JPH0192279A - Corrosion-resistant coating - Google Patents

Abstract

PURPOSE:To obtain the titled coating virtually free from pollution, capable of suppressing corrosion cracking, hydrogen brittleness, pittings, coating film blisters, etc., for use in metallic materials, by incorporating a film-forming resin with a phosphoric acid ion source and vanadic acid ion source. CONSTITUTION:A mixture made by incorporating (A) a film-forming resin with 0.1-50pts.wt., based on 100pts.wt. of the whole solid content of the final coating, of (B) a phosphorus compound (e.g., magnesium phosphate) and (C) a vanadium compound (e.g., pentavalent vanadium compound) in the molar ratio P2O5/V2O5=0.3-100 and, if needed, (D) a network modifying ion source and/or glassy substance is calcined followed by grinding, thus obtaining the objective coating having both oxidizer and deposition functions under corrosive conditions due to water and oxygen to give rustproof performance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an anticorrosive coating that protects metals from corrosive environments.

(Prior art and its problems) Paints basically form a coating film on the surface of a base material in order to prevent corrosion of the base material. However, among these paints, those with particularly enhanced anti-corrosion properties are generally referred to as anti-corrosion paints and are used for various purposes.

The anticorrosive properties of anticorrosive paints are usually imparted by compounds that release chromate ions and are incorporated into the paint. This chromate ion (Cry) reacts with, for example, a(Fe), forming stable γ-Fe on the steel surface.
The so-called oxidizer (ox i
d 1zer) function and the so-called deposition, in which lower chromium oxides (e.g., Or! 03) produced by the reduction of chromate ions adhere to the steel surface.
There are two functions: ion) function. These two functions form a physical barrier film on the steel surface, which exhibits an extremely excellent anti-corrosion effect and maintains a stable steel surface.

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 is actively being conducted into substances that exhibit anti-corrosion effects that are non-polluting or have low-pollution properties. For example, phosphate-based substances, particularly zinc phosphate, silica phosphate, condensed aluminum phosphate, etc., have attracted attention, and some of them have been put into practical use. However, a phosphoric acid-based substance is a substance produced by a reaction with a metal, and has only the above-mentioned deposition function to protect the metal, and does not have an oxidizer function to oxidize the metal surface. Therefore, these have inferior rust prevention ability compared to chromate ions.

(Contents of the Invention) The present inventors have discovered that by including a phosphate ion source and a vanadate ion source in an anticorrosive paint, the oxidizer function lacking in the phosphate ions can be compensated for by the vanadate ions, and the present invention is provided. We have achieved this.

That is, the present invention provides a phosphate ion source that releases phosphate ions in an environment where water and oxygen exist, a vanadate ion source that releases vanadate ions in an environment where water and oxygen exist, and a film-forming resin. Provides an anticorrosive paint containing:

The anticorrosive paint of the present invention only needs to release both phosphate ions and vanadate ions in an environment where water and oxygen are present, and the paint itself does not need to contain these ions. Therefore, in the case of a paint system that can exist in the form of phosphate or vanadate ions, this refers to a paint that contains these ions, and if it cannot exist in the form of such ions, it refers to a paint system that contains water in the cured coating. and a substance that releases those ions in an environment where oxygen exists.

Phosphate ions rarely exist alone in aqueous solutions, and exist in various forms, for example, as condensates, but even in such cases it is understood that they are included in the concept of "phosphate ions" in this specification. Ru.

Furthermore, the term vanadate ion is understood to include condensed vanadate ions. Phosphate ion sources and vanadate ion sources are primarily provided as anticorrosion pigments. The anticorrosion pigment used in the present invention is obtained by firing and pulverizing a mixture containing a phosphorus compound, a vanadium compound, and, if necessary, a network-modifying ion source and/or a glassy substance.

