JPS5847428B2 - Kousetsuchiyakuseiboseitoriyousobutsu - Google Patents

Description

[Detailed description of the invention] The present invention relates to anti-rust paint compositions.

More specifically, the present invention relates to a coating composition that does not contain harmful substances and has excellent adhesive coating film density and rust prevention properties on metal substrates.

Typical rust-preventive pigments conventionally used in rust-preventive paints include lead-based pigments such as red lead, and chromate-based pigments such as zinc chromate and strontium chromate. Rust pigments pose a serious pollution problem and become a source of water pollution, requiring equipment to prevent them from escaping from factories and workshops, 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 [Z
n3(PO4)2・2H20 or 4H20], silica phosphate (2Si02・P205), titanium phosphate (3Ti
O2・P205), calcium phosphosilicate, barium metaborate (BaB204・H20), calcium borosilicate, basic iron oxide, etc. are known.

These anti-corrosion pigments are inhibitor pigments based on the anti-rust 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. sex is significantly reduced.

On the other hand, inorganic pigments containing aluminum, silicon, and iron as main components have been developed as rust-preventing pigments based on a rust-preventing mechanism based on the adsorption of pigments onto metal substrates.

When these pigments are added to paints, they are effective in preventing the formation of blisters in the paint film, but their effectiveness in blocking corrosive liquids and gases such as water and sulfur dioxide gas is insufficient, and therefore the rust prevention of the paint film is insufficient. Sex is not enough.

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

That is, the present invention provides a paint in which an alkyd resin, an alkyd melamine resin, an epoxy resin, or a maleated oil is the main color vehicle, and in which an iron, zinc, nickel, or copper chelate compound of 8-/n drooxyquinoline is added to the paint solid. It relates to a highly adhesive rust-preventing paint composition characterized by containing more than half the volume of the present invention.

In other words, the anticorrosive paint formed by adding 8-hydroxyquinoline metal chelate to a resin composition for forming a coating film has excellent adhesion to metal substrates such as steel, and the interface between the coating film and the metal substrate is excellent. Because of its high adhesive fracture resistance, it can highly prevent the occurrence of blisters.

In addition, 8-hydroxyquinoline 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 also prevents the infiltration, permeation and diffusion of corrosive liquids and gases, and has excellent rust prevention properties.

The metal chelate compound of 8-hydroxyquinoline used in the present invention has the structural formula ++
, Ni ++, Ni +++, Cu 10 or Cu+ 10.

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

In the present invention, at least one of the above chelate compounds
The seeds are added to the paint in an amount equal to or more than 2 volumes φ of the solid content of the paint.

That is, if the amount of the chelate compound added is less than 2 volumes, 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. Coating film forming properties Since various physical properties such as the strength of the coating film and the ability to shield corrosive factors are reduced, it is preferable that the volume is less than about 40 φ, and the addition of about 3 to 25 volumes is particularly effective. A rust prevention effect can be obtained.

Further, a coating film formed by adding a chelate compound of Fe++++Zn or Ni++ among the above-mentioned chit, -trito compounds has an even better rust-preventing effect and is preferable as a rust-preventing paint.

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 paints can be added with only the metal chelate compound of 8-hydroxyquinoline, or in combination with ordinary extender pigments and/or coloring pigments, or even other non-polluting rust-preventing pigments. can also achieve that goal.

These extender pigments, coloring pigments, non-polluting rust preventive pigments, etc. can be added up to 43 volumes 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 8-hydroxyminoline shown in the examples in water was measured by the following method.

First, put about 21ml of pigment into a hard beaker, add about 200ml of ion-exchanged water, and add about 200ml of ion-exchanged water, and add 50ml of pigment to it while stirring thoroughly.
After keeping the temperature at 60°C for 1 hour, the solution was allowed to cool slowly to room temperature, and after checking the liquid temperature, the solution was passed through the oven several times using oven paper A4 specified in JIS-P-3801.

Accurately collect 100rrll of this furnace liquid into an evaporation dish with a known weight using a whole pipette, dry it in a dryer at 110±5°C until it reaches a constant weight, and then put it in a desiccator.
After cooling, the weight was measured, and the solubility of each pigment in the solution 100 was determined from the amount remaining after evaporation.

Example 1 Soybean oil modified long oil phthalic acid resin varnish (oil length 62φ, non-volatile content 70%) Zinc white, iron oxide, talc and 8-hydroxyquinoline iron (Fe110) (specific gravity 2.01 solubility S
21.

An appropriate amount of xylene was added to 2.0 x 10-2 g/100-1 aqueous solution, and the mixture was uniformly kneaded in a pot mill according to the formulation shown in Table 1. A dryer was then added to create 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 8-hydroxyquinoline zinc (Z
n++χ Specific gravity 1.7 Solubility 0.2XIO”g/1
0 0772/! An aqueous solution (below) was added to prepare a test paint in the same manner as in Example 1 using the formulations shown in Table 1, and then painted and subjected to a comparative test.

The results are shown in Table 2.

Example 3 Copper 8-hydroxyquinoline (Cu
++) (Specific gravity 1.64 Solubility 0.3 xio 'y/
Example 1 using the mixture of ioo (aqueous solution) and other pigments as shown in Table 1.
The paint and test coatings were treated in the same manner as above.

The test results are shown in Table 2. Comparative Example 1 Soybean oil-modified long-oil phthalic acid resin varnish (oil length 62%, non-volatile content 70%) Zinc white, iron oxide, talc, P-5 super with an appropriate amount of xylene added and carried out using the formulation shown in Table 1. Example 1
Paint and test coatings were prepared in the same manner as above.

