JPS5847427B2 - Kousetsuchiyakuseiboseitoriyosobutsu - Google Patents

Description

[Detailed description of the invention] The present invention relates to anticorrosion coating compositions.

More specifically, the present invention relates to a coating composition that does not contain harmful components and has excellent adhesion to metal substrates, dense coating film, and rust prevention properties.

Conventional rust-preventive pigments for anti-rust paints include lead-based pigments such as red lead, chromate-based pigments such as zinc chromate and strontium chromate, but among these, anti-rust pigments containing hexavalent chromium are particularly popular. Pigments pose a serious pollution problem and are a source of water pollution, requiring equipment to prevent them from escaping from factories and workshops to the outside, which is inconvenient in terms of cost and application.

As a non-polluting anti-rust pigment that eliminates this drawback, molybdates (Japanese Unexamined Patent Publication No. 49-5-5
132, U.S. Pat. No. 3,353,979). Zinc phosphate [Zn
3(PO4)2・2H20 or 4H20], silica phosphate (2 Si02・P205), titanium phosphate (3
TiO2/P205), calcium phosphosilicate,
Barium metaborate (BaB204.H20), calcium borosilicate, basic iron oxide, etc. are known.

These anti-rust pigments are inhibitor pigments based on the anti-corrosion mechanism based on electrochemical action, passivation action, etc., similar to the above-mentioned heavy metal-based anti-rust pigments.

However, these non-polluting rust preventive pigments have inferior rust preventive properties compared to chromate and lead-based rust preventive pigments, and if they are mixed into paint and applied, they tend to cause blisters on the paint film, resulting in poor rust prevention of the paint film. decreases significantly.

On the other hand, inorganic pigments containing aluminum, silicon, and iron as main components have been developed as rust-preventing pigments based on the rust-preventing mechanism of adsorption of pigments onto metal substrates, but when these pigments are added to paints, blistering of the paint film occurs. Although it is effective in preventing the occurrence of corrosion, it is insufficiently effective in blocking corrosive liquids and gases such as water and sulfur dioxide gas, and therefore the rust prevention properties of the coating film are not sufficient.

The present invention aims to eliminate the above-mentioned drawbacks.

That is, the present invention provides a paint containing an alkyd resin, an alkyd melamine resin, an epoxy resin, or a maleated oil as a main color vehicle,
The present invention relates to a highly adhesive rust-preventing paint composition containing an iron, zinc or nickel chelate compound of anthranilic acid at 2% by volume or more based on the solid content of the paint.

In other words, the anticorrosive paint formed by adding anthranilic acid metal chelate to a resin composition for forming a coating film has excellent adhesion to metal substrates such as steel, and has excellent adhesion resistance at the interface between the coating film and the metal substrate. Since it is highly destructive, it can highly prevent the occurrence of blisters.

In addition, anthranilic acid metal chelate has a high cohesive failure strength of the coating film, and therefore has good adhesion with the coating film-forming resin and forms a dense coating film. It has excellent rust prevention properties by preventing the infiltration, permeation and diffusion of liquids and gases.

The metal-chelated anthranilic acid used in the present invention and pc++, pe++1-+, Zn"y
It is a chelate compound with a metal ion represented by Ni'' or Ni+ + +.

When these chelate compounds have a sufficiently low solubility in water and are added to paint, the amount of chelate compounds eluted from the paint film by external water, humidity, etc. can be ignored, and they are sufficient as rust-preventing pigments. It is practical.

In the present invention, at least one of the above chelate compounds is added to the paint in an amount of 2% or more by volume of the solid paint.

That is, if the amount of the chelate compound added is less than 2% by volume, the blister resistance and density of the paint film will decrease, making it impossible to obtain a sufficient rust prevention effect, and if the amount added is extremely large, the paint will deteriorate. Since various physical properties such as coating film forming properties, coating film strength, and shielding properties against corrosive factors are deteriorated, the amount is preferably about 40% by volume or less, and is added in an amount of about 3% to about 25% by volume. By doing so, a particularly good rust prevention effect can be obtained.

In the present invention, the paint to which the chelate compound is added is a paint containing a conventionally known alkyd resin, alkyd melamine resin, epoxy resin, or maleated oil as a main color vehicle.

These coatings can be used either by adding only the metal chelate compound of anthranilic acid, or by adding them in combination with ordinary extender pigments and/or color pigments, or even other non-polluting rust-preventing pigments. You can achieve your purpose.

These extender pigments, coloring pigments, non-polluting antirust pigments, etc. can be added up to 43% by volume of the solid content of the paint.

