JPH0550444B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a rust-preventive pigment to be incorporated into coating compositions and the like. (Prior art and its problems) Metals generally corrode in the presence of water, oxygen, and electrolyte ions. The reason for this is believed to be that a local battery is formed on the metal surface and an electrochemical reaction progresses. In order to prevent this corrosion of metals, a stable extremely thin film, a so-called passive film, is formed on the metal surface. A typical method is to contact a metal material with chromate ions. This chromate ion has a so-called oxidizer function, in which chromate ion (CrO ₄ ^2- ) reacts with steel (Fe) to generate stable γ-Fe ₂ O ₃ on the steel surface. and lower chromium oxides (e.g.,
There are two functions by which Cr ₂ O ₃ ) adheres to the steel surface, the so-called deposition function. These two functions form a physical barrier film on the steel surface, which exhibits an extremely excellent rust prevention effect. However, hexavalent chromium, which has a high rust-preventing ability, is highly toxic, and its use is severely restricted in Japan by various laws and regulations. Therefore, research into non-polluting or low-pollution rust preventive agents is being actively conducted. For example, phosphate-based substances, especially zinc phosphate,
Silica phosphate, condensed aluminum phosphate, etc. have attracted attention, and some have been put into practical use. However, a phosphate-based substance is a substance produced by a reaction with a metal material and has only the above-mentioned deposition function to protect the metal material, and does not have an oxidizer function to oxidize the surface of the metal material. Therefore, these have inferior rust prevention ability compared to chromate ions. (Progress of the invention) The present inventors have already proposed that the oxidizer function, which is lacking in phosphate-based substances, can be compensated for by soluble vanadium ions (Japanese Patent Application No. 1983-
No. 204794). The present inventors investigated rust-preventing pigments in order to further develop this technology. JP-A-61-115965 and JP-A No. 61-162558 disclose water glass-based inorganic paints containing silicon polyphosphate and vanadate; in this case, silicon polyphosphate is used as a hardening agent for water glass. It does not work as an anti-rust pigment. (Contents of the invention) That is, the present invention comprises (a) a phosphorus compound that releases phosphate ions in an environment where water is present, and (a) a phosphorus compound that generates vanadate ions in an environment where water or both water and oxygen exist. A rust-preventive pigment obtained by firing and pulverizing a mixture containing b) a vanadium compound and (c) a network-modifying ion source, wherein the network-modifying ion source is manganese oxide (MnOx: 1.5<x≦2.0).
Alternatively, the present invention provides a rust-preventing pigment characterized by being a combination of manganese oxide and another network-modifying ion source. The present invention comprises (a) a phosphorus compound that releases phosphate ions in the presence of water; (b) a vanadium compound that produces vanadate ions in the presence of water or both water and oxygen; d) Anticorrosion pigments obtained by firing and grinding mixtures containing glassy substances are also provided. The present invention also provides (a) a phosphorus compound that releases phosphate ions in an environment where water is present, and (b) a vanadium compound that produces vanadate ions in an environment where water or both water and oxygen are present. A rust-preventing pigment is provided by firing and pulverizing a mixture containing (c) a network-modified ion source and (d) a glassy substance. Furthermore, the present invention uses (a) a phosphorus compound that releases phosphate ions in the presence of water, and (b) a vanadium compound that produces vanadate ions in the presence of water or both water and oxygen. A rust-preventive pigment obtained by mixing is provided. Furthermore, the present invention provides (a) a phosphorus compound that releases phosphate ions in the presence of water, and (b) a vanadium compound that produces vanadate ions in the presence of water or both water and oxygen. , and (c)
A rust-preventive pigment obtained by mixing a network-modified ion source is provided. The anticorrosion pigment of the present invention can be obtained by mixing or by firing/pulverizing, but in the case of the mixing method, the phosphate ion source is a phosphorus compound that releases phosphate ions in an aqueous solution, and the vanadate ion source is also a phosphorus compound that releases phosphate ions in an aqueous solution. It is a compound that produces vanadate ions in existing aqueous solutions. On the other hand, in the case of firing and pulverizing, it is sufficient that the fired reaction product meets the requirements for a steam rust-preventing pigment.
The phosphate ion source is a phosphorus compound that releases P ₂ O ₅ when heated, and the vanadate ion may be a vanadium compound. The antirust pigment of the present invention is obtained by firing and pulverizing a mixture containing (a) a phosphorus compound and (b) a vanadium compound. In addition to the above two types of compounds, (c) a network-modifying ion source and/or (d) a glassy substance may be mixed during this firing. Furthermore, the anticorrosive pigment of the present invention may be mixed with a phosphorus compound that releases phosphate ions and a vanadium compound that generates vanadate ions in an aqueous solution. Alternatively, the reaction may be carried out together with (c) the network-modified ion source under pressure. The present invention will be described below. The present invention includes a mixing mode and a baking mode. First, the baking mode will be explained. The phosphorus compound (a) used in the present invention can be heated to
Compounds that produce P ₂ O ₅ components, such as orthophosphoric acid: condensed phosphoric acid; orthophosphates or condensed phosphates of various metals; phosphorus pentoxide; phosphate minerals; commercially available complex phosphate pigments; or a mixture thereof. Orthophosphoric acid (salt) herein includes its monohydrogen salt (HPO ₄ ^2- salt) and dihydrogen salt (H ₂ PO ₄ ^- salt). Furthermore, the range of condensed phosphates also includes its hydrogen salts.
