JPS59184266A - Corrosion-resistant paint and production thereof - Google Patents

Abstract

PURPOSE:To obtain paint having a high corrosionproofing function and giving a coating film which is not peeled off, by adding to paint a fine cationic resin powder on which an OXO acid anion of Group VI metal is adsorbed and from which an alkaline cation is removed. CONSTITUTION:A particulate activated anion exchange resin such as Diaion SA (a product of Mitsubishi Kasei K.K.) is washed with pure water to remove an alkali cation and reacted with an OXO acid of Group VI metal, such as chromic acid, to produce a fine cationic resin powder on which an OXO acid anion is adsorbed. The resulting fine cationic resin powder is added to paint to obtain the desired corrosion-resistant paint. Alternatively, the cationic resin powder on which the OXO acid anino of Group VI metal is adsorbed, is dispersed in water, treated with a cation exchange resin to remove the alkali cation and then blended with paint to obtain the desired corrosion-resistant paint.

Description

[Detailed description of the invention] The present invention does not cause blistering or peeling of the coating film, and
This article relates to a method for manufacturing a corrosion prevention method that has a high degree of corrosion prevention function.

The anti-corrosion effect of anion exchange resins has been known for a long time, and such resins generally have a tendency to swell when exposed to copper in water. ,
It has not been put to practical use in the paint field because of its low temperature, instability in heat, and difficulty in crushing.

In order to improve the above ten drawbacks, a polyvalent amine compound having a triazine nucleus, guanidine, and Artech I.
The anion exchange 'b'r which is condensed with v -c qh
3 resins were opened (Japanese Patent Publication No. 44-31.720@), and as an anion exchange resin for paints with heat resistance, water resistance, weather resistance, and anticorrosion function, especially the right 1. Paint'
A: It has attracted attention in the field of 1. In organic solvent-based anticorrosion paints, the vehicle is hydrophobic +1, so the presence of a small amount of water-soluble salt is allowed to control ionization, and the use of various anti-corrosion pigments is possible. The situation is completely different with the anti-corrosion coating 'Mi1', the presence of water-soluble salts causes the gelation of the paint and the formation of lumps and is not acceptable, so the anti-rust coating 'Mi1'31 still uses strontium chromate, Ri-1. ] is limited to a very small number of sparingly soluble salts such as lead murate.Even in water-based paints, it has been possible to comfortably obtain a small amount of negatively charged ani-A as the vehicle, including the above-mentioned pigments. However, with the positively charged cationic type Mizutake coating, the paint itself is necessary for rust prevention and reacts with romate ion A, causing gelation, insolubilization, and lump formation of the paint. Use is extremely important.

An example of a way to solve such problems is the Japanese Patent Application Publication No. 1987-
No. 151,227, Japanese Patent Application No. 57-72,258, etc., there is a method that has an excellent anti-corrosion effect [1-mate salts are coated with a water-insoluble binder to form so-called microcapsules to prevent ionization and gelation of paints]. It was proposed that However, it is difficult to make an effective Cassellization, and the effect of the C method is very limited.

Recently, problems such as gelation of the coating film, anti-corrosion properties, and physical properties of the coating film have also been improved. Stars and the like have become a new problem, and are becoming an important requirement for anticorrosion paints, regardless of whether they are organic solvent-based or water-based.

From a basic review of the exchange reaction of ion exchange resins, the present inventors found that the activation and regeneration of moxibustion resin particles (APR) reaction (1) Force\non-determined Although sluggish and slow, AER”-CI-1 large excess 0f-1-→AER+-
0N−−+−CI−−−−’(t) Reaction of adsorbing C(−) of this 1 reaction (2) △ to R” −01−1−
−1・CI −−→AER” −CI −→−0
1- "...We found that (2) occurs stoichiometrically in the acid-alkali equivalence relationship as 'jilt I+'9 and relatively easily.In this way, AE
R-CI is only possible with a large excess of alkaline solution (1)
Compound 1 is extremely stable because residual reactions occur. Chromate ion (Cr0a −) has a rust-preventing effect instead of 0.
The product sucked up is also stable, and there is almost no elution of Q-Oa-. It tends to be thought that if this is used as a rust preventive agent, it will not react with the base metal and will not become a rust preventive. It is explained electrochemically as follows.
At the BIX level, 0l-1- is generated, and if there is an anode near the anode, it reacts with metal ions, forming stable rust, and corrosion does not progress much.

