JPS5849758A - Corrosionproofing method for metal - Google Patents

Abstract

PURPOSE:To apply a coating layer having excellent durability to the surface of a metal, with small number of coating operations, by applying a specific coating composition to the surface of the metal, and coating the resultant corrosion- resistance coating layer with a top-coating paint. CONSTITUTION:A corrosion-resistant coating layer is applied to the surface of a metal such as steel, by applying a single layer of a coating composition containing (A) 100pts.wt. of a mixture composed of 99.9-60wt% vegetable oil or fat and/or a phthalic acid resin and 0.1-40wt% tricyclodecene (derivative) and (B) 1-500pts.wt. of one or more compounds selected from an oxyacid salt such as chromic acid salt, metallic lead, and oxide (or salt) of metallic lead, to the metal surface at an average dry thickness of 50-200mu. The surface of the corrosion-resistance coating layer is coated with top-coating paint (preferably phthalic acid resin coating agent) in one or more layers, and dried to obtain a protective coating layer having excellent corrosionproofing effect to metal.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a corrosion-preventing method capable of increasing the number of coatings and forming a coating layer with excellent durability.

Various paints have been applied to various metals, mainly steel, for the purpose of protecting them. However, with recent environmental pollution such as air pollution, corrosive factors are increasing, and in order to cope with this, there is an increasing demand for a corrosion prevention method that is more durable than K.

Currently, we are producing various types of zinc rich paints, synthetic resin paints, vinyl resin paints, urethane resin paints, chloride plum paints, unsaturated/IJ ester resin paints, silicone resin paints, phenolic resin paints, etc. Coating systems based on one type or a combination of synthetic resin paints have been developed and are now in use.

On the other hand, it has excellent painting workability, low-pollution thinner can be used, and the degree of surface treatment of the object to be coated, which requires a lot of cost and number of steps during the painting process, can be relatively rough. In addition, the cost of the paint is relatively low, and the so-called oil-based or phthalate resin paints, which are a mixture of vegetable oils, 7-thalate resins, and other synthetic resin paints, have advantages that cannot be obtained with other synthetic resin paints. Used from

Has a proven track record.

Generally, it is said that the durability of metal corrosion protection by a paint film is roughly proportional to the thickness of the paint film, but the oil-based or Fi7 talic acid resin paints can only be coated in a single coat of about 40 microns at most. In order to obtain the specified film thickness required for metal inspection, it was necessary to apply multiple coats 4 to 5 times.

After application, oil-based paints or phthalate resin paints absorb oxygen in the air and become a cured film through the 11-polymerization reaction. , gradually progressing into the coating film. In this case, if the coating film is too thick, only the surface layer will harden, and the deep part of the coating will not harden very much. It becomes K. As a result, there is a large difference in hardening between the surface and the inside of the paint film, and the surface of the paint film becomes wrinkled.

Certain anti-corrosion effects and camouflaged finishes imposed on the paint film make it impossible to obtain the condition.

For the reasons mentioned above, oil-based phthalate resin paints have a coating thickness of 140 to 160, which is necessary for metal protection.
It was not possible to finish with one coat of micron thick film.

On the other hand, it is generally said that a paint coat in painting costs approximately three times as much as the paint cost.Therefore, from the viewpoint of not only saving painting costs but also shortening the painting period, it is recommended to apply 100% in one coat.
At present, there is a strong desire for a corrosion prevention method using an oil-based or 7-talic acid resin paint that can be applied to Bacron or higher.

The present invention was developed in view of the above points, and has the advantages of oil-based or phthalate resin paints, such as ease of painting workability and easy surface treatment, and allows for thick coating in one coat. To provide a corrosion-preventing method capable of forming a highly durable paint film layer, exhibiting normal paint film appearance and corrosion-proofing performance without causing insufficient drying inside the paint film or wrinkles on the paint film surface. The purpose is to

That is, one aspect of the present invention is.

(1) On the metal surface ■ Vegetable oil and/or phthalic acid resin 99.9-6a
Weight s and tricyclodecene and/or its derivative 0.1
100 parts by weight of a mixture consisting of ~40 parts by weight, and ■ at least one component selected from oxyacid salts, gold lead, oxides thereof, or salts thereof.
...1 to 500 parts by weight.