Further, the term condensed phosphoric acid (salt) includes metaphosphoric acid (salt), and of course includes ordinary polyphosphoric acid (salt) as well as polymetaphosphoric acid (salt). Specific examples of the phosphorus compound (a) include phosphate minerals, such as monetite, torfylite, witrockite, xenotime, stercolite, strubite, orchidite, etc.; commercially available composite phosphate pigments, such as polyphosphoric acid silica, etc. condensed phosphoric acids, such as pyrophosphoric acid, metaphosphoric acid; condensed phosphates, such as metaphosphate, tetrametaphosphate, hexametaphosphate, pyrophosphate, acid pyrophosphate, tripolyphosphate, etc.; or mixtures thereof; Can be mentioned. The metal species that form the phosphate are not particularly limited, and include alkali metals, alkaline earth metals (e.g., magnesium, calcium), and metal species of other typical elements (e.g., aluminum, tin, etc.)
and transition metals (e.g. manganese, cobalt,
iron, nickel), etc. Examples of preferred metal species include alkali metals. The fired product when an alkali metal phosphate is used tends to dissolve in water, and if it is directly blended into a paint or the like, it may actually deteriorate the coating performance.
However, when using an alkali metal phosphate, it may be used if its solubility in water can be controlled at the time of producing the rust preventive pigment or at any other time. Such control includes various aspects such as the use of a matrix material or coating to prevent solubility in water. In particular, when a glassy substance is used as the matrix material, it exhibits excellent rust prevention properties. In addition to the above-mentioned phosphorus compounds, zinc phosphate-treated sludge (main component: zinc iron phosphate) of iron materials can also be used after removing impurities (coarse particles, electrolytes such as chloride ions) by sieving, washing with water, etc. Good too. The vanadium compound (b) used in the present invention is a compound having a vanadium valence of 0, 2, 3, 4, or 5, or two or more types, and includes oxides, hydroxides, and various metals of vanadium. Examples include oxidized acid salts, vanadyl compounds, halogen compounds, sulfates, and metal powders. These decompose when heated to produce P ₂ O ₅
It acts on the ingredients, reacts with oxygen in the atmosphere during firing, and becomes higher grade. For example, a metal powder or a divalent compound is finally changed into a trivalent, tetravalent, or pentavalent compound. Preferably, it contains a pentavalent vanadium compound as one component. Zero-valent metal powder, such as vanadium metal powder, can be used for the reasons mentioned above, but it is not preferred in practice because it has problems such as insufficient oxidation reaction. Pentavalent vanadium compounds generate vanadate ions, which react with phosphate ions under heat to easily form heteropolymers. Specific examples of the vanadium compound (b) include vanadium () compounds, such as vanadium oxide (), vanadium hydroxide (); vanadium () compounds, such as vanadium oxide ();
(V ₂ O ₃ ); Vanadium () compounds, such as vanadium oxide () (V ₂ O ₄ ), vanadyl halides (VOX ₂ ), etc.; Vanadium () compounds, such as vanadium oxide () (V ₂ O ₅ ); vanadate,
Examples include various metal orthovanadates, metavanadates, or pyrovanadates, vanadyl halides (VOX ₃ ), etc.; or mixtures thereof. The metal species of vanadate include the same metal species as those shown for phosphate. This may be made by firing vanadium oxide and various metal oxides, hydroxides, carbonates, etc. at 600°C or higher. In this case as well, alkali metals are not very preferred due to their solubility, but their use is acceptable if the solubility is controlled by appropriate treatment as explained for phosphates. The same applies to halides and sulfates. Alkali metals may also be used when a matrix material (eg, a glassy substance) is used. Network modifying ion refers to a compound containing metal ion species added to modify the network structure formed by the fired product of a phosphorus compound and a vanadium compound, and specifically includes various metal ion species, such as alkali metals. ions, alkaline earth metal ions, metal ions of other typical elements, and transition metal ions. Examples of preferred network-modifying ions include those described for metal salts of phosphoric acid. Examples of the network-modifying ion source (c) include oxides, hydroxides, carbonates, sulfates, organic acid salts, silicates, borates, sulfates, and chlorides of the above metal species, and most preferably They are oxides, hydroxides, and carbonates. When alkali metals are used among the metal ion species mentioned above, or when sulfates or chlorides are used as the ion source, these compounds tend to dissolve too much in water, and when used in paints, etc. On the contrary, it may worsen the coating performance. Even in such a case, the solubility in water may be suppressed by taking appropriate measures as described above, such as using a matrix material (eg, a glassy substance) or coating the particles. Among the network-modified ion sources (c), manganese oxide (MnOx: 1.5<x≦2.0) exhibits a special effect. Manganese oxide has an oxidizing effect and suppresses the decrease in oxidizing power due to the lowering of vanadate ions. The glassy substance (d) used in the present invention includes not only glass forming a matrix such as silicate glass and borate glass, but also various metal elements,
For example, it means one containing network-modifying ions. Relevant glassy substances include silica (quartz) glass; silicate glasses, such as soda-lime silicate glass ( _Na2O -CaO- _SiO2 system), lead-silicate glass ( _Na2O- PbO-SiO ₂ system), aluminosilicate glass (Al ₂ O ₃ -CaO-SiO ₂ system), borosilicate glass (Na ₂ O-B ₂ O ₃ -SiO ₂ system); lead-borate glass (PbO −B ₂ O ₃ series, commonly known as solder glass); alumino-borophosphate glass (B ₂ O ₃ −