However, under the paint film, the Ka-1~ and anode parts are localized quite far apart, and in this case stable rust is difficult to form. In particular, alkali metal ions such as aluminum, potassium, calcium, and other alkaline earth metal ions, amines, and alkaline cavities such as unpure or their interfaces will form a cathode site. These cations stabilize the 01-1- generated in the cathode site (3) H20+e -→OH
+H2(3) progresses rapidly. If it is painted (J), the generated hydrogen gas will cause the paint film to blister, corrode the metal, (
Severe film peeling. At this time, A that adsorbed 0 to part g-
If ER-CI-0a is present, it is equivalent to the presence of OH- at the opening degree (1), and ), 01-1- is wrapped around 1 and AER″-01-1-
O ~ 04- is soaked instead, and its excellent anticorrosion effect can be demonstrated in the first stage. As mentioned above, this performance is offset by the fact that the presence of alkaline cations with the same polarity as AER stabilizes the 01-1-1 more quickly and accelerates corrosion. Corrosion prevention function is not achieved. Therefore, in both aqueous and non-aqueous systems (paddy systems, 5 amounts of AER[:1-04 exist Y1 stably, and when corrosion stops, Cl-04- is released. Even if it exhibits a corrosion-preventing function, it will not be effective if alkali 1-1 kajin Δan is present in the system, and in fact, the apparent sagging will progress and cause blistering and flaking of the paint film. This has been clarified.

Therefore, the present invention was completed by considering various specific methods for removing these harmful cations from the system.

Therefore, according to the present invention (,!, an adsorbed car 1-Δnl'l iB
An anticorrosive paint that contains fine powder of 1 fat added to the coating and does not contain alkaline cations! 1. The cationic resin used in the present invention (J, primary to tertiary amine or 11th class as the anion exchange group) is known as an anionic father-exchanged resin having ammonium. It is possible to use any type of resin C.When such feed fat is provided with a stable form of -C (j,j) with adsorbed chloride ions, etc., it is activated by the reaction of formula 1) and used. be given Commercially available l,:;1-type anion exchange resins include, for example, Tire Ion SΔ (Mibiyo Kasei), Anhalide IRA (To Si T, Deco A Lai 1- (Sumitomo Chemical), and Dow Utsux). <Taugmical), balm at (
There is a genus palmput.

For the present invention, it is not necessary to arrange the grains in the same granular form as commercially available products, so it is better to select from a wider range. Periodic table\/1
When a group metal (eg, chromium, -[ribtene, trifluoride, etc., particularly preferably chromium]) is treated with an oxoacid, a cationic resin in which the oxoacid anion is adsorbed is obtained.

In the present invention, fine powder of cationic resin with adsorbed oxoacid anions of group VI metals of the periodic table is used as a paint (water-based or solvent-based paint, as it is added as a rust preventive agent). However, it is essential that alkaline cations be removed from the system in order to exhibit the rust prevention function and effectively prevent fristering, peeling, etc. of the paint film. , for example, Special Publication No. 44-31'720
This technology is completely different from the technology described in the above issue in which fine anion exchange resin powder treated with (31 chromic acid) ~ lium (Example 2 of the same publication) is added to paint. te d9ru.

The edict ``1 alkaline cation'' covers cations of alkaline metals or alkaline earth metals, amines, or ammonium ions.

The cationic resin used in the present invention is, for example, RN (C
H3) Since the anion exchange group in 3 is a hydrophobic group such as R bonded to -N(CH3)3, it is suitable for oil-based anticorrosive paints as it is easily soluble in solvents; j, etc. Since the cation and the oxoacid anion are ionicly bonded, it has hydrophilic properties and is easily dispersed in large C water, so it has the characteristic that it can be suitably incorporated into water-based anticorrosive paints.