(11) coating the surface of the corrosion-resistant coating layer with at least one layer of a coating composition containing the following: A method of applying more than one layer of topcoat paint and allowing it to dry to obtain a durable coating layer.

This invention pertains to a method for preventing corrosion of metals, including various processes.

The vegetable oil used in the present invention is an esterification reaction product of various fatty acids and glycerin.

The vegetable oils and fats used in the present invention include:

Examples include N, linseed oil, linseed oil, soybean oil, cottonseed oil, rice bran oil, peanut oil, olive oil, castor oil, coconut oil, rapeseed oil, corn oil, and soybean oil. Among these, linseed oil, soybean oil, and linseed oil, which are drying oils with an iodine value of 120 or more, are most preferred in view of the drying properties of the coating film. The above-mentioned vegetable oils and fats also include blown oils and thermally polymerized oils obtained by slightly oxidizing or polymerizing natural oils.

In addition, the phthalic acid resin used in the present invention includes polyhydric alcohols, polybasic acids (containing some monobasic acids if necessary)
and a resin having an oil length of 40 to 8011i1& obtained by esterifying fatty acids by a conventional method.

Examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolethane, trimethylolethrite, diglycerol, ethylene glycol,
Furo♂ Rengelicol% 113-butylene dalicol,
Examples include dihydric or higher polyhydric alcohols such as butyne diol, neopentyl glycol, diethylene glycol, dipropylene glycol, bisphenol dioxyethyl ether, bisphenol dioxyethyl ether, and the like.

Examples of the polybasic acid (-basic acid) include succinic acid, adipic acid, maleic anhydride, maleic acid, fumaric acid, citraconic acid, itaconic acid, benzoic acid, p-teranyabutylbenzoic acid, and phthalic anhydride. acid, 0-phthal 11
% m-7thalic acid, p-phthalic acid, tetrahydrogenated phthalic anhydride, tetrachlorophthalic anhydride, Hett's acid, trimellitic acid,
Examples include monobasic polybasic acids such as trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride, or their anhydrides.

Particularly preferred are systems in which phthalic acid alone or phthalic anhydride is used as the main component in combination with other acid components.

Further, the fatty acids include, for example, linseed oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, rice bran oil fatty acid, peanut oil fatty acid, olive oil fatty acid, castor oil fatty acid, coconut oil fatty acid, 4-mucosal oil fatty acid, etc. can be mentioned.

In the coating composition conveniently used to obtain the corrosion-resistant coating layer of the present invention, it is possible to use the vegetable oil or phthalic acid resin alone, or they can be mixed in any proportion. May be used.

In the above, when the phthalic acid resin is used alone, the phthalic anhydride content is 30% or less, more preferably 25%
It is preferable that the phthalic anhydride content in the mixture is 30% by weight or less, more preferably 25% by weight or less when mixed with vegetable oil or fat. It is preferable to use the ratio t-adjusted.

In the present invention, the phthalic anhydride content in the phthalic acid resin or the mixture of vegetable oil and phthalic acid resin is 50%.
If the weight exceeds -, it becomes difficult to obtain the thick film drying effect by adding tricyclodecene and/or its derivatives, which will be described later, and it also causes a decrease in the physical properties of the #1 film, which is not very preferable.

Tricyclodecene and its derivatives used in the present invention are represented by the following structural formula.

However, R is a polyhydric alcohol residue Ro represents a calcaric acid residue. vinegar.

Examples of R in the derivatives include glyceryl/, trimethylolethane, trimethylolpro/4, pentaerythritol, diglycerol, ethylene glycol, glopylene glycol, 1,3-1 ethylene glycol, buty/diol, neo Examples include residues such as pentyl glycol, diethylene glycol, diethylene glycol, bisphenol dioxyethyl ether, and bisphenol dioxyethyl ether.