By appropriately adjusting the amount added within this range, strength and sufficient thickness can be imparted to the coating film, or the coating film can be colored.

The anticorrosion coating composition of the present invention does not contain highly toxic antirust pigments, so it is easy to handle and use, and the coating film has excellent anticorrosion properties with great blister resistance and density.

The present invention will be explained below with reference to Examples.

? The solubility of the metal chelate compound of anthranilic acid shown in the examples in water was measured by the following method.

First, take about 2g of pigment into a hard beaker 300rfLl,
Add about 200 ml of ion-exchanged water, keep at 50-60°C for 1 hour while stirring thoroughly, then slowly cool to room temperature. After checking the liquid temperature, add finished paper/l6 as specified in JIS-P-3801. .Repeat the process several times in 4.

Using a whole pipette, accurately collect 100M of this furnace liquid into an evaporation dish of known weight, dry it in a dryer at 110±5°C until it reaches a constant weight, put it in a desiccator, let it cool, and then reduce the weight. The solubility of each pigment in 100 ml of solution was determined from the evaporated residual amount.

Example 1 Soybean oil modified long oil phthalic acid resin varnish (oil length 62%, non-volatile content 70%), zinc white, iron oxide, talc and iron anthranilate (Fe + + ) chelate compound (specific gravity d =
1.55, solubility S21'C=2. I X1 0
-2g/10 07727l! An appropriate amount of xylene was added to the aqueous solution), the mixture was uniformly kneaded in a pot mill according to the formulation shown in Table 1, and then a dryer was added to prepare a test paint.

This paint was applied with a brush to a JIS-G-3141 polished mild steel plate, dried at room temperature for 7 days, and then subjected to a comparative test.

The results are shown in Table-2. Example 2 Nickel anthranilate (Ni++) in soybean oil-modified long-oil phthalate resin varnish (oil length 62%, non-volatile content 70%)
Chelate compound (specific gravity d=1.7, solubility S2・c=0
．． 5 X 10-”.!9/100ml water solution (
A paint was prepared in the same manner as in Example 1 by adding an appropriate amount of xylene to zinc white, iron oxide, and talc, and using the formulation shown in Table 1.
We conducted a test.

The results are shown in Table-2. Example 3 Zinc anthranilate (Zn++) (specific gravity d = 17, solubility 821°C = 1.0 6 X 10
-J/100TLl aqueous solution) Add an appropriate amount of xylene to zinc white, iron oxide, and talc and make the formulation shown in Table-1 Example 1
Paints were created in the same way as the above, and tests were conducted.

The results are shown in Table-2. Comparative Example 1 As in Example 1, p5 super (first
Table Note 1) A suitable amount of xylene was added to zinc white and iron oxide talc to prepare paints according to the formulations shown in Table 1, and tests were conducted.

The results are shown in Table-2. Comparative Example 2 Similar to Example 1, triphenylguanidine dichromate (organochrome: Table 1, Note 2) was added to soybean oil-modified long-oil phthalic acid resin varnish (oil length 62%, non-volatile content 70%).
), zinc white, iron oxide, and talc, and an appropriate amount of xylene was added to prepare paints according to the formulations shown in Table 1, and tests were conducted.

The results are shown in Table-2.

Example 4 A suitable amount of water was added to water-soluble maleated linseed oil (non-volatile content, 85%), zinc white, talc, and iron anthranilate (Fe++), and the composition shown in Table 3 was prepared using three mouths. The mixture was kneaded with Lumil, the paint was adjusted, and it was used as a test paint.

This paint was applied with a brush to a JIS-G-3141 polished mild steel plate, dried at room temperature for 10 days, and then subjected to a comparative test.

The results are shown in Table-4. Example 5 Water-soluble maleated linseed oil (non-volatile content, 85% zinc white,
A suitable amount of water was added to talc and nickel anthranilate (Ni''), and paints and test coated plates were prepared in the same manner as in Example 4 using the formulations shown in Table 3.

The test results are shown in Table-4.

Example 6 Add an appropriate amount of water to water-soluble maleated linseed oil (nonvolatile content, 85%), zinc white, talc, and zinc anthranilate,
Paints and test coated plates were prepared in the same manner as in Example 4 using the formulations shown in Table 3.

The test results are shown in Table-4.

Comparative Example 3 Water-soluble maleated linseed oil (non-volatile content, 85% zinc white,
Appropriate amounts of water were added to talc and P-5 Super, and paints and test coated plates were prepared in the same manner as in Example 4 using the formulations shown in Table 3.