Al ₂ O ₃ −P ₂ O ₅ system); alumino-borate glass (BaO−Al ₂ O ₃ −B ₂ O ₃ system); alumino-phosphate glass (P ₂ O ₅ −Al ₂ O ₃ − ZnO-based); etc. Examples of preferred glassy materials include soda-lime-based (C-glass), such as Nippon Glass Fiber glass flakes (CCF-150); aluminosilicate glasses (E-glass), such as Nippon Glass Fiber glass flakes (CEF-150); ); borosilicate glasses, such as Pyrex manufactured by Corning. 1g of fine powder of glassy substance in 100ml of water
It is preferable that the conductivity of the liquid when dispersed/suspended in the liquid is 500 μS/cm or less. If it exceeds 500μS/cm, the rust prevention ability will decrease. Phosphorus compound (a) and vanadium compound (b), and if necessary a network modification ion source (c), glassy substance (d)
The anticorrosive pigment of the present invention can be obtained by firing the mixture, cooling it, and then pulverizing it. If necessary, other inorganic substances such as matrix materials other than glassy substances may be mixed into the mixture. Firing is carried out at a temperature higher than the melting temperature (T ₁ ) of the fired product of the mixture consisting of the above components, specifically at 600°C or higher,
Preferably 1000℃ or higher, more preferably above
It is carried out at a temperature equal to or higher than the higher of T ₁ and the melting temperature of the glassy substance (d). Below this temperature, the reaction is insufficient and the components simply remain mixed. The blending amounts of the phosphorus compound (a) and the vanadium compound (b) are 0.3 to 100 in terms of the molar ratio of P ₂ O ₅ /V ₂ O ₅ ,
Preferably it is 1-10. The added amount of the network-modifying ion source (c) is such that the amount of all metal cations (M) in the anticorrosion pigment of the present invention is determined by adjusting the amount of all metal cations (M) in the oxide form (MO, M ₂
O ₃ , M ₃ O ₄ , MO ₂ or M ₂ O),
It is added in an amount not more than 3 times the sum of the moles of V ₂ O ₅ and P ₂ O ₅ , preferably 0 to 2.0 times. The oxide form of M is M ₂ O when M is a monovalent metal, and M 2 O when M is a monovalent metal.
MO if it is a valent metal, M ₂ if M is a trivalent metal
O ₃ Furthermore, M is a mixed valence of divalent and trivalent (e.g.
Mn tends to be divalent or trivalent depending on the firing conditions)
If M is tetravalent, it will be represented by M ₃ O ₄ , and if M is tetravalent, it will be represented by MO ₂ . In addition, when manganese oxide is added to avoid lowering of vanadate ion, 0.1 mol or more of manganese oxide is added per 1 mol in terms of V ₂ O ₅ . If the amount is 0.1 mol or less, lowering of vanadium cannot be prevented. in this case,
The firing temperature is preferably 700 to 1400°C. At temperatures below 700℃, no oxygen is generated from manganese oxide,
If the temperature exceeds 1400°C, lowering of vanadium cannot be suppressed. Glassy substance (d) is a phosphorus compound
(a), vanadium compound (b) and network modified ion source
It is blended in an amount of 5 to 500 times, preferably 10 to 100 times, the total weight of (c). If it exceeds the above range, sufficient rust prevention cannot be obtained. The concept of rust prevention in this specification is broadly understood and is understood to include not only the prevention of general rust, but also the prevention of blisters, etc. of the paint film. The firing time is usually 0.2 to 10 hours, but even if it exceeds 10 hours, the physical properties of the anticorrosion pigment will not be affected much.The firing efficiency will be improved if each component to be fired is preferably mixed in particles of 100 μm or less. It gets expensive. Therefore, each component may be pulverized in advance and then mixed, or may be mixed as coarse particles and then pulverized. This operation may be carried out in a wet or slurry state with water or other medium. The anticorrosive pigment of the present invention is cooled and then pulverized and classified by conventional methods to obtain particles having a particle size of 10 μm or less, preferably 2 μm or less. Cooling from the molten state may be either slow cooling or rapid cooling as long as phase separation does not occur. If a light colored pigment is required as the fired pigment, each component (a to d) may be light colored, or each component may be selected so that the fired pigment becomes light colored. For example, the phosphorus compound has the formula: yM ₂ O.P ₂ O ₅ or yMO.P ₂ O ₅ [wherein 1≦y≦3, M represents a metal atom, preferably calcium or magnesium. ] and as a vanadium compound, the formula: xM ₂ O.V ₂ O ₅ or xMO.V ₂ O ₅ [wherein 1/2≦x≦3, preferably 1≦x≦
2], a pale white pigment is likely to be obtained when the P/V molar ratio is 5 to 30. The above anti-rust pigment can be obtained by firing, but if each component, especially the phosphorus compound (a) and the vanadium compound (b), are selected, it can be used as a simple mixture or a mixture under pressure. Effective as a rust-preventing pigment. Furthermore, in the case of the phosphorus compound (a), the vanadium compound (b), and the network-modified ion source (c), it is more useful to mix them under pressure. When used as a mixture, the phosphorus compound can be heated to
Among the phosphorus compounds that generate P ₂ O ₅ , it releases phosphate ions in aqueous solution. Phosphate ions rarely exist alone in an aqueous solution, and exist in various forms, for example, as condensates, but such cases are also included in the term "things that release phosphate ions" in the present invention. It is understood that
Examples of such compounds include orthophosphates, condensed phosphates, heterocondensates of phosphoric acid (for example, phosphomolybdates), and the like among the above-mentioned phosphorus compounds. These phosphorus compounds are preferably PH in aqueous solution.
5 to 9, conductivity (κ) is 30 μS/cm to 3 mS/cm, more preferably κ is 100 μS/cm to 2 mS/cm. The conductivity was measured by dispersing and suspending 1 g of fine powder in 100 ml of water and using a commercially available conductivity meter. Phosphorus compounds exhibit the strongest rust prevention properties within this range, but even compounds outside this range can exhibit excellent rust prevention properties if they are brought within this range through appropriate treatment. Examples of such materials include zinc phosphate treated sludge. As the phosphorus compound, phosphate treatment sludge may be used. Phosphating sludge refers to the treatment of iron, steel, etc. using a known zinc phosphate treatment agent.