Further, as R7 in the above derivative, for example, acetic acid, ft
sbio/acid, butyric acid, Kaguro/#R1 stearic acid, crotonic acid, linoleic acid, glycolic acid, oxalic acid, succinic acid, maleic acid, fumaric acid, resorcinic acid, dioxybenzoic acid, naphthoic acid, gallic acid, phthalic acid , trimellitic acid, pyromellitic acid, acrylic acid, methacrylic acid,
Examples include residues such as monomethyl maleate, monoethyl maleate, monoglovir maleate, monooctyl maleate, monomethyl fumarate, monoethyl fumarate, monoglovir fumarate, monomethyl itaconate, and monoethyl itaconate.

Polyhydric alcohol f in the tricyclodecene derivative
The i group (a) has an ether bond with cyc eI5m, and is also bonded with K and carunic acid via an ester bond.

The mixing ratio of the vegetable oil and/or phthalic acid resin of the present invention and tri-7 clodecene and/or its derivatives is 99.9 to 60, preferably 98 to 80.
The latter has a coulometric power of 0.1 to 40 tS, preferably 2 to 20 tS, relative to the weight. In the above, if the amount of tricyclodecene and/or its derivative is less than 0.1 weight, no effect will be obtained at all, and on the contrary, if it exceeds 40 weight tst! ! ! This results in a significant decrease in film properties, increases paint costs, and reduces its value as an industrial product.

Oxygen #1 salts of the present invention include chromic acid, phosphorus # (including #combined sulfuric acid), boric acid, molybdic acid, phosphomolybdic acid, silicomolybdic acid, tungstic acid, phosphotungstic acid, silicotungstic acid, and sulfuric acid. etc. a! It is a salt consisting of acid and various metals.The main ones are strontium chromate, calcium chromate, lead chromate, zinc chromate, zinc chromate, zinc molybdate, calcium molybdate, and potassium molybdate. , lead gestate, calcium tungstate, magnesium tungstate, zinc phosphate, lead orthophosphate, lead pyrophosphate, lead metaphosphate, aluminum phosphate, tin orthophosphate, tin pyrophosphate, lead orthophosphate, tetraboron acid zinc,
Examples include zinc metaborate, lead metaborate, lead tetraborate, I4lium metaborate, lead sulfate, and ferric sulfate.

In addition, the metal of the present invention, its oxide, or its t components include metallic lead, lead zinc oxide, -lead oxide, lead dioxide, curved lead oxide, lead white, cyanamide lead, calcium lead acid, and basic sulfuric acid. Typical examples include lead and basic lead chromate.

In the present invention, at least 1 dl of the component selected from oxyacid salts, metallic lead, oxides thereof, or salts thereof is preferably phosphoric acid, boric acid, molybdic acid,
Components obtained from chromic acid, zinc, lead, and aluminum can be used as metallic lead, its oxide, or its salt, such as metallic lead, zinc oxide, -lead oxide, lead dioxide, curved lead oxide, white lead, and cyanamide. Containing at least one component selected from lead, calcium leadate, basic lead sulfate, and basic lead chromate as an essential component is more effective in drying thick coating films. Although the mechanism is not clear, it is assumed that metal ions ionized in the coating film provide a catalytic effect when tricyclodecene and/or its derivatives undergo oxidative polymerization.

In the present invention, one of the oxyacid salts, metal lead, oxides thereof, or salts thereof is combined with vegetable oil and/or phthalic acid resin (60 to 99.9% by weight) and tricyclodecene/
and /Maku are mixed in a proportion of 1 to 500 parts by weight per 100 parts by weight of a mixture of 40 to 0.1ilt*xD. It goes without saying that within the above range, if the amount of pigment exceeds 500 parts by weight, the object of the present invention cannot be achieved.
This is not preferable because the physical properties of the coating film are deteriorated.

In the present invention, coloring pigments known and generally used as paint pigments, such as iron oxide, titanium dioxide, yellow lead, cargo/black, phthalocyanine blue, zinc dioxide, calcium carbonate, precipitated sulfuric acid, etc. In addition to extender pigments such as aluminum, calcium silicate, carbonate/silica, talc, clay, mica, and silica, the anti-coating film in the method of the present invention! The compositions forming - are accompanied by oxidative polymerization during the drying of the coating film, so naphthenic acid co-f, naphthenic lead, naphthi/acid ma:/f! 7. It is a matter of course that it contains a so-called metal dryer such as calcium naphthenate, and if necessary, the surface #s4
1 agent, anti-sagging agent, anti-settling agent, anti-skinning agent, surfactant or toluene, xylene, mineral spirit,
It goes without saying that solvents such as hexane, various naphthas, and nitrofluoronol can also be added.