The results are shown in Table-4. Comparative Example 4 Water-soluble maleated linseed oil (non-volatile content, 85% zinc white,
A suitable amount of water was added to talc and triphenylguanidine dichromate (trade name: Organochrome), and paints and test coated plates were prepared in the same manner as in Example 4 using the formulations shown in Table 3.

The results are shown in Table-4.

Example 7 Short oil alkyd resin (oil length 40%, non-volatile content 50%),
Titanium oxide, precipitated barium sulfate, iron anthranilate (
A test coating was prepared by uniformly kneading and dispersing Fe++), melamine resin (non-volatile content: 60%), and xylene in the formulation shown in Table 5 using a pot mill.

This paint was applied by air spray onto a JIS-G-3141 polished mild steel plate, baked and dried at 130°C for 20 minutes, and then tested.

The comparative test results are shown in Table-6.

Example 8 Short oil alkyd resin (oil length 40% non-volatile content 50%),
A paint and a test coated plate were prepared in the same manner as in Example 7 using the formulations shown in Table 5 of titanium oxide precipitated barium sulfate, nickel anthranilate (Ni++), melamine resin (nonvolatile content 60%), and xylene.

The test results are shown in Table-6. Example 9 Short oil alkyd resin (oil length 40%, non-volatile content 50%),
Titanium oxide, precipitated barium sulfate, zinc anthranilate, melamine resin (non-volatile content 60%) and xylene are listed.
A paint and a test coated plate were prepared in the same manner as in Example 7 using the formulation shown in 5.

The test results are shown in Table-6.

Comparative Example 5 Short oil alkyd resin (oil length 40%, non-volatile content 50%),
A paint and a test coated plate were prepared in the same manner as in Example 7 using titanium oxide, precipitated barium sulfate, p5 super, melamine resin (nonvolatile content 60%), and xylene in the formulation shown in Table 5.

The test results are shown in Table-6.

Comparative example 6 Short oil alkyd resin (oil length 40%, non-volatile content 50%),
The same paint and tests as in Example 7 were made using the formulation of titanium oxide, precipitated barium sulfate, triphenylguanidine dichromate (trade name, Organochrome), melamine resin (nonvolatile content 60%), and xylene as shown in Table 5. A painted board was created.

The test results are shown in Table-6.

Example 10 Epoxy resin varnish (bisphenol type epoxy resin,
Add an appropriate amount of xylene to 70% non-volatile content, mixed solution of ethylene glycol monoethyl ether and xylene), iron oxide, talc, and iron anthranilate (Fe++), and mix uniformly with a pot mill according to the composition shown in Table 7. After kneading, polyamide resin varnish non-volatile content 50%,
A test paint was prepared by adding a mixed solution of ethylene glycol monoethyl ether and xylene.

Then, it was applied and dried in the same manner as in Example 1, and then subjected to a comparative test.

The results are shown in Table-8. Example 11 A test coated plate was obtained in the same manner as in Example 10, except that zinc anthranilate ( 2 n+ + ) was used instead of iron anthranilate.

The results of the comparative test are shown in Table-8.

Example 12 A test coated plate was obtained in the same manner as in Example 10, except that nickel anthranilate (N i++ ) was used instead of iron anthranilate.

The results of the comparative test are shown in Table-8.

Comparative Example 7 A coated plate for rice testing was obtained in the same manner as in Example 10 except that P-5 super was used instead of iron anthranilate.

The results of the comparative test are shown in Table-8.

Comparative Example 8 A test coated plate was obtained in the same manner as in Example 10 except that triphenylguanidine dichromate was used instead of iron anthranilate.

The results of the comparative test are shown in Table-8.

It is clear from the comparison test results table of Examples 1 to 12 and Comparative Examples 1 to 8 that the coating films obtained from the anticorrosion coating composition of the present invention are superior to those of conventional coating compositions using commercially available antirust pigments. It has excellent salt spray resistance, moisture resistance, water resistance, salt water immersion resistance, etc., and the adhesive strength of the coating film is also high, making it very useful as a rust-preventing paint.

Furthermore, the pigment used in the present invention is non-polluting, and in this respect as well, it is very useful industrially.

Claims (1)

[Scope of Claims] 1. In a paint whose main color vehicle is an alkyd resin, alkyd melamine resin, epoxy resin or maleated oil, an iron, zinc or nickel chelate compound of anthranilic acid is contained in an amount of at least 2% by volume of the solid content of the paint. A highly adhesive rust-preventing paint composition comprising: