JPH04311773A - Paint composition - Google Patents

Abstract

PURPOSE:To provide a paint composition containing powder of an acidic organic phosphoric acid amine salt compound, capable of imparting the surface of a coating film with rust-proofing effect lasting over a long period and converting brown rust into colorless substance and useful for the coating of steel structure, metallic ware, general buildings, etc. CONSTITUTION:The objective composition contains 2-75wt.% (preferably 5-50wt.%) (based on the solid content of the paint) of an organic phosphoric acid amine salt compound powder having particle size of about 1-30mum and a water-solubility of preferably about <=0.5g/100ml and produced by reacting (A) an acidic organic phosphoric acid salt having one or more acidic phosphoric acid groups of formula I or formula II with (B) one or more kinds of amine compounds preferably selected from melamines, guanamines, imidazoles and aromatic amines.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to tanks, bridges, vehicles,
The present invention relates to a coating composition for preventing rust and rust contamination of iron structures such as ships and plants, light electrical equipment, metal products such as steel furniture, and general buildings.

0002

[Prior Art and Problems to be Solved by the Invention] Conventionally, lead-based rust preventive pigments such as red lead, litharge, and lead cyanamide, zinc chromate, and chromium have been used for iron structures and metal products. It consists of a combination of an undercoat anti-corrosion paint containing a chromate compound such as strontium oxide, a phosphate compound such as zinc phosphate, or aluminum phosphate, and a top coat that does not contain these anti-rust pigments and is intended for an aesthetic finish. It has a multi-layer coating.

[0003] Normally, undercoat anti-rust paints have the effect of slowing down the corrosion rate of base metals, but they have little effect on preventing rust from forming in pinholes and scratches in the paint film, and once rust has formed, it is difficult to prevent rust from occurring due to rainwater or water. Condensation water, and even seawater spray on ships and steel structures in coastal areas, causes rust fluid to flow out.
This usually stains the surface of the topcoat film with a brown color, resulting in an unsightly appearance, and conventional combinations of undercoat and topcoat have not been able to prevent such rust stains.

[0004] Furthermore, JP-A-58-219273 discloses that the above-mentioned rust staining can be prevented by containing a salt consisting of a polyvalent metal cation such as calcium and an organic polyphosphonic acid in the paint. ing. However, even if the above-mentioned salt is contained, if a small amount is used, the effect of preventing rust contamination is small, and if a large amount is used, not only the rust prevention property will be reduced, but also the resulting coating film will be more likely to blister. There were fatal problems, and there were also problems in that it was difficult to pulverize and the kneading and dispersion time was correspondingly long.

[0005]

[Means for Solving the Problems] In view of the above problems, the present inventors have developed a paint that has rust prevention properties equivalent to conventional rust prevention paints and that protects the paint surface from rust contamination over a long period of time. As a result of intensive studies, the present invention has been arrived at. The present invention applies an acidic organic phosphate amine salt compound powder to a conventional paint, that is, a paint composition consisting of a binder resin, a solvent, an extender pigment, a coloring pigment, a rust preventive pigment, an additive, etc., which are blended as necessary. The present invention relates to a coating composition containing the following.

The present invention will be explained in detail below. The acidic organic phosphate amine salt compound used in the present invention has a functional group in one molecule.

[0007]

[Chemical formula 1]

It is a compound obtained by reacting an acidic organic phosphoric acid having one or more acidic phosphoric acid groups represented by the following formula with an amine compound. Specific examples of the acidic organic phosphoric acid include the following.

[0009]

[Chemical 2]

[0010] Also included are acidic organic phosphoric acid oligomers having the above-mentioned acidic phosphoric acid group in their structure. Examples of the amine compounds used in the reaction with acidic organic phosphoric acid to produce acidic organic phosphoric acid amine salt compounds include aliphatic primary amines such as butylamine, amylamine, hexylamine, octylamine, etc. , dipropylamine,
Aliphatic secondary amines such as dibutylamine and diamylamine; aliphatic tertiary amines such as triethylamine, tripropylamine, and tributylamine; alicyclic amines such as amylamine, diallylamine, triallylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine; Aromatic amines such as aniline, dimethylaniline, toluidine, benzylamine, aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, aromatic diamines such as phenylenediamine, diaminodiphenylmethane, melamine, and benzoguanamine, Representative examples include guanamines such as acetoguanamine, formoguanamine, phenylacetoguanamine, and methoxyguanamine, imidazoles such as imidazole, 2-methylimidazole, and 2-phenylimidazole, dicyandiamide, pyridines, and pyrazines. Among these, the above-mentioned melamine, the above-mentioned guanamines, the above-mentioned imidazoles, and the above-mentioned aromatic amines are particularly preferred, and the salts obtained by reaction with acidic organic phosphoric acid are poorly soluble in water.