The phosphorus compound used in the present invention is characterized by acting on a vanadium compound by heating to create a fired product that is not a mere mixture, and includes orthophosphoric acid; condensed phosphoric acid; condensed phosphate;
Phosphorus pentoxide phosphate mineral; commercially available complex phosphate pigment;
or a mixture thereof. Among the orthophosphates mentioned here, the monohydrogen salt (HPO4” salt),
It shall also include dihydrogen salts (salts of H!P O,). Further, condensed phosphates also include hydrogen salts. Further, the term condensed phosphate includes metaphosphate, and also includes ordinary polyphosphate and polymetaphosphate. Specific examples of phosphorus compounds include phosphate minerals such as monetite, torfylite, witrockite, xenotime, starcolite, stroopite, orchidite, etc.; commercially available composite phosphate pigments such as polyphosphoric acid silica; condensation Phosphoric acids such as pyrophosphoric acid, metaphosphoric acid, synthetic phosphates such as metaphosphates, tetrametaphosphates, hexametaphosphates, pyrophosphates, acid pyrophosphates, tripolyphosphates; or mixtures thereof. The metal species that form the phosphate are not particularly limited, and include alkali metals,
Examples include alkaline earth metals, other typical elemental metal species, and transition metals. Examples of preferred metal species include magnesium, calcium, strontium, barium, titanium, zirconium, manganese, iron, cobalt, nickel, zinc, aluminum, lead, tin, and the like. In addition, oxocations such as vanadyl, titanyl, and zirconyl are also included. Particularly preferred are calcium and magnesium. The use of large amounts of alkali metals is not very desirable. When alkali metal phosphates are used, the calcined product tends to be too soluble in water. However, when using an alkali metal phosphate, it may be used if its solubility in water can be controlled during the production of the rust preventive or at other times. Such controls can be, for example,
Various embodiments include the use of a matrix material (particularly a glassy substance) or coating to prevent solubility in water.

The vanadium compound used in the present invention is a compound having a vanadium valence of 0.2, 3.4 or 5, or two or more thereof, and oxides, hydroxides, and oxyacid salts of various metals. , vanadyl compounds, halides, sulfates, metal powders, etc. These decompose when heated and react with oxygen in the atmosphere during firing to become higher grade. For example, a metal powder or a divalent compound is finally changed into a 3-, 4-, or 5-valent 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 above reasons, but it is not preferred in practice because it has problems such as insufficient oxidation reaction. 5
The valent vanadium compound has vanadate ions and easily reacts with phosphate ions by heating to form a heteropolymer. Specific examples of vanadium compounds include vanadium (n) compounds, such as vanadium oxide (■) and vanadium hydroxide (■).
); vanadium (I [I) compounds, such as vanadium oxide (I [) (v, o, i); vanadium (IV) compounds, such as vanadium (IV) oxide (v, o, ), vanadium halides (v o x t) etc.; Vanadium (V)
Compounds such as vanadium oxide (VXv to s);
Vanadates such as orthovanadates, metavanadates or pyrovanadates of various metals, vanadyl halides (VOX3), etc.; or mixtures thereof. The metal species of vanadate include the same metal species as those shown for phosphate. This includes vanadium oxide and various metal oxides, hydroxides, carbonates, etc.
It may also be produced by firing at a temperature of 0°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.

The network modifying ion used in the present invention refers to a metal ion species added to modify the network structure formed by the fired product of a phosphorus compound and a vanadium compound, and specifically refers to various metal ion species, such as alkali Examples include metal ions, alkaline earth metal ions, metal ions of other typical elements, and transition metal ions. Examples of preferred network modifying ions include those found in metal salts of phosphoric acid. Examples of network-modifying ion sources include oxides, hydroxides, carbonates, nitrates, organic acid salts, silicates, borates, sulfates, and chlorides of the above metal species, and most preferably oxides, hydroxides, sulfates, and chlorides. They are oxides and carbonates.

When an alkali metal is used among the metal ion species, or when a sulfate or chloride is used as the ion source, these compounds tend to dissolve too much in water. Even in such cases, the solubility in water may be controlled by appropriate measures, such as the use of a matrix material or coating of the particles, as described above.

The glassy substances used in the present invention include not only matrix-forming glasses such as silicate glasses and borate glasses, but also those containing metal elements such as network-modifying ions, and which melt at 600°C. It is. Relevant glassy substances include silica (quartz) glass; silicate glasses, such as soda lime silicate glass (NawO
CaO5tOW system), lead-silicate glass (NatO-
PbO-9iOz system), aluminosilicate glass (A (
l! 03Cao-8tow series), borosilicate glass (NatO-Bt'35lot series); lead-borate glass (P bo -B, 0. series, commonly known as solder glass); alumino-borophosphate glass (Bt03 AQtO3
Pt05-based) alumino-borate glass (BaOA(l
tos BtOa system); alumino-phosphate glass (
P! 05-AQtO3-ZnO system); and the like. Examples of preferred glassy materials include soda-lime-based (C-glass), such as Nippon Glass Fiber glass flakes (CCP-150); aluminosilicate glasses (C-glass), such as Nippon Glass Fiber glass flakes (CEF);
-150); Examples include borosilicate glasses, such as Pyrex manufactured by Corning. When 1 g of fine powder of a glassy substance is dispersed and suspended in 100 m of water (!), it is preferable that the conductivity of the liquid is 500 μs/cm or less. 500
When it exceeds μs/cm, the rust prevention ability decreases.

The rust preventive used in the present invention is obtained by firing a mixture consisting of a phosphorus compound, a vanadium compound, and, if necessary, a glassy substance and a network-modifying ion source, cooling it, and then pulverizing it. Other inorganic substances such as matrix materials may be mixed into the mixture as necessary. The firing is carried out at a temperature higher than the melting temperature (T) of the fired product of the mixture consisting of the above components, specifically at 600°C or higher, preferably at 1000°C.
It is carried out at a temperature of at least .degree. C., more preferably at a temperature not higher than the higher of the melting temperatures of the TI and the glassy substance. Below this temperature, the reaction is insufficient and the components simply remain mixed. In such a case, the anticorrosion performance of the coating film deteriorates. The amount of phosphorus compound and vanadium compound is P
The molar ratio of tOs/VtOs is 0.
3-100, preferably 1-10. The amount of the network-modifying ion source added is based on the amount of all metal cations (M) in the rust preventive used in the present invention, and the oxide form that M can take (M O,
M 203, M , 04.

MOt or M, O)<7) Expressed in the form, ■, 0. and P.

It is added in an amount not more than 3 times the sum of the moles of 0 and 0, preferably 0 to 2.0 times. The oxide forms that M can take are MtOl if M is a monovalent metal; MOL if M is a divalent metal.
If M is a trivalent metal, it is M t 03, if M is tetravalent, it is Mo2, and if M is a mixed valence of divalent or trivalent, (for example, Mn tends to be divalent or trivalent under the firing conditions). ) shall be represented by M, 04. The glassy substance is blended in an amount of 5 to 500 times, preferably 10 to 100 times, the total amount of the phosphorus compound, vanadium compound, and network-modifying ion source. If it exceeds the above range, sufficient rust prevention cannot be obtained.

The anticorrosive paint of the present invention contains a film-forming resin as a main component in addition to the above-mentioned rust preventive agent. Any conventionally used film-forming resin may be used, such as maleated resins, epoxy resins, alkyd resins, acrylic resins, urea resins, blocked isocyanate resins, melamine resins,
Examples include areinated polybutadiene resin, polyvinyl butyral, polyvinyl alcohol, silicate ester, silicone resin, polyacrylic ester, and the like.

The anticorrosive paint of the present invention may take any form, including water-based paints, solvent-based paints, powder paints, electrodeposition paints, spray paints, brush-coated paints, and clear paints.

