zn alloy particles had no cracks and cracks. In Comparative Examples 9 to 12, the average particle diameter of the Zn alloy particles was Out of the scope of the present invention, in Comparative Examples 13 to 16, the content of the dispersant was out of the scope of the present invention, and the quality of the coating film did not reach the level of the present invention. In Comparative Example 21, the ratio of the Zn metal particles to the Zn alloy particles is out of the range of the present invention. In Comparative Examples 22 to 24, the Mg content in all the metal particles is out of the range of the present invention. The level was not reached. In Comparative Examples 17 to 20, the metal particles in the dried coating film were out of the scope of the present invention. In Comparative Examples 25 to 28, the coating film thickness was out of the scope of the present invention, and the quality of the coating film did not reach the level of the present invention. .

Claims (12)

  The dispersant contains 0.01% to 10% of one or both of a saturated fatty acid amide and an unsaturated fatty acid amide by mass% with respect to the organic solvent. 200 μm Zn alloy particles are dispersed as a pigment, and the Zn alloy particles contain Mg: 0.01 to 30% by mass, the balance being Zn and inevitable impurities, and the surface of the Zn alloy particles It has a physically crushed surface and / or a crack with a length of 0.01 μm or more or a crack with a depth of 0.01 μm or more, and is used for a highly corrosion-resistant rust-preventive paint with excellent workability paste.   The paste for high corrosion resistance and rust preventive paint excellent in utilization processability according to claim 1, wherein the organic solvent is toluene and / or xylene.   Furthermore, the said Zn alloy particle | grain contains the 1 type (s) or 2 types of Al: 0.01-30% and Si: 0.01-3% by the mass%, The Claim 1 or 2 characterized by the above-mentioned. High corrosion resistance paste for rust prevention paint.   The paste for high corrosion resistance rust preventive paint according to any one of claims 1 to 3, wherein the Zn alloy particles have a Mg solid solution phase and a Zn-Mg intermetallic compound on a physically crushed surface. 5. The high corrosion resistance according to claim 4, wherein the Zn—Mg intermetallic compound includes at least one of MgZn ₂ , Mg ₂ Zn ₁₁ , Mg ₂ Zn ₃ , MgZn, and Mg ₇ Zn _3. Anti-rust paint paste.   The paste for high corrosion resistance rust preventive paint according to any one of claims 1 to 5, wherein the Zn alloy particles are non-spherical polyhedron and have two or more faces.   A high corrosion resistance rust preventive paint using the paste for high corrosion resistance rust preventive paint according to any one of claims 1 to 6, wherein the Zn alloy particles are 30% or more in terms of dry coating film mass% A highly corrosion-resistant rust preventive paint characterized by containing 85% or less.   In addition to the Zn alloy particles, a high corrosion resistance rust preventive paint in which Zn metal particles composed of Zn having an average particle diameter of 0.05 to 50 μm and inevitable impurities are dispersed, and is expressed in mass% (the amount of the Zn alloy particles ): (Zn metal particle amount) The value of the ratio is 1 / x, and x is 300.0 or less.   The content of Mg is 0.01 to less than 30% when the total of the mixed particles of the Zn alloy particles and the Zn metal particles is 100% in terms of mass%. High corrosion resistance rust-proof paint.   The high corrosion resistance rust preventive paint according to any one of claims 7 to 9, wherein the binder of the high corrosion resistance rust preventive paint is an inorganic binder or an organic binder.   A high corrosion resistance steel material having a coating thickness of 2 to 50 µm, wherein the steel material surface is coated with the high corrosion resistance rust preventive paint according to any one of claims 7 to 10.   A steel structure comprising the highly corrosion-resistant steel material according to claim 11 in part or in whole.