Refers to the precipitation of phosphates that is produced as a by-product when galvanized steel, etc. is subjected to chemical conversion treatment. The vanadium compound used in this embodiment is one that generates vanadate ions in an aqueous solution among the above-mentioned ones, and includes vanadyl compounds, vanadate,
A fired condensate of vanadate or a heterocondensate of vanadate is suitable. In this case, the aqueous solution may or may not contain oxygen. The vanadate ion generated in an aqueous solution changes the pH of the solution.
It changes into various forms depending on concentration and other conditions.
Most of these become condensed vanadate ions or their hydrogen-containing ions. In this specification, vanadate ions generated in an aqueous solution are understood to include such condensates. The above vanadium compounds are usually vanadium oxide () and metal oxides, metal hydroxides, metal carbonates,
It is obtained by firing reaction with a metal nitrate or a metal organic acid salt. Alternatively, the reaction reagent may be obtained by reacting the above reaction reagent in a liquid phase. In addition to the vanadium compounds mentioned above, solid-phase reaction of the same reaction reagents, that is, those obtained by heterogeneous reaction at a temperature below the melting point, may be used. The vanadium compound preferably has a pH of 5 in aqueous solution.
~9, conductivity (κ) 30 μS/cm ~ 2 mS/cm.
Vanadium compounds exhibit the strongest rust prevention properties within this range. Even if it falls outside this range, it can be made to fall within this range by appropriate processing. The above phosphorus compounds and vanadium compounds contain small amounts of other components such as titanium, zirconium,
It may also contain silicate ions and the like. Some commercially available reagents contain these, and these may be used. The anticorrosive pigment of the present invention can be obtained by mixing the above-mentioned phosphorus compound and vanadium compound. The blending amounts of the phosphorus compound and the vanadium compound may be changed as necessary. In general, it is better to use a smaller amount of a compound that dissolves in a large amount, and to increase the amount of a compound that dissolves in a small amount. In the present invention, the rust prevention property is greatly exhibited when the concentration of dissolved phosphate ions is higher than the concentration of dissolved vanadate ions, so the combination of phosphorus compound and vanadium compound is determined by the conductivity κp of the phosphorus compound, the amount (weight) is Cp, conductivity of vanadium compound is κv,
A combination in which κp > κv or a combination in which Cp > Cv is preferred, where the blending amount is Cv. More preferably, the combination satisfies κp>κv and Cp>Cv. An example of the most preferable combination is n of a vanadium compound to dibasic magnesium phosphate.
When written in the form of (metal oxide)・(V ₂ O ₅ ),
1.8<n< for nMgO・V ₂ O ₅ or nCaO・V ₂ O ₅
2.2; 1<n<3.5 for ZnO・V ₂ O ₅ ; nCoO・V ₂ O ₅
or 1<n<3.5 for nCo ₃ O ₄ V ₂ O ₅ , CaHPO ₄
For nCaO・V ₂ O ₅ , 2≦n<2.2; nMn ₃
O ₄・V ₂ O ₅ , nMn ₂ O ₃・V ₂ O ₅ or nMnO・V ₂ O ₅
Then, 1<n<3.5. The above mixing mode also shows that when the phosphorus compound (a) that releases phosphate ions in an aqueous solution, the vanadium compound (b) that generates vanadate ions in an aqueous solution, and the network-modified ion source (c) are mixed, it becomes a simple mixture. can be obtained without requiring special processing conditions such as high temperatures. The phosphorus compound (a) used in this embodiment includes dibasic calcium phosphate, tribasic calcium phosphate, dibasic magnesium phosphate, and tribasic magnesium phosphate. A preferred vanadium compound (b) is vanadium oxide (). Examples of suitable network-modified ion sources (c) include calcium oxide, calcium hydroxide, magnesium oxide or magnesium hydroxide. In this case, mixing is usually carried out using a hammer mill, mortar, or ordinary attrition type grinder. Such mixing, ie, reaction under impact or shear force, is sometimes referred to as mechanochemical reaction. The mechanochemical reactant may optionally be heated at a temperature of 100-300°C, preferably 150-250°C. The rust-preventing pigment preferably has a particle size that is normally used as a pigment for paints, for example, 10 μm or less, preferably 2 μm or less. Therefore, treatments such as pulverization are performed as necessary. The anticorrosive pigment of the present invention may be subjected to treatment to improve dispersion stability, if necessary. The dispersion stability treatment is carried out by a method such as adsorption treatment of a dispersant on the surface of the pigment. The antirust pigment of the present invention is used by being blended into antirust waxes, paints, linings, and the like. The paint may be one commonly used, and the antirust pigment of the present invention may be added to a commercially available paint liquid. Also,
In the usual manner, it may be prepared into a coating liquid together with extender pigments, coloring pigments, vehicles, solvents, and various additives. The vehicle may be any commonly used vehicle, and the solvent may be any solvent as long as it is compatible with the resin. Examples of resin vehicles include epoxy, tar-modified epoxy, urethane-modified epoxy, melamine, melamine alkyd, alkyd, oil-modified alkyd, phenol, epoxy-modified phenol, chlorinated resin, polyester, silicone resin, acrylic resin, polyurethane resin,
Examples include petroleum resins, polyethylene, polypropylene, fluorine resins, and oils. The solvent is hydrocarbons,
Examples include ketones, esters, alcohols, water, and the like. Other additives commonly used in paints (plasticizers, surfactants, desiccants, curing agents, dispersants,