Furthermore, the anticorrosive paint of the present invention can be considered as a concept that includes water-based paints containing aluminum powder, zinc-rich paints, and the like. For example, in the case of a water-based paint containing aluminum powder, the above-mentioned anti-corrosion properties are useful not only for the base metal, but also for the metal powder, especially the aluminum powder pigment, and prevent the oxidation of metal powder, which is unique to water-based paints. is prevented and imparts a high metallic luster. In addition, in the case of zinc-rich paint, white rust is likely to occur on the paint film, and if the secondary surface treatment process is increased or if oil-based paints or alkyd-based resin paints are overcoated on the zinc-rich paint film, delamination may occur. However, phosphate ions and vanadate ions moderately suppressed the activity of zinc and improved white rust and topcoat adhesion. It has surprisingly been found that in the case of anionic electrodeposition paints containing the rust preventive of the present invention, not only the rust prevention properties but also the throwing power are greatly improved.

Depending on the various forms of the above-mentioned paint, the anti-corrosion paint of the present invention includes:
It may also contain a solvent, a colored pigment, an extender pigment, and various other additives (for example, an anti-sagging agent, a flow control agent, an ultraviolet light inhibitor, etc.). The anticorrosive paint of the present invention contains a total of 0.1 to 50 parts, preferably 0.5 to 20 parts, of both a phosphate ion source and a vanadate ion source per 100 parts by weight of the total solid content of the paint. In the case of a zinc-rich paint, a total of 0.3 to 30 parts of the phosphate ion source and the vanadate ion source are added to 100 parts by weight of zinc powder contained in the seasonal paint.

Metal materials to which the present invention is applied include steel, high strength steel, high tensile strength steel,
Examples include plated steel sheets, alloys such as stainless steel, cast iron, aluminum and alloys thereof.

Corrosion conditions under which the anticorrosive paint 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 ions that are thought to promote corrosion are present. (for example, 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 This method prevents corrosion by electrically reducing the oxidation protection, but on the other hand, it tends to cause significant paint film deterioration. The anticorrosive paint of the present invention effectively suppresses this paint film deterioration (which is included in corrosion in a broad sense). The optimum corrosion conditions for the present invention are pI4 within the range of 2-9. It has a strong blister inhibiting effect at pH 2 to 5, and a strong general corrosion inhibiting effect at pH 5 to 9. If it exceeds this range, the antirust effect will decrease.

(Operations and Effects of the Invention) When the anticorrosive paint of the present invention is applied, water and oxygen permeate into the paint film, and vanadate ions and phosphate ions from the rust preventive pigment in the paint film are appropriately dissolved. Vanadate ions supplement the oxidizer function lacking in the aforementioned phosphate ions; this ionic species forms an in-solution redox couple under corrosive conditions in the presence of water and oxygen, exhibiting a significant redox potential; It performs the oxidizer function mentioned above. On the other hand, phosphate ions form a poorly soluble precipitate film under corrosive conditions.
Has a deposition function.

As described above, the anticorrosive paint 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 anticorrosion coating for metal materials that is non-polluting and low-pollution. Corrosion suppressed by the anticorrosive coating of the present invention includes corrosion weight loss, corrosion cracking, hydrogen embrittlement, thread end corrosion, pitting corrosion, end face corrosion, corrosion at processed parts such as bending, and blistering of the coating film.

(Examples) The present invention will be explained in detail below using examples. The present invention is not limited to these examples.

Reference Example 1 A rust preventive agent was prepared by mixing the components shown in Table 1 below.

Reference Example 2 A rust preventive agent containing both a phosphate ion source and a vanadate ion source was obtained by pulverizing the components shown in Table 2 under the conditions shown in the same table.

Reference Example 3 A rust preventive containing a phosphate ion source and a vanadate ion source was prepared by baking the components shown in Table 3 at the temperatures shown in Table 3, cooling and pulverizing them.

Reference Example 4 The rust preventive agent of the present invention was obtained by mixing the components shown in Table 4 below, melting, cooling, and pulverizing.

Examples 1 to 4 and Comparative Examples 1 to 4 This example is an example in which the anticorrosion performance of various paints containing the rust preventive agent of Reference Example 1 described above was investigated.