The method of the present invention involves uniformly mixing and dispersing the above-mentioned composition using a known general manufacturing method such as an Evadisper, a roll bar, a sand mill, a roll mill, etc. After adjusting, apply one coat to the metal surface using any known coating method such as brush, roller, Airs Gray, Airless Gray, etc. so that the average dry film thickness is 50 to 200 microns, and leave it for a specified time to dry. Finally, a corrosion-resistant coating film 1- is obtained. Next, the surface of the corrosion-resistant coating film is coated with at least 11- or more phthalic acid resin paint, iron oxide (Mlca
ceous Iron Oxide) phenolic resin paint and phthalic acid resin paint containing as t-pigment, the phenol resin paint and chlorinated rubber d1i family, the phenol resin paint and epoxy resin, and/or the polyurethane resin paint t-1. Skin cover #) Apply the same method as above to a dry thickness of about 25 to 100 microns and dry under specified conditions to obtain a retentive coating layer, resulting in a corrosion-resistant l! I membrane layer ~
It may be a laminated film consisting of a retaining coating layer.

Thus, the 900 million film layer obtained by the method of the present invention exhibits excellent effects in both metal corrosion resistance and dry photographic properties69. Alternatively, it has improved thick film drying properties that could never be achieved with phthalic acid resin paints, and its effects are significant from the standpoint of saving resources and greatly increasing work efficiency.

EXAMPLES The effects of the present invention will be specifically explained below with reference to Examples. In addition, in practical examples and comparative examples, "part" or "excellent" means part by weight or weight q.
k. Incidentally, in Examples and Comparative Examples, "part" or "part" means "part by weight" or "weight".

Examples and Comparative Examples Linseed oil (dile oil, iodine value 158
~184, viscosity #IL1.0~1.4so)'t, phthalic acid resin paint (7111 heat residue 7
091, soybean oil modified, phthalic anhydride containing t24±2chi,
oil length 65 ± 2 inches) and tricyclo[5,2,1,02e6]dec4-ene- as a tricyclodecene derivative.
Table 1 (Examples of the present invention) and II
A coating composition for forming a corrosion-resistant coating layer was exploded according to the formulation in Table J (Comparative Example).

Then, only the anticorrosive coating layer was subjected to tests for thickness and rust prevention, and the results shown in Table 41 and Table 2 were obtained.

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(1) Phenolic paint containing iron oxide pigment (A) Phenol resin varnish 30 parts (Dainippon Ink & Chemicals Co., Ltd., trade name Betucosol 2503) Scale-shaped iron oxide 50 Calcium carbonate 10 Dryer
2 [Mixture of 15-lead naphthenate 70%; 5% naphthenic acid salt 131s; 5-manganese naphthenate 17-] Mineral spirit 8 (2)
Phthalate resin paint (8) Long-oil phthalate resin varnish 47 parts [Dainippon Ink & Chemicals Co., Ltd. #Product name Petsukosol P470] Titanium dioxide 25 Calcium carbonate 15 Dryer (
Same as above) 2.7 Methyl ethyl ctoxy 0.3 Mineral spirits 10+3)
Chloride-based paint (C) Chloroble/(molecular weight 10.000) 1
2-part chlorination rough-in 5 used, oil length 65, non-volatile content 70] Talc 25 Lead oxide 15 Dryer (same as above) 1.5 Xylene -33,5 (4) Epoxy resin paint (0) Bisphenol mold epoxy resin 15116 talc
30 Titanium dioxide/
5 Polyamide tree H effect varnish
15 [Product name: Tomidena 410, manufactured by Fuji Kasei Kogyo Co., Ltd.] Xin/10 Butyl alcohol 15 Menal isobutyl ketone 10 (5) Urethane resin paint (ε) Acrylic resin varnish 40 parts [Dainippon Ink & Chemicals Co., Ltd.] mProduct name Acrylic A301) Polyisocyanate varnish 10 [Shikinichi Yakuhin Kogyo Co., Ltd. Product name Takenate 011ON) IIs Silicone solution 0. Titanium oxide 20 Butyl acetate 15 Xylene
14.9 The above-mentioned corrosion-resistant coating layer of the present invention 1 (1 time 1 jl?), 1o.