Thickeners, anti-sag agents, etc.) may be added. The paint is applied in a conventional manner and, depending on the properties of the resin vehicle, is dried at room temperature or cured by baking. The cured coating film contains the antirust pigment of the present invention and has an oxygen permeability coefficient (P) of 1×10 ^-16 to 1×
10 ^-7 (ml (STP)・cm/cm ²・s・cmHg), higher rust prevention properties are exhibited. The antirust pigment composition of the present invention has a total solid content of 100
0.1 to 50 parts is preferred. Examples of metal materials to which the present invention is applied include steel, high-strength steel, high-tensile steel, plated steel plates, alloys such as stainless steel, cast iron, aluminum, and alloys thereof. Corrosion conditions under which the anticorrosion pigment of the present invention acts effectively are generally conditions in which water or oxygen is present, or conditions in which paint film blisters are likely to occur, and other conditions that are considered to promote corrosion. Ions (eg, chloride ions), etc. may be present. Paint film blistering is a form of paint film deterioration that occurs under various conditions, but especially under temperature gradient conditions (when there is a difference in temperature between the front and back surfaces of the paint film) or cathodic protection conditions (such as when Although this method prevents oxidative corrosion by electrically reducing the oxidative corrosion of The anticorrosion pigment of the present invention also effectively suppresses this paint film deterioration (included in corrosion in a broad sense). The optimum corrosion conditions for the present invention are within the pH range of 2-9. The blister suppression effect is strong at pH 2 to 5, and the general corrosion suppression effect is strong at PH 5 to 9. If it exceeds this range, the antirust effect will decrease. (Operations and effects of the invention) When a coating film containing the antirust pigment of the invention is applied,
Water and oxygen permeate into the coating film, and vanadate ions and phosphate ions from the rust-preventing pigment in the coating film are appropriately dissolved. Vanadate ions supplement the oxidizer function that is lacking in the aforementioned phosphate ions. This ionic species constitutes an in-solution redox couple under corrosive conditions in the presence of water and oxygen, exhibits a noble redox potential, and performs the oxidizer function described above. On the other hand, phosphate ions form a poorly soluble precipitated film under corrosive conditions and have a deposition function. As described above, the rust-preventive pigment of the present invention has a rust-preventive function caused by both phosphate ions and soluble vanadium ions, and exhibits a rust-preventive ability equal to or greater than that of chromate ions. The present invention provides an excellent antirust pigment for metal materials that is non-polluting and low-pollution. Corrosion suppressed by the present invention includes corrosion weight loss, corrosion cracking, hydrogen embrittlement, thread rust, pitting corrosion, end face corrosion, corrosion at processed parts such as bending, and coating blisters. (Example) The present invention will be explained in more detail with reference to Examples. Examples 1 to 20 and Comparative Examples 1 and 2 The phosphorus compound (a) and vanadium compound (b) shown in Table-1 were taken at the molar ratio shown in Table-1, and mixed with a pestle for 30 minutes. It was placed in a crucible and fired in an electric furnace at the heating temperature and time shown in Table 1. The melt in the crucible was then cooled at a cooling rate of 100°C/min. The cooling rate was calculated from the formula (furnace temperature - temperature of the cooled fired product)/(time required for cooling). During cooling, a cold copper plate was pressed onto the fired product in order to adjust the cooling rate, etc. The cooled calcined product is pulverized and classified by a conventional method, and the
It was made into a fine powder of less than m. Note that some of the vanadium compounds were created by firing at 1200°C with the compositions shown in the table. 10g/dispersion of the obtained fine powder (3%
JIS G 3141
SPCC (SB) polished steel plates were immersed, and the corrosion loss was measured after 30 days and compared with the corrosion loss of the same amount of strontium chromate. ○ indicates superiority to strontium chromate, Δ indicates equivalent, and × indicates inferior. This example also shows an example regarding blister suppression. Blisters are used under conditions where there is a difference in temperature between the front and back sides of a painted steel plate (temperature gradient conditions) or cathodic protection (forced polarization of the potential of the metal in a less noble direction so that the metal such as steel exhibits a reduction reaction). ), the experiment was conducted under these conditions. Preparation of Paint A paint was prepared by mixing the following formulation in a sand mill. Ingredient parts by weight Coal tar pitch varnish 30 Polyol resin varnish 12 Extender pigment 20 Rust preventive pigment of the present invention 2 Anti-sagging agent 0.5 Methyl isobutyl ketone 5 Xylol 20.5 Reaction product of toluidine isocyanate and polyol 10 (Coronate 55 manufactured by Nippon Polyurethane Co., Ltd.) Obtained Dull steel plate (JIS G 3141
SPCC SD) with air spray to dry film thickness 200 μm
It was painted and dried for 10 days at room temperature. A blister test of the obtained coated steel plate was conducted as follows. Blister test under temperature gradient: Immersed in water under a temperature gradient of 40°C on the painted side/20°C on the back side.
Blisters after being left for 14 days were visually evaluated. ◎− Much better than the comparative sample. ○-Good. △ - Same level as the comparison sample. × - Inferior to comparative sample. The comparative sample in this case is shown in Comparative Example 1, in which only an extender pigment is used and no rust-preventing pigment is used. Peelability under galvanic corrosion: Zinc metal wires were connected to a painted steel plate, left in 3% saline solution for one month (30°C), and evaluated by the creep width (l/mm) from the scratch. 0<l≦2 ◎ 2<l≦5 ○ 5<l≦8 △ 8<l≦12 × 12<l XX The results are shown in Table-1.

【table】

[Table] Examples 21 to 27 and Comparative Example 3 Using the anticorrosive pigment of Example 5, salt spray resistance was tested depending on the amount added. The anticorrosive pigment, extender pigment, and coloring pigment of the present invention were added to a thermosetting resin epoxy polyurethane resin in the compounding ratio shown in Table 2 to give a total of 100 parts by weight to obtain a paint. This paint was applied to a JIS G 3141 SPCC-SD (dull steel plate) to a thickness of 20 μm and baked at 190° C. for 1 minute. A salt spray (JIS Z 2371) test was conducted on the obtained coated board to determine peelability and blistering. Furthermore, as a room temperature curing resin, an epoxy resin paint (Kopon Mastic Primer manufactured by Nippon Paint Co., Ltd.) is used, and as an example of a water-based resin, Power Top U-30 commercially available from Nippon Paint Co., Ltd. (an example using an electrodeposition paint) is used. was also carried out. The results are shown in Examples 26 and 27, respectively. As the rust-preventive pigment of the present invention, 5 parts by weight of the above Example 13, 15 parts by weight of extender pigment and color pigment,
A vehicle of Coponmastic Primer was combined to make 80 parts by weight, and the same steel plate as above was spray-painted and kept at room temperature for 10 days to harden. The dry film thickness was 50 μm. In addition, 2 parts by weight of the rust-preventing pigment of Example 14 above was added to 100 parts by weight of the solid content in the paint, and added to Power Top U-30 to obtain a paint. This was electrodeposited on the above steel plate at 150V for 3 minutes and baked at 170°C for 30 minutes. The film thickness was 25 μm. Peelability evaluation was performed by making a scratch that reached the substrate with a knife and measuring the peeling width on one side from the cut part.
Evaluation was made on a four-level scale: ◎, excellent, △, equivalent, and inferior ×. Blistering property evaluation is performed by placing a scratch-free painted steel plate in a salt spray tester (35℃ x 500h).
Evaluation was made on a three-level scale: ◯ for almost no blister, △ for a small amount of blister, and × for a large amount of blister.

[Table] Examples 28 to 44 The phosphorus compound (a), the vanadium compound (b), and the network-modified ion source (c) shown in Table-3 were taken at the molar ratio shown in Table-3, and the mixture was prepared as in Example 1. A similar experiment was conducted. The results are shown in Table-3.

【table】

[Table] Examples 45 to 51 and Comparative Example 4 Using the anticorrosive pigment of Example 31, salt spray resistance depending on the amount added of Example 21 to
27 and Comparative Example 3. Display the results -
4.

[Table] Examples 52 to 63 and Comparative Examples 5 and 6 Experiments regarding blister suppression were conducted in the same manner as in Example 1. However, a rust preventive pigment was prepared in the same manner as in Example 28 under the conditions shown in Table 5.

[Table] Examples 64 to 73 Phosphorus compounds (a), vanadium compounds (b), and glassy substances (c) shown in Table-6, and if necessary, network-modified ion sources (d) shown in Table-6. It was prepared in the same manner as in Example 1, with the molar ratios being the same, and a corrosion test was conducted. The results are shown in Table-6. The heating temperature was 1200°C for 2 hours in all cases.