Water-based emulsion paint (Water-based Nippe Wide manufactured by Nippon Paint Co., Ltd.), a thermosetting resin such as melamine alkyd resin, and a room temperature curing epoxy resin each with a rust preventive added thereto, painted on a steel plate, and dried naturally for 10 days or at 140°C. The bake was dry for 30 minutes.

The dry film thickness was 50 μλ. JIS on the obtained painted board
Z 2371 Tsurtosbrae test was performed to determine peelability and blistering.

For comparison, a similar experiment was conducted using a device that did not have either a phosphate ion source or a vanadate ion source. The results are shown in Table-5.

Evaluation method: Peelability of Tsuruto Brake Test One side peeling width from the thick part 1. The pigment of the present invention supplemented with another extender pigment was ranked according to the following ranking, with the peeling width being 1.

× Worse than standard value 1.2〈ratio △ Same as standard 0.7〈ratio〈1.2
[○ Better than standard 0.2〈Ratio＜0.7◎
Very better than the standard Ratio<0.2 Put into the Tsurutosbrae test without blister cuts and judge the appearance with the naked eye after 500 hours.

○ Few blisters △ Few blisters × Many Examples 5 to 13 and Comparative Examples 5 to 6 5 parts by weight of the compounds shown in Table 6 were added to room temperature curing epoxy resin paint (trade name: Copon Mastic Primer) manufactured by Nippon Paint Co., Ltd. Got the paint. The resulting paint was air-sprayed onto a sandblasted steel plate to a dry film thickness of 100 μm.
It was painted so as to cover any scratches and dried for 10 days at ambient temperature. A blister test of the obtained coated steel plate was conducted as follows.

Blister test under temperature gradient: tatami soaked in water under temperature gradient of 40℃ on painted side/20℃ on back side
Blisters after being left for one day were visually evaluated.

◎− Much better than the comparative test.

〇-Good.

△- Comparative data is at the same level.

× - Inferior to comparative materials.

In this case, the comparative data is a case in which the extender pigment shown in Comparative Example 5 is used, but no antirust pigment is used.

Table 6 A paint was prepared by mixing the following formulation in a sand mill.

Ingredients Parts by weight Coal tar pitch varnish 30 Polyol resin varnish 12 Extender pigment
20 Rust preventive agent of Reference Example 3
2 Anti-sagging agent 0.
5 Methyl isobutyl ketone 5 Kijirol 20.5 The obtained paint was applied to a dull steel plate (JISG3141 5PCCSD) with air spray so as to create a dry film thickness of 200μ, and
It was dried for IO days at room temperature. The obtained coated plate was evaluated in the same manner as in Example 1 by conducting a Tsuruto spray (JIS Z2371) test.

The results are shown in Table-7.

Table-7 In this example, thread rust resistance was tested.

5 parts by weight of the rust preventive agent of Reference Example 4 shown in Table 8 below was added to a melamine alkyd resin paint, which was applied to a cold rolled steel plate by a conventional method and cured by baking at 140°C for 30 minutes.

The yarn end test was carried out for 24 hours using the Tsuruto Brake test, and then left standing under 80% relative humidity (at 35°C).
The average length of filamentous rust after 45 hours was compared with a comparative example of paint containing the same amount of strontium chromate, and ◎ was excellent, △ was equivalent to 01, and poor. The items that are true are marked on a four-point scale of ×. The results are shown in Table-8.

Table-8 The present invention shows an example of use in an anionic electrodeposition paint.

Anionic aqueous fat synthesis 8 stone polybutadiene B-1000g 1500*') Antigen 6C*li 10g maleic anhydride 250g deionized water 20g diethylamine
0.5g Propylene Glycol 100g Ethysolp
340g *manufactured by Nippon Petrochemical Co., Ltd.; Mn1
500, vinyl 65%, trans 14%, cis 16% *3) Sumitomo Chemical Co., Ltd.: N-methyl-N'-(1,3
-dimethylbutyl), p-phenylenediamine chilled bone-in 2 (2 Kolben, 8-stone polybutadiene B-15001
000g and add 6Clog of antigen and 25g of maleic anhydride.