The combinations shown in Table 6 above were coated on .mu.) to obtain the coating layer of the present invention, which was then subjected to a comparative test. In addition, the above-mentioned corrosion-resistant coating layer (3 coats, 100μ) of the comparative example was coated with a combination of top coats as shown in Table 4 to obtain a coating film 1- of the comparative example, which was then subjected to a comparative test. . In addition, in the comparative example, after applying 100P of corrosion-resistant coating layer at once, the top #! I tried to apply a 1-sheet coating, but the surface of the corrosion-resistant coating I- had a lot of wrinkles, and the inside did not harden and a normal coating did not form, so I could not use it for the rust-prevention test. Ta.

7' As is clear from the test results in Tables 1 to 4 of the previous ruby, according to the method of the present invention, it is possible to form a corrosion-resistant coating layer with a thickness of *b in one go,
Moreover, there was no similar abnormality in combination with the upper coating film, and a coating film I- with extremely excellent rust prevention properties could be formed. On the other hand, in the comparative example, when obtaining corrosion protection A or L, it was necessary to apply the coating five times in order to obtain a coating film with a normal predetermined thickness.

Procedural amendment Nose Showa year, month, day Director of the Japan Patent Office Kazuo Wakasugi 1, Indication of the case 1982 Patent Application No. 147163 2, Title of the invention Method for preventing corrosion of metal 3, Person making the amendment Relationship with the case Applicant .

Name (332) Dainippon Toyo Co., Ltd. 4, Agent 5, Date of notification: April 6, 1957, 1, Particulars (1) above (in the middle): (1) Correct the above 1) Urarisura 1 in the front.

Claims (1)

[Claims] (111) ■ Vegetable oil and/or phthalic acid resin 99.9 to 60 on the metal surface
100 parts by weight of a mixture consisting of tricyclodecene and/or 0.1 to 40 parts by weight of tricyclodecene and/or its derivatives; At least one selected component: 1 to 500 parts by weight. (11) applying at least 411 layers on the surface of the corrosion-resistant coating layer; A method for preventing corrosion of metals, which includes the steps of applying a top coat of paint and drying it to obtain a protective coating layer. (2) The method for preventing corrosion of metals according to claim (1), wherein the vegetable oil is 1% linseed oil, soybean oil, or linseed oil. +31 The phthalic acid resin marked with # has an oil length of 40 to 80 and a phthalic anhydride content of 25 or less by weight. A method for preventing corrosion of metal according to claim (1). (4) The oxyacid can be obtained from phosphoric acid, boric acid, molybdic acid, chromic acid, and zinc, lead, or aluminum.
It is at least one type of salt. Claim No. (1)
Corrosion prevention method for metals described in Section 1. (5) #Metal lead, its oxide, or its salt is metal lead, lead zinc oxide, -lead oxide, lead dioxide, trilead tetroxide, white lead, lead cyanamide, and calcium leadate. A method for preventing corrosion of metal according to claim (1), in which at least 1% of basic lead sulfate or basic lead chromate is used. (6) The topcoat paint is a phthalate resin paint. A method for preventing corrosion of metal according to claim (1). (7) The method for preventing corrosion of metals according to claim II (1), wherein the top coat is a phenolic resin paint containing iron oxide as a pigment and a phthalic acid resin paint, which is allowed to contain 1% abrasive. (8) The method for preventing corrosion of metal according to claim 11(1), wherein the top coat is a layered coating of a phenolic resin paint containing iron oxide as a pigment and a chloride plum paint. (9) The metal coating according to claim (1), wherein the top coat is a layered coating of a phenolic resin paint containing iron oxide as a pigment and a polyurethane resin paint and/or a urethane resin paint. Corrosion prevention method.