[0011] The acidic organic phosphoric acid amine salt compound used in the present invention can be prepared by dissolving the amine compound in water, hot water, or a polar solvent such as alcohol, and dropping the acidic organic phosphoric acid compound into the solution. By doing so, both react and can be manufactured, but the manufacturing method is not limited to these. Both reactions are acid-base neutralization reactions, and when they react, a salt (i.e., an acidic organic phosphoric acid amine salt compound) is produced in the solution, and the salt is purified, dried, and pulverized to a particle size of approximately 1. ~30 μm is used.

[0012] When the paint of the present invention is applied indoors, there is no particular problem; however, when applied outdoors, the acidic organic phosphate amine salt compound powder has a solubility in water of about 5 g/100 ml or less. Preferably. These poorly soluble materials have low solubility in the paint film due to rainwater, etc., so they have excellent rust prevention and rust stain prevention effects, and are also soluble in organic solvents commonly used in paints. Therefore, even if it is blended into a paint, it does not cause the paint to gel, and has excellent storage stability.

[0013] The acidic organic phosphoric acid amine salt compound powder is present in an amount of 2 to 75% by weight, preferably 5 to 50% by weight in the solid content of the paint.
It is appropriate to include it. The coating composition of the present invention is
As mentioned above, the coating composition is the same as the conventionally known coating composition except that the acidic organic phosphoric acid amine salt compound powder is blended. That is, examples of the binder resin include acrylic resin, alkyd resin, vinyl chloride vinyl acetate copolymer resin, oil-free polyester resin, fluororesin, silicone resin,
Examples include epoxy resins, unsaturated polyester resins, polyurethane resins, and chlorinated rubber resins. These resins can be used alone, or two or more compatible resins can be used in combination. Further, a mixture of modifying resins such as petroleum resin and xylene resin can also be used.

Examples of the solvent include various solvents such as aliphatic or aromatic hydrocarbon, alcohol, glycol ether, glycol ether ester, ketone, ester, and water. Typical extender pigments include calcium carbonate, barium sulfate, and talc; typical coloring pigments include titanium dioxide and iron oxide; and rust preventive pigments include zinc phosphate and phosphoric acid. Aluminum, sodium zinc molybdate,
Typical examples include barium metaborate, zinc white, potassium chromate, zinc chromate, red lead, and litharge.

The coating composition of the present invention can be applied to various types of coatings such as organic solvent type, water-based type, and non-solvent type, and drying methods include room temperature drying type, forced drying type, baking drying type, and active energy ray type. It can be applied to various types of paints such as hardening type. In addition to being applied directly to iron parts, the coating composition of the present invention can be used as a top coat on top of a general undercoat. In addition, even if the objects themselves do not rust, such as concrete structures or wooden buildings, they may be used for finishing objects that may be contaminated by rust due to their proximity to iron parts. can also be used.

The coating amount of the coating composition may be determined by the coating amount of the acidic organic phosphate amine salt compound powder necessary for preventing rust staining, and the amount of the compound is usually 5 to 60 g/m2, preferably 10 to 40 g/m2. A coating amount such that The method for applying the coating composition of the present invention is to remove and clean dust, oil, rust, etc. adhering to the surface of the object to be coated (it may be a pre-painted object), and then use a brush, roller, etc. It can be painted by normal painting means such as spraying.

[0017]

[Effects of the Invention] The coating composition of the present invention has a novel function of preventing rust on iron structures, and at the same time, converting brown rust generated from defective parts of the coating film into a colorless substance to preserve the aesthetic appearance. It is a paint composition. This can protect ships, bridges, vehicles, and the exterior walls of metal or concrete buildings from corrosion of iron parts and brown rust contamination.

[0018]

EXAMPLES The present invention will be further explained below with reference to synthesis examples and examples. In addition, "part" and "%" in Examples are shown on a weight basis.