Addition polymerization reaction of maleic acid to polybutadiene is carried out while stirring and maintaining the internal temperature at 190 to 200°C. Approximately 5 hours after the temperature was raised, it was confirmed that the reaction was completed by a dimethylaniline color reaction. Thereafter, the internal temperature was cooled to 100° C., and a mixture of 20 g of deionized water and 0.5 g of diethylamine was added dropwise over about 30 minutes. After the dropwise addition was completed, stirring was continued for about 1 hour, and the acid value was confirmed to be 140. Thereafter, 100 g of propylene glycol was added and reacted at 110° C. for 3 hours, and the total acid value was confirmed to be 125. Thereafter, 340 g of ethyl cellosolve was added, and after stirring at 80° C. for about 1 hour, the synthesis was completed (solid content: 80%).

Preparation of pigment paste 125 g of the above maleated polybutadiene resin was collected,
13 g of triethylamine was added to this, and then 250 g of deionized water was gradually added to dissolve it uniformly.
It was set as a 6% festival. Next, the rust preventive agent and other pigments shown in Reference Examples were added, and the mixture was mixed and stirred using a disper for about 1 hour.

After adding glass peas to this mixture, the particle size was 20μ with SG.
After dispersing the glass peas in the following and zeroing them out, 1112 g of deionized water was added to complete the production (solid content 20%).

Paint preparation An anionic electrodeposition paint was prepared using the following components.

Ingredients: Parts of maleated polybutadiene 125.0 Resin triethylamine 14.0 Newcol 710F'*') 1.0 Cobalt naphthenate 1.5 Deionized water
358.5 Above pigment paste
100.0*3) Manufactured by Nippon Nyukazai Co., Ltd.: Nonionic surfactant maleated polybutadiene resin, β-hydroxyphenol ether compound A1 triethylamine, Nucor 710F, and cobalt naphthenate were added, stirred, and emulsified and dispersed with ionized water as described later. A uniform emulsion was obtained. A pigment paste was added to this emulsion to obtain an anionic electrodeposition paint.

Two 5 pcc dull steel plates (manufactured by Nippon Test Panel Co., Ltd.) that had been degreased using this electrodeposition paint were lined up at a 1 cm interval and electrodeposited. The conditions for electrodeposition coating are a temperature of 28℃.
±0.5℃, voltage is 30 to 35 μm for zinc phosphate treated steel plate (SPCC dull steel plate treated with Granozin 5D-5000 (manufactured by Nippon Paint Co., Ltd.))
It was set to a value that would result in a coating film with a film thickness of . The resulting panels were cured at 170° C. for 25 minutes, and the film thickness of the resulting coating was measured on the surface facing the panels (inner surface) and the surface facing outward (outer surface). The results are shown in Table-9. In the paint of Example 1, the coating film thickness was larger on the inner surface, that is, the surface where electric current is difficult to penetrate and which is normally difficult to be painted.

In addition, this paint was applied to a 5S-41 shot blasted steel plate (
The coating was applied to a surface (manufactured by Nippon Test Panel Co., Ltd.) with a roughness of about 50 μm and an average film thickness of 30 to 35 μm. A salt spray test was conducted on the resulting coating film to determine its spot rust resistance and corrosion width.
The blister resistance was compared with that of Comparative Example 1O. The results are shown in Table-9.

Table 9, Examples 33 to 36 and Comparative Example 11 This example uses the rust preventive agent produced in the reference example as a water-based metallic paint (flake-shaped aluminum pigment with a length of approximately 25 μm and a thickness of approximately 0.8 μm). ) by adding 0.5 part by weight to
After this paint was allowed to stand at 50°C, hydrogen gas generated during one hour was captured and its amount (amount of hydrogen gas generated per 50 g of paint) was determined, and the results are shown in Table 10.

The water-based paint was manufactured as follows.