The test results are shown in Table 2. Comparative Example 2 An appropriate amount of xylene was added to soybean oil modified long oil phthalic acid resin varnish (oil length 62%, nonvolatile content 70φ), zinc white, iron oxide, talc, triphenylguanidine dichromate,
Paints and test coated plates were prepared in the same manner as in Example 1 using the formulations shown in Table 1.

The test results are shown in Table 2.

Example 4 Water-soluble maleated linseed oil (non-volatile content, factor 85: zinc white, talc, 8-hydroxyquinoline iron (Fe++))
An appropriate amount of water was added to the mixture, and the composition shown in Table 3 was kneaded in a three-roll mill to prepare a paint, which was then used as a trial 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 (nonvolatile content: 85%), zinc white, talc, 8-hydroxyquinoline zinc (Zn++
) and an appropriate amount of water to prepare paints and test coated plates 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 Water-soluble maleated linseed oil (85% non-volatile content), zinc white, talc, copper 8-hydroxyquinoline (Cu++)
A suitable amount of water was added to the mixture to prepare paints and test coated plates 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 Add an appropriate amount of water to water-soluble maleated linseed oil (non-volatile content 85%), zinc white, talc, and P-5 super, and use the formulation shown in Table 3 to prepare paint and test materials as in Example 4. Created a painted board.

The test results are shown in Table 4. Comparative Example 4 Appropriate amount of water-soluble maleated linseed oil (non-volatile content, 85%), zinc white, talc, triphenylguanidine dichromate (trade name, Organochrome) A paint and a test coated plate were prepared in the same manner as in Example 4 by adding water and using the formulation shown in Table 3.

The test results are shown in Table 4.

Example 7 Short oil alkyd resin (oil length 60%, non-volatile content 50%),
Add an appropriate amount of xylene to titanium oxide, precipitated barium sulfate, 8-hydroxyquinoline iron (Fe++), and melamine resin varnish (non-volatile content: 60%), and uniformly knead with a pot mill according to the composition shown in Table 5. A test paint was created.

This paint was air-sprayed 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 60%, non-volatile content 50%),
Titanium oxide, precipitated barium sulfate, 8-hydroxyquinoline nickel (N; 10+) (specific gravity 1.5 solubility 8
A suitable amount of xylene was added to the melamine resin (3.2×10-2 phantom 0.11°C aqueous solution), and a paint and a test coated plate were prepared in the same manner as in Example 7 using the formulations shown in Table 5.

The test results are shown in Table 6. Example 9 An appropriate amount of xylene was added to short oil alkyd resin (oil length 60%, nonvolatile content 50φ), titanium oxide, precipitated barium sulfate, zinc 8-hydroxyquinoline (Zn++), and melamine resin, and the mixture shown in Table 5 was added. A paint and test coated plate were prepared in the same manner as in Example 7 using the same formulation.

The test results are shown in Table 6.

Comparative example 5 Short oil alkyd resin (oil length 60%, non-volatile content 50%)
, titanium oxide, precipitated barium sulfate, P-5 super,
A suitable amount of xylene was added to the melamine resin, and paints and test coated plates were prepared in the same manner as in Example 7 using the formulations shown in Table 5.

The test results are shown in Table 6. Comparative Example 6 Short oily alkyd resin (oil length 60%, non-volatile content 50%),
Titanium oxide, precipitated barium sulfate, triphenylguanidine dichromate/(trade name, Organo Chromium),
Appropriate amounts of key and silene were added to the melamine resin, and paints and test coated plates were prepared in the same manner as in Example 7 using the formulations shown in Table 5.

The test results are shown in Table 6.○ Example 10 Epoxy resin varnish (bisphenol type epoxy resin,
A suitable amount of xylene was added to a mixed solution of ethylene glycol monoethyl ether and xylene (nonvolatile content 70%), iron oxide, talc, and 8-hydroxyquinoline iron (Fe++), and the mixture was prepared using a pot mill as shown in Table 7. Knead the mixture uniformly and apply polyamide resin varnish (
A test paint was prepared by adding a mixed solution of ethylene glycol monoethyl ether and xylene with a non-volatile content of 50%.

This paint 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 In the formulation of Example 10, 8-hydroxyquinoline iron was replaced with 8-hydroxyquinoline zinc (2
A test coated plate was obtained in the same manner except that n++) was used.

The results of the comparative test are shown in Table 8. Example 12 In the formulation of Example 10, 8-hydroxyquinoline copper (Cu+
A test coated plate was obtained in the same manner except that +) was used.

The results of the comparative test are shown in Table 8. Comparative Example 7 A test coated plate was obtained in the same manner as in Example 10, except that P-5 super was used instead of iron 8-hydroxyquinoline.

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 8-hydroxyquinoline.

The results of the comparative test are shown in Table 8. Examples 1 to 12
It is clear from the comparison test results table of Comparative Examples 1 to 8 that the coating film obtained from the anti-rust paint composition of the present invention has better salt water resistance than that of the conventional paint composition using a commercially available anti-corrosion pigment. It had excellent sprayability, moisture resistance, water resistance, salt water immersion resistance, etc., and the adhesive strength of the coating film was 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, an alkyd melamine resin, an epoxy resin or a maleated oil, an iron, zinc, nickel or copper chelate compound of 8-hydroxyquinoline is added to the solid content of the paint. A highly adhesive rust-preventing paint composition characterized by containing 2 or more volumes of.