The anticorrosive paint of the present invention has an anti-corrosion property in which the oxo-acid of the VB metal in the Periodic Table 111 is adsorbed by the reaction with the activated anion. Apply fine resin powder to 111 and apply the fine resin powder ('fA manufacturing method of anti-corrosion paint added to Mi1, wash the activated anion exchange resin particles with pure water or wash the activated anion exchange resin particles with pure water. This method is characterized by treating the adsorbed cavionic resin fine powder with a cation exchange resin in the presence of an aqueous medium to remove alkaline cations. 1υ1 Schedule Adsorbed cation III of oxoacid anion of Group VI metal +&
+ Various modes can be used depending on the method of adjusting the fat fine powder and the method of removing alkaline cations from the system. The inventors have discovered that the alkaline cations that impair the functionality of the rust preventive agent used in the present invention can be removed extremely easily and effectively using a cation exchange resin, and that the removal of the cations is effective in preventing corrosion. We have made the important discovery that this process can be carried out effectively at any stage of paint preparation or after it has been made into a paint. Therefore, the present invention provides extremely versatile methods for producing anticorrosive paints for removing alkali'[4 cations]. It will be done.

First, there is a method in which the alkaline cation is removed before reacting with the oxoacid anion. Anion exchange resins that are commercially available in granular form are easy to clean and can be used as they are.

In particular, quaternary salt anion exchange resins can be used because they must be washed with water during activation treatment.

However, in this water washing, pure water, especially specific conductivity clay, is 2M3.
It is desirable that the extraction is carried out at a purity of /cm or less, and that alkaline cabuone is not contained in the extract obtained by immersion for a long time, preferably in one liquid. It is sufficient if the specific conductivity vessel is sufficiently small.

Next cycle? 1! Table V The cationic resin fine powder on which the oxoacid anion of the Group 4 metal has been adsorbed may be washed with water to remove the alkaline Kajin A. In this case, the oxoacid anion may also be eluted to a very small extent, so that the specific conductivity does not become small as described above, and therefore, alkaline cation removal is not complete. However, it goes without saying that it satisfactorily achieves its purpose in normal use.

The above method is necessary when it is not possible to completely remove alkaline cations by mixing 10%, such as with oil-based paints, but with water-based paints, it is necessary to remove alkaline cations at that point, especially when using a lifting platform that is used after dilution, such as with den@paints. Can be removed.

This method can be said to be an extremely advantageous feature since it can be employed to remove alkaline Kaji-A, which is inevitably mixed in during the paint manufacturing process.

To remove alkaline cations, treat with a cation exchange resin, or add a cation exchange resin to the paint to capture alkaline cations.
Giru.

Therefore, as a source of the oxoacid anion of the group V1 metal of the periodic table, not only the C oxoacid but also the A formate can be used, but from the viewpoint of increasing the number of post-treatment steps, oxoacid is preferred.

The anticorrosive paint of the present invention is 1 part water! I and t) Oily C and C
It is an extremely useful anti-corrosion paint that does not cause blistering or peeling of the paint film, as it contains a unique anti-corrosion agent that exhibits its anti-corrosion function only during corrosion. .

The present invention will be explained below using Examples and Comparative Examples.

Example Periodic Table VIbχ Cr, Mo, and W are recovered from the metals, and these oxoacids are C, r 03 , and M.
o C3 and WO3 were taken up. Cationic resin
C A commercially available anion exchange resin was taken up. For details, we used deolide manufactured by Sumitomo Chemical Co., Ltd., and used styrene type (quaternary ammonium type and tertiary amine type. Since the tertiary amine type is 01-1 type, it can be used as is in IM.
It was washed with S/am pure water and used as C. The quaternary ammonium type is commercially available as type C1, so it must be treated with sorter C.
Activated to p L OH type. At this time, the precautions to be taken when washing with pure water are the same as those mentioned above. The leakage is also 0.3 to 0.
The particle size is 5n+m, and washing can be done by the usual column method or by using the method 5.
By employing the method described in No. 7 202434, high purity cleaning could be carried out efficiently.