Mokusho starvation (manufacture of polyester resin) 134 parts by weight of bishydroxyethyl taurine and 1 part of neopentyl glycol were added to a 212 Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter.
A total of 30 parts by weight, 236 parts by weight of azelaic acid, 186 parts by weight of phthalic anhydride, and 27 parts by weight of xylene were charged, and the temperature was raised. Water produced by the reaction is azeotroped with xylene and removed.

After about 2 hours from the start of reflux, the temperature was brought to 190°C.
Stirring and dehydration are continued until the oxidation value corresponding to the carboxylic acid reaches 145, and then the mixture is cooled to 140°C.

Next, the temperature was maintained at 140°C, and the "Cardura ElO"
(Persatic acid glycidyl ester manufactured by Shell)
C. 314 was added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The obtained polyester resin had an acid value of 59, a hydroxyl value of 90, and an Mn of 1054.

Production of resin particles> In a 1 g reaction vessel equipped with a stirrer, a cooler, and a temperature control device, 282 parts by weight of deionized water, 10 parts by weight of the polyester resin obtained by the above method, and 0 parts by weight of dimethylethanolamine were added.
．． 75 parts by weight of azobiscyanovaleric acid was charged, dissolved while stirring and maintaining the temperature at 80°C, and 4.5 parts by weight of azobiscyanovaleric acid was added to 45 parts by weight of deionized water and 4 parts by weight of dimethylethanolamine.
．． Add 3 parts by weight of the solution. Next, 70.7 parts by weight of methyl methacrylate, 9 parts by weight of n-butyl acrylate
A mixed solution consisting of 4.2 parts by weight of styrene, 70.7 parts by weight of styrene, 30 parts by weight of 2-hydroxyethyl acrylate, and 4.5 parts by weight of ethylene glycol dimethacrylate was added dropwise over 60 minutes.

After the dropwise addition, 1.5 parts by weight of azobiscyanovaleric acid dissolved in 15 parts by weight of deionized water and 1.4 parts by weight of dimethylethanolamine was added and stirring was continued for 60 minutes at 80°C, resulting in a non-volatile content of 45%. , pH 7.2, viscosity 92
cps (25°C), an emulsion with a particle size of 0° and 156 μm is obtained. This emulsion was spray-dried to remove water, and 100 parts by weight of the resin particles were redispersed in 200 parts by weight of xylene to prepare a xylene dispersion of resin particles. Particle size is 0
．． It was 3μ.

<Production of resin for metallic paint> 76 parts by weight of ethylene glycol monobutyl ether was charged into an IQ reaction vessel equipped with a stirrer, a temperature controller, and a cooling tube, and 45 parts by weight of styrene, 63 parts by weight of methyl methacrylate, and 2-hydroxy Ethyl methacrylate 4
8 parts by weight, 117 parts by weight of n-butyl acrylate, 27 parts by weight of methacrylic acid, 3 parts by weight of lauryl mercaptan,
After adding 61 parts by weight of a monomer solution consisting of 3 parts by weight of azobisisobutyronitrile and dropping the mixture while stirring at a temperature of 120°C, stirring was continued for 1 hour. Further, 28 parts by weight of dimethylethanolamine and 200 parts by weight of deionized water were added to reduce the non-volatile content to 50% and the number average molecular weight of the resin to be 16.0%.
An acrylic resin varnish of No. 0 was obtained. The special number of this resin is 08
The value was 70, the acid value was 58, and the sp value was 11.3.

Preparation of Metallic Paint> 140 parts by weight of the above resin varnish, 30 parts by weight of the above organic solvent-swollen resin particle dispersion, 10 parts by weight of each aluminum pigment, and 30 parts by weight of Cymel 303 as a crosslinking agent were stirred and mixed, and the mixture was deionized. It was diluted with water and diluted with a No. 4 food cup for 25 to 30 seconds (20°C) to obtain a metallic paint.