[Table] Examples 74 to 80 and Comparative Example 7 Examples 21 to 27 about salt spray resistance depending on the amount added using the antirust pigment of Example 73
And tested in the same manner as Comparative Example 3. Table 7 of the results
Shown below.

[Table] Examples 81 to 84 and Comparative Examples 8 and 9 An experiment regarding blister suppression was conducted in the same manner as in Example 1. The results are shown in Table-8.

【table】

[Table] Examples 85 to 119 In this example, the rust-preventing ability of the anti-rust pigment of the present invention was compared with that of chromate ion. Table in 3% saline-
Adding 1% by weight of the rust-preventing pigment shown in 9.
If the corrosion loss of cold-rolled plate (JIS S 3141 SD) at 25℃ is smaller than when chromate ions are added to 3% saline solution, mark it as ○, if it is approximately the same, mark it as △, if it is larger, mark as ×. It is shown in Table 9. Chromate ions were added in the form of sodium chromate, and the amount added was adjusted to match the molar concentration of phosphate ions and vanadate ions eluted from the antirust pigment. The corrosion weight loss was calculated by the following operation. The weight of a cold rolled steel plate of 70 x 150 mm is added to the test solution.
After soaking the ag for 20 days, deposits such as rust were removed with a sponge, etc., and then dried and its weight was measured (weight bg). (Corrosion loss) = a-b/210 (g/cm ² ) Furthermore, add phosphorus compounds shown in Table 10 to 3% saline solution.
(a), a vanadium compound (b), and a network-modifying ion source (c) were blended at the molar ratio shown in the table, and the mixed anticorrosive pigment was tested in the same manner.

【table】

[Table] 1 A mild steel plate was treated with a zinc phosphate treatment solution (Granodin SD 2500 series manufactured by Nippon Paint) under standard conditions, and a sludge containing zinc phosphate and iron () as the main components was collected. 500 g of this sludge was dispersed in ion-exchanged water, stirred, and washed by centrifugation.
After repeating this operation several times, the pH of the dispersion was
4.8, κ 0.33mS/cm. After adding calcium hydroxide to this and stirring for 10 hours (25℃), the pH
6.5, κ 0.19mS/cm. The lake was removed by centrifugation and dried at 200°C for 5 hours to obtain 350 g of fine powder. 2 Pigment ZPT mainly composed of zinc tripolyphosphate
(manufactured by Sakai Chemical Industries) 500g was dispersed in 1 part of ion-exchanged water, and the pH was 4.1. Calcium hydroxide was added to this under stirring (25°C), and after stirring for 10 hours, the pH was 7.5 and κ was 0.41 mS/cm. The lake was removed by centrifugation and dried at 150° C. for 5 hours to obtain 450 g of fine powder. 3 Ca(OH) ₂ and metaphosphoric acid were mixed so that the molar ratio of CaO/P ₂ O ₅ was 1/1 and melted at 900° C. for 2 hours. After cooling, it was ground to a size of 1 mm or less using a hammer mill, and then ground to a size of 10 μm or less using a jet mill. 4 K White 82 manufactured by Teikoku Kako Co., Ltd. 5 LF Bousei 6 manufactured by Kikuchi Color Industries Co., Ltd. Phosphorus compounds are expressed in weight without crystal water. a. Mix vanadium pentoxide and trimanganese tetroxide uniformly at a molar ratio of 1:1, and heat the mixture at 1100°C.
The reaction was carried out by firing for a period of time. After pulverizing the resulting glassy substance to 1 mm or less with a hammer mill,
It was pulverized to 10 μm or less using a jet mill. The vanadium compound was obtained by almost the same method as a unless otherwise noted. b Vanadium pentoxide (V ₂ O ₅ ) and manganese oxide (MnO ₂ ) were mixed at the molar ratio shown in the table, and Examples 90 to 94 were carried out at 1100°C, Examples 95 and 96 were carried out at 1200°C. Example 97 was fired at 900°C, Example 98 at 1400°C, and Examples 99 to 101 were fired at 1150°C for 2 hours and pulverized. c Mix V ₂ O ₅ , Ca (H ₂ PO ₄ ) and Ca (OH) ₂ in a molar ratio of 0.7:0.5:1.4, and mix in an automatic mortar for 5 minutes.
Stir for hours. When stirred, the powder generated heat and temporarily became sticky. The resulting reaction product was stirred at 100° C. for 1 hour, and then ground with milk for another 1 hour.