Synthesis Example 1 <Preparation of monobutyl phosphate melamine salt compound powder> Deionized water was poured into a flask equipped with a stirrer and a reflux condenser.
00 parts, 126 parts of melamine (manufactured by Katayama Chemical Co., Ltd.) 1
The temperature was raised to 00°C to dissolve the melamine. Then, while stirring, add monobutyl phosphate (trade name: MP, manufactured by Daihachi Kagaku Co., Ltd.).
-4) 77 parts were added dropwise from the dropping funnel over 30 minutes, and stirring was continued for 1 hour at 100°C to form a white precipitate. After cooling to room temperature, the resulting white precipitate was washed with deionized water, filtered, dried at 110°C, and ground to obtain a white powder with an average particle size of 3 μm. (Pigment A)

0020
] Synthesis Example 2 <Preparation of di-2-ethylhexylphosphate imidazole salt compound powder> In a flask equipped with a stirrer and a reflux condenser, 2500 parts of ethylene glycol monoethyl ether,
187.2 parts of benzoguanamine was charged and the temperature was raised to 50°C to dissolve the benzoguanamine. Then, while stirring, 322 parts of di-2-ethylhexyl phosphate (trade name DP-8, manufactured by Daihachi Kagaku Co., Ltd.) was added dropwise from the dropping funnel over 30 minutes, and stirring was continued at 50°C for 1 hour to form a white precipitate. I let it happen. After cooling to room temperature, the white precipitate formed was washed with deionized water, filtered, dried at 110°C, and ground to obtain a white powder with an average particle size of 3 μm. (Pigment B)

Synthesis Example 3 <Preparation of Phytic Acid Melamine Salt Compound Powder> In a flask equipped with a stirrer and a reflux condenser were charged 2500 parts of deionized water and 126 parts of melamine, and the mixture was heated to 100° C. and dissolved. Then, while stirring, 220 parts of a 50% phytic acid aqueous solution (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added dropwise from the dropping funnel over 30 minutes.
Subsequently, stirring was continued at 100° C. for 1 hour to generate a white precipitate. After cooling to room temperature, the white precipitate formed was washed with deionized water, filtered, dried at 110°C, and ground.
A white powder with an average particle size of 3 μm was obtained. (Pigment C)

00
22] Synthesis Example 4 <Preparation of phytic acid benzoguanamine salt compound powder> In a flask equipped with a stirrer and a reflux condenser, 2500 parts of ethylene glycol monoethyl ether and 1 part of benzoguanamine were added.
87.2 parts were charged and the temperature was raised to 50°C to dissolve benzoguanamine. Then, while stirring, the phytic acid 50
% aqueous solution was added dropwise from the dropping funnel over 30 minutes, and stirring was continued for 1 hour at 50°C to form a white precipitate. After cooling to room temperature, the white precipitate formed was washed with deionized water, filtered, dried at 110°C, and ground.
A white powder with an average particle size of 3 μm was obtained. (Pigment D)

00
23] Synthesis Example 5 <Preparation of phytic acid-2-phenylimidazole salt compound powder> 2000 parts of ethylene glycol monoethyl ether and 864 parts of 2-phenylimidazole were charged into a flask equipped with a stirrer and a reflux condenser, and the temperature was raised to 50°C. warm, 2
- Phenylimidazole was dissolved.

[0024] Then, while stirring, add 50% of the phytic acid.
1320 parts of the aqueous solution was added dropwise from the dropping funnel over 1 hour.
Subsequently, stirring was continued at 50° C. for 1 hour, producing a pale yellow precipitate. After cooling to room temperature, the resulting pale yellow precipitate was washed with deionized water, filtered, dried at 110°C and pulverized to obtain a pale yellow powder with an average particle size of 3 μm. (Pigment E)

[
Synthesis Example 6 <Preparation of phytic acid N,N-dimethylaniline salt compound powder> In a flask equipped with a stirrer and a reflux condenser, 220 parts of the above 50% phytic acid aqueous solution and 690 parts of deionized water were charged and mixed by stirring. while N,N-dimethylaniline 1
21.2 parts were added dropwise from the dropping funnel over 30 minutes, and stirring was continued for 1 hour to form a white precipitate. The precipitate was filtered, washed with methanol, dried at 110°C, and ground to obtain a white powder with an average particle size of 5 μm. (Pigment F
)

Example 1 5 parts of pigment A, 40 parts of alkyd resin varnish (trade name: "Beccosol J557" manufactured by Dainippon Ink Chemical Industries, Ltd.), 15 parts of rutile titanium oxide, and 22 parts of mineral spirit were kneaded in a ball mill for 10 hours. After that, 15 parts of the above varnish and 3 parts of additives such as desiccants were added to prepare a paint.

[0027] The particle size of the obtained paint is JIS K540.
The diameter was 5 μm using the 4.4 mm A method. This paint,
It was applied to a degreased polished mild steel plate using an air spray gun to a dry film thickness of 35 μm and allowed to air dry for 7 days. The obtained coated plate was subjected to a salt spray test and a moisture resistance test. The results are shown in Table 2.

Examples 2 to 8 Paints were prepared in the same manner as in Example 1 from the ingredients shown in Table 1 below, and coated plates were prepared and tested. The results are shown in Table 2. ━━━
━━━━━━━━━━━━━━━━━━━━
Table 1
Example
━━━━━━━━━━━━━
━━━━━━━━━━
2 3 4 5
6 7 8━━━━━━━━━━
━━━━━━━━━━━━━━━━━━━━━━━━
Alkyd resin varnish 50 50
50 50 50 50
50 Pigment A 15
25 Pigment B
15 Pigments
C
15 Pigment D

15 Pigment E

15 Pigment F

15 Titanium oxide
15 15 15
15 15 15 15
Mineral Spirit 17 17
17 17 17 17 1
7 Additives 3
3 3 3 3
3 3━━━━━━━━━━━━━━━
━━━━━━━━━━━━━━━━━━━

[0029]
Example 9 15 parts of pigment A, acrylic polyol varnish (trade name "Acridic A-801" manufactured by Dainippon Ink Chemical Industries, Ltd.)
40 parts, rutile titanium oxide 15 parts, xylene 10 parts,
After kneading 10 parts of butyl acetate in a ball mill for 10 hours, 10 parts of the above varnish was further added to prepare a main ingredient. The particle size of the obtained base agent was 5 μm.

A curing agent solution [60 parts of a polyisocyanate compound (trade name "Sumidur 75" manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 40 parts of butyl acetate] is added to 100 parts of the main resin. 18.7
A paint was prepared. After adjusting the viscosity of this paint with 25 parts of xylene, 5 parts of butyl acetate, and 5 parts of ethylene glycol monoethyl ether acetate, a coated plate was prepared in the same manner as in Example 1 and used for testing.

Example 10 15 parts of pigment A, 45 parts of alkyd resin varnish (trade name "Hitaloid 235-50" manufactured by Hitachi Chemical Co., Ltd.), 15 parts of rutile titanium oxide, and 7.5 parts of xylene were kneaded in a ball mill for 10 hours. After combining, 12.5 parts of melamine resin (trade name "Yuban 20SE-60" manufactured by Mitsui Toatsu Chemical Co., Ltd.) and 5 parts of n-butanol were further added to prepare a paint.

The particle size of the resulting paint was 5 μm. This paint was mixed with 15 parts of xylene and n-
After adjusting the viscosity with 5 parts of butanol, dry film thickness was 35 μm using an air spray gun on a defatted polished mild steel plate.
After setting for 20 minutes, apply 120
C. for 30 minutes to prepare a coated plate, which was then used for testing.

Comparative Example 1 A paint was prepared in the same manner as in Example 1 except that condensed aluminum phosphate was used in place of Pigment A, and a coated plate was prepared and tested. The results are shown in Table 2.

Comparative Example 2 A paint was prepared in the same manner as in Example 1 except that 5 parts of calcium phytate powder (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used instead of 5 parts of pigment A, and a coated plate was prepared and tested. provided. The results are shown in Table 2.

Comparative Example 3 A paint was prepared in the same manner as in Example 3 except that 25 parts of the calcium phytate powder was used instead of 25 parts of Pigment A, and a coated plate was prepared and tested. The results are shown in Table 2.

[0036]

[Table 1]

Note 1) JIS K5400 7.8
According to. Make a cross cut in the upper half of the painted board, and make 12
0 hour salt spray test (1) Rust width at cut part...Width of rust progression from the cut part ○: Within 2 mm on one side, △: 3 to 4 mm on one side
, ×: 2 mm or more on one side, (2) Flow of rust juice... Distance from the bottom end of the cut where brown rust juice flowed ○: Within 10 mm, △: 11 to 29 mm, ×: 30
mm or more, (3) Blisters other than the cut part○: No blisters, △: Slightly blisters, ×: Significant blistersNote 2) According to 5.18 of JIS K5652○
: No abnormality, △: Blister area less than 10%, ×: Blister area 10% or more. As is clear from Table 2, the coating composition of the present invention in Examples has excellent corrosion resistance, etc., and the flow of rust juices has been reduced. It was not noticeable, and no coating defects such as blisters occurred.

On the other hand, in Comparative Example 1 in which condensed aluminum phosphate, which is a conventional rust preventive agent, was blended, corrosion resistance was excellent, but the flow of rust liquid was noticeable. Furthermore, in Comparative Examples 2 and 3 in which a polyvalent metal cation salt of phytic acid was blended, when the amount was small, the flow of rust juice was noticeable, and conversely, when the amount was large, many blisters occurred.

Claims (2)

[Claims] 1. A coating composition comprising an acidic organic phosphate amine salt compound powder. 2. The amine compound forming the acidic organic phosphate amine salt compound powder is at least one selected from the group consisting of melamines, guanamines, imidazoles, and aromatic amines. paint composition.