Next, the exchange capacity of this OH type anion exchange resin was determined as follows. That is, about 3g of drained shinobi after washing as above.
Weigh it accurately and stir it with 50ml of pure water in a 100+nl beaker using a magnetic cooler. Approximately 2 ml of a saturated KCI aqueous solution is added to this, and K O+-1 is liberated by the reaction of the following formula.

△ER-Of-1+Kcl AER-C
l →-KOto1 This K O+-1 is 0.1N-1-
Titrated with 1c1. The end point was a plate in which the red change of phenolphthalein was P+i2. The reaction time of the above formula K O+-1 was slow and required more than 60 minutes for the slow titration of C',-.

The exchange capacity determined in this way is 0.8~1,0m eq
/gResin and 111, which showed considerable variation among each sample, showed TTi yield transfer. Although the regeneration of the column method was low, 1) the method described in Application No. 67-202434 yielded a product significantly 1° lower.

Next, neutralize this a1 with oxo acid.
. Since Cr03 is highly soluble in water, the reaction was extremely easy, but MO03 and WO:4 had a considerable amount of 1
” Unreacted material remained even after the reaction. The difference was no longer observed in the next pulverization step.

Next, a small amount of sample was pulverized using an automatic hole pulverizer for about 20 hours.
/ '(Iruri: I got hit by H1.) I used the anti-jij agent of the present invention, which removes the C211 grains, if appropriate.

These were added to the anion 1) 1 water - 1 no l r<A3+, and the various properties were investigated and the results are listed in Table 1.

(Left below) A roll mill was used to produce a large ff14 in the upper stage of crushing. Even in commercial water, it is difficult to secure pure water of 1 μS/cm, and removal of alkaline cations A is not complete.

Since the cationic electrolyte coating liquid has a non-volatile content of around 20%,
JK 115 ion exchange treatment is carried out. This treatment can be done using the usual method Cb using the column method, but Patent Application No. 57 20
The method described in No. 2434 is particularly preferred because it is efficient and completely removes alkaline cations in the practice of the present invention. Although the Kadion electric coating film is currently considered to be the best anticorrosive coating for cold-rolled steel sheets, in recent years galvanized mesh has been increasingly used, and the drawback of the coating film being easily peeled has become apparent. are doing. As a result of applying the rust preventive agent of the present invention in such cases, this peeling could be significantly reduced.

Claims (9)

[Claims] (1) An anticorrosive paint containing no alkaline cations and containing fine cationic resin powder adsorbed with an oxoacid anion of a group VI metal of the periodic table. (2) The anticorrosive paint according to claim 1, wherein the oxoacid ason of a group VI metal of the periodic table is a chromate anion. (3) The anticorrosive paint according to claim 1 or 2, wherein the paint is a water-based paint. (4) A cationic resin fine powder with the oxoacid anion adsorbed is obtained by a reaction between an oxoacid of a group VI metal of the periodic table and activated anion exchange resin particles, and the resin fine powder is added to a paint. In d5 of the method for producing an anticorrosion paint, the activated anion exchange resin particles are washed with pure water, but the cationic resin fine powder with the oxoacid anions adsorbed is treated with a cation exchange resin in the presence of an aqueous medium. , a method characterized in that alkaline cations are removed. (5) After removing alkaline cations from a granular activated anion exchange resin by washing with pure water, a fine resin powder obtained by reacting it with an oxoacid of a group VI metal of the periodic table is added to the paint. The method according to claim 4. (6) A cationic resin fine powder with adsorbed oxoacid anions of Group VI metals of the periodic table is dispersed in water, and after removing alkaline jy thione by treatment with a cation exchange resin, it is blended into the paint. The method according to claim 4. (7) A patent claim characterized in that fine cationic resin powder in which oxoacid anions of group VI metals of the periodic table are adsorbed is added to a water-based paint, and then treated with a cation exchange resin to remove alkaline cations. The method described in scope item 4. (8) The method according to claim 4, characterized in that the cationic resin fine powder in which the oxoacid anion of a group VI metal of the periodic table is adsorbed is added to an aqueous paint containing a cation exchange resin. (9) Water-based paint is electrolayer bath coated! ! 9. The method according to claim 8, which is '3+.