【table】

Claims (1)

[Scope of Claims] 1. (a) A phosphorus compound that releases phosphate ions in an environment where water is present, and vanadate ions that are generated in an environment where water or both water and oxygen are present.
(b) A vanadium compound and (c) A rust-preventive pigment obtained by firing and pulverizing a mixture containing a network-modifying ion source, wherein the network-modifying ion source is manganese oxide (MnOx: 1.5<x≦2.0). or a rust-inhibiting pigment characterized in that it is a combination of manganese oxide and other network-modifying ion sources. 2. The anticorrosive pigment according to item 1, wherein the manganese oxide is 0.1 mol or more per 1 mol of the vanadium compound in terms of V ₂ O ₅ . 3 Release phosphate ions in the presence of water (a) Generate vanadate ions in the presence of phosphorus compounds and water or both water and oxygen
A rust-preventing pigment obtained by firing and pulverizing a mixture containing (b) a vanadium compound and (d) a glassy substance. 4 Phosphorus compound (a) is phosphorus pentoxide, orthophosphoric acid,
4. The anticorrosive pigment according to item 3, which is a condensed phosphoric acid, a metal orthophosphate, or a metal condensed phosphate. 5. The antirust pigment according to item 4, wherein the metal species of the metal orthophosphate and the metal condensed phosphate is an alkali metal. 6. The antirust pigment according to item 3, wherein the vanadium compound (b) is a pentavalent vanadium compound. 7. The anticorrosive pigment according to item 6, wherein the pentavalent vanadium compound is vanadium (V) pentoxide or an alkali metal vanadate. 8 The third type in which the glassy substance (d) is silicate glass
Rust-preventing pigments listed in section. 9 The ratio of phosphorus compound (a) to vanadium compound (b) is
4. The anticorrosive pigment according to item 3, which has _{a P2O5/V2O5 molar ratio} of 0.3 to ₁₀₀ . 10 Third stage where firing is carried out at a temperature of 600°C or higher
Rust-preventing pigments listed in section. 11 (a) a phosphorus compound that releases phosphate ions in the presence of water; (b) a vanadium compound that generates vanadate ions in the presence of water or both water and oxygen; (c) a network An anticorrosive pigment obtained by firing and grinding a mixture containing a modified ion source and (d) a glassy substance. 12. The anticorrosive pigment according to item 11, wherein the phosphorus compound (a) is phosphorus pentoxide, orthophosphoric acid, condensed phosphoric acid, metal orthophosphate, or metal condensed phosphate. 13. The anticorrosive pigment according to item 12, wherein the metal species of the metal orthophosphate and the metal condensed phosphate is an alkali metal. 14. The antirust pigment according to item 11, wherein the vanadium compound (b) is a pentavalent vanadium compound. 15. The anticorrosive pigment according to item 14, wherein the pentavalent vanadium compound is vanadium pentoxide or an alkali metal vanadate. 16 Item 11, wherein the network-modifying ion source (c) is a metal oxide, metal hydroxide, metal carbonate, metal nitrate, metal organic acid salt, metal silicate, or metal borate, or a complex thereof. Rust-preventing pigments listed. 17. The antirust pigment according to item 16, wherein the metal species of the network-modifying ion source is an alkali metal. 18. The anticorrosive pigment according to item 11, wherein the glassy substance (d) is a silicate glass. 19. The anticorrosive pigment according to item 11, wherein the ratio of the phosphorus compound (a) to the _vanadium compound (b) is 0.3 to 100 in terms of _the molar ratio of _P2O5 / _V2O5 . 20 The network modification ion source (c) controls the amount of all metal cations (M) in the anticorrosion pigment in the form of an oxide (MO, M ₂ O ₃ , M ₃ O ₄ or M ₂ O) in which M can take 12. The anticorrosive pigment according to item 11, which is added in an amount not more than three times the sum of the moles of V ₂ O ₅ and P ₂ O ₅ expressed in the form. 21. The anticorrosive pigment according to item 11, wherein the glassy substance (d) is blended in an amount of 5 to 500 times the total weight of the phosphorus compound (a), the vanadium compound (b), and the network-modifying ion source (c). 22 The first type in which firing is performed at a temperature of 600°C or higher
The antirust pigment described in item 1. 23 By mixing (a) a phosphorus compound that releases phosphate ions in the presence of water and (b) a vanadium compound that produces vanadate ions in the presence of water or both water and oxygen. The resulting anti-rust pigment. 24. The anticorrosive pigment according to item 23, wherein the phosphorus compound (a) is an orthophosphate, a condensed phosphate, or a heterocondensate of phosphoric acid. 25. The anticorrosive pigment according to item 23, wherein the vanadium compound (b) is a vanadyl compound, a vanadate, a fired condensate of a vanadate, or a heterocondensate of vanadate. 26 (a) a phosphorus compound that releases phosphate ions in the presence of water; (b) a vanadium compound that produces vanadate ions in the presence of water or both water and oxygen; and (c) Rust-preventive pigment obtained by mixing a network-modified ion source. 27. The anticorrosive pigment according to item 26, wherein the phosphorus compound (a) is phosphorus pentoxide, orthophosphoric acid, condensed phosphoric acid, metal orthophosphate, or metal condensed phosphate. 28 The second metal orthophosphate and metal condensed phosphate in which the metal species is a metal other than an alkali metal
The antirust pigment described in item 7. 29. The antirust pigment according to No. 26, wherein the vanadium compound (b) is a pentavalent vanadium compound. 30. The anticorrosive pigment according to item 29, wherein the pentavalent vanadium compound is vanadium pentoxide or a vanadate other than an alkali metal. 31. The antirust pigment according to item 26, wherein the network-modifying ion source (c) is a metal oxide, metal hydroxide, metal carbonate, metal nitrate, metal organic acid salt, metal silicate, or metal borate. . 32. The anticorrosive pigment according to item 31, wherein the metal species of the network-modifying ion source is other than an alkali metal.