Preparation of water-based clear paint> Same as above <Production of resin for metallic paint>, 65.8 parts by weight of n-butyl acrylate, 11.8 parts by weight of methyl methacrylate, 16 parts by weight of hydroxyethyl methacrylate.
．． A polymer was prepared using 2 parts by weight, 6.1 parts by weight of methacrylic acid, and 5 parts by weight of azobisisobutyronitrile.

This weight was 100% neutralized with dimethylethanolamine and then diluted with water to obtain a water-soluble resin varnish with a non-volatile content of 50%.

The obtained water-soluble resin varnish was blended using hexamethoxymethylolmelamine (Cymel 303, manufactured by Mitsui Toatsu Co., Ltd.) as a crosslinking agent so that the resin solid content ratio was 70/30, and deionized water was added. The solution was diluted with a No. 4 food cup for 30 to 35 seconds (20°C) to obtain a water-based clear paint.

Coating Experimental Example The above-mentioned metallic paint and then the above-mentioned clear paint were air-sprayed onto an intermediate coated steel plate at a temperature of 23° C. and 60% so that the dry film had a dry film thickness of 20 microns and 30 microns for the latter. The former was applied in two stages with an interval of 1 minute, then dried at 80°C for 5 minutes, and the latter was applied in one stage and allowed to set for 7 minutes. Next, put the painted board in the dryer! Bake at 50℃ for 20 minutes,
A test board was created.

Table-IO A zinc-rich paint was prepared using the following formulation.

Ingredients Parts by weight Ethyl silicate 28 52.1 (manufactured by Nippon Colcoat) Isopropanol 38.9 Water
8.60
, IN hydrochloric acid 0.4 pigment) parts by weight Zinc powder (manufactured by Mitsui Kinzoku Mining Co., Ltd., 70.4 CS product) Rust preventive agent of Reference Example 1-a 3.2 clay (manufactured by Angel Hard Co., Ltd. 17.7 ASP2)
00) The remaining components except water and hydrochloric acid among the above components were placed in a reaction vessel, stirred at 40°C, and water and hydrochloric acid were added dropwise over 1 hour. After the completion of the dropping, stirring was continued for 1 hour to prepare a coating liquid. A zinc-rich paint was prepared by mixing and dispersing the obtained coating liquid and the above pigment.

The resulting zinc-rich paint was air-sprayed onto a sandblasted steel plate to a dry film thickness of 15±2 μl.
After drying for 7 days at 20°C and 75% relative humidity,
Tested. The tests included a salt spray test and a topcoat comparison test.

? (1) Salt spray test (test is JIS Z 2371)
A salt water spray test was conducted for 240 hours, and the state of red rust was determined by ASTM (D610), and the state of white rust was found to be good.

(2) Overcoat adhesion test (commercially available oil-based anti-corrosion paint was applied two times, left outdoors for 6 months, and a second coat test was conducted, and peeling was determined according to JIS K 5400. The width of the coat was 5 x m. The top coat adhesion was good in both cases.

For comparison, a zinc-rich paint without the rust preventive of the present invention was prepared in the same manner and the same tests were conducted, and both salt spray and topcoat adhesion were poor.

Patent applicant: Nippon Paint Co., Ltd.

Claims (1)

[Claims] 1. A phosphate ion source that releases phosphate ions in an environment where water and oxygen exist, a vanadate ion source that releases vanadate ions in an environment where water and oxygen exist, and film formation. Anti-corrosion paint containing synthetic resin. 2. The anticorrosive paint according to item 1, wherein the phosphate ion source and the vanadate ion source are antirust pigments. 3. The anticorrosive paint according to item 2, wherein the anticorrosive pigment is obtained by firing and pulverizing a mixture containing a phosphorus compound, a vanadium compound, and optionally a network-modifying ion source and/or a glassy substance. 4. The anticorrosive paint according to item 2, wherein the anticorrosive pigment is a mixture of a phosphorus compound that releases phosphate ions and a vanadium compound that releases vanadate ions. 5. The anticorrosive paint according to item 1, wherein the anticorrosive paint is a water-based paint, an anionic electrodeposition paint, or a zinc-rich paint.