JPH01210475A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition which can form a cured film within a short time, can be handled without any danger and can prevent the deposition of, for example, marine life for a long time, by mixing a paint with a reaction product of a hydroxylated liquid diene polymer with maleic acid (anhydride). CONSTITUTION:A coating composition is obtained by kneading a paint with a reaction product of a hydroxylated liquid diene polymer (e.g., hydroxylterminated polybutadiene) with maleic acid or maleic anhydride. This composition as such or mixed with a solvent is applied to an object and is heated for a short time to form a cured film, and the cured film is excellent in an effect of preventing the deposition of marine life and can retain its effect for a long time. Further, this paint composition can be handled without any danger and is excellent in safety. Further because of its excellent waterproofness and rust-preventive property, it can be effectively used as a marine paint, a paint for underwater and submarine pipes, alga-repelling paint, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coating composition, and more particularly to a coating composition capable of preventing the adhesion of marine organisms.

[Prior art and problems to be solved by the invention] Conventionally, maleated polybutadiene obtained by adding maleic anhydride to liquid polybutadiene was esterified with an unsaturated fatty acid glycidyl ester, and then neutralized using a base. A coating composition in which a metal salt is added is known (Japanese Patent Publication No. 60-53017). This coating composition is a water-based coating that does not use organic solvents, and its dried coating film is water resistant. Because of its excellent properties, it is preferably used as a paint for ships and marine structures.

However, this paint has disadvantages in that it takes a long time to obtain a cured coating film, and aquatic organisms such as Fujibo, sea lettuce, and sea squirt tend to adhere to the coating film.

Additionally, paints that contain heavy metal compounds such as mercury and copper, and paints that contain organic compounds such as alkaloids, are known, but these do not have sufficient effectiveness in preventing marine organisms from adhering to them, and the heavy metals and alkaloids are toxic substances. Therefore, it is dangerous to handle, and there is a risk of it leaching into the sea and contaminating the ocean.

[Means to solve the problem]

As a result of repeated studies to obtain a coating composition free from such drawbacks, the present inventor found that a coating containing a reaction product of a hydroxyl group-containing liquid diene polymer and maleic acid or maleic anhydride is effective. They have found that this is the case and have completed the present invention.

That is, the present invention provides a coating composition comprising a coating composition containing a reaction product of a hydroxyl group-containing liquid diene polymer and maleic acid or maleic anhydride.

The hydroxyl group-containing liquid diene polymer used in the present invention has a hydroxyl group inside or at the end of the molecular chain and has a number average molecular weight of 300 to 25,000, preferably 500 to 10.
000 liquid diene polymer is used. Here, the content of hydroxyl groups is usually 0.1=l Omeq/g, preferably 0.3 to 7 meq/g.

Examples of these liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specifically, butadiene homopolymer.

Isoprene homozelimer, chloroprene homopolymer,
Examples include butashiconine-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, and the like. These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in a liquid reaction medium in the presence of hydrogen peroxide.

In the present invention, a product obtained by reacting the hydroxyl group-containing liquid diene polymer with maleic acid or maleic anhydride is blended into a paint. The reaction conditions for both are as follows: 5 to 30 parts by weight, preferably 10 to 25 parts by weight, of maleic acid or maleic anhydride are mixed with 100 parts by weight of the hydroxyl group-containing liquid diene polymer; Preferably, the reaction may be carried out at a temperature of 50 to 120°C for 2 to 30 hours, preferably 5 to 25 hours. Here, if the blending amount of maleic acid or maleic anhydride is less than the above ratio, the hydroxyl group-containing liquid diene polymer will not be sufficiently maleated, making curing difficult; Containing a large amount of acid is undesirable because it results in a lack of storage stability.

In the present invention, the paint to which the above reaction product (maleide) is blended may be either a natural paint or a synthetic paint, and specifically, copal and danfur. Examples include natural paints such as Urac, and synthetic paints such as alkyd paints, melamine paints, epoxy paints, and acrylic paints. As for the blending ratio, per 100 parts by weight of paint,
If there is too little Malayan, marine organisms will easily adhere to it, and even if it is blended in an amount exceeding the above ratio, there will be no effect commensurate with the amount blended.

The coating composition of the present invention can be obtained by blending and kneading the above raw materials. The kneading may be carried out by a commonly used method, such as melt-kneading using a Banbury mixer or the like at a temperature of 0 to 120°C, preferably 15 to 70°C, for 30 seconds to 1 hour, preferably 1 minute to 30 minutes. do it.

Since the coating composition of the present invention forms a cured product by heating for a short time, when used as a coating material, a cured coating film can be obtained in a short time. When used as a paint, the composition may be used alone or after being mixed with a suitable solvent if necessary, using a spray gun.

It can be applied to the target object using a brush, roll coater, flow coater, etc. and heated for a short time. Furthermore, since the composition of the present invention has the effect of preventing the adhesion of aquatic organisms, it can be used on ship bottoms, underwater/undersea piping, and marine structures.

Suitable for painting fishing nets, etc. Note that there are various aquatic organisms that are the subject of the present invention, such as (
Fujibbo species such as Ra Fujibbo, Shirusushi Fujibbo, Red Fujibbo, and Shiro Fujibbo; Oysters.

Oysters such as yellowtail; sea squirts such as white sea squirt and eboya; moss insects such as bush moth, long-bearded moth, chigo moth, and membranipora; green lettuce.

Examples include seaweed such as aonori.

〔Example〕

Next, the present invention will be explained by examples.

Production example Polybutadiene containing a hydroxyl group at the end (R-45HT
, manufactured by Idemitsu Arco ■, number average molecular weight 2800° hydroxyl group content 0.79a+eq/g) 100 parts by weight and 4-
0.2 parts by weight of t,-butylcatechol was stirred at 30°C for 5 minutes, 8 parts by weight of maleic anhydride was added, and the mixture was heated at 80°C.
After mixing for 8 hours, the temperature was lowered to room temperature to obtain a reaction product (maleide). The obtained maleate has an acid value of 43 KOH/gJ and a degree of 150 poise/30
It was °C.

Example 1 50 parts by weight of the maleate obtained in the production example was added to 100 parts by weight of an alkyd resin paint (Sanphthal 30. Nippon Paint ■, acrylic modified phthalic acid paint), and 25 parts by weight of the maleate obtained in the production example was added.
A coating composition was obtained by kneading at °C for 30 minutes.

The obtained composition was placed on a 0.8 x 100 x 150 steel plate.
．． The coating was applied to a thickness of 3 rMfn and cured at 140° C. for 30 minutes to obtain a coated steel plate.

When this steel plate was suspended 3 meters below the sea surface and the status of marine life adhesion was observed after 6 months, although some dirt was observed on the surface, no marine life was observed.

Example 2 The same operation as in Example 1 was performed except that epoxy resin paint (Apppe Eboxy Finish, manufactured by Hhon Paint ■) was used instead of alkyd resin paint, and the results showed that marine organisms No adhesion was observed.

Comparative Example Polybutadiene (1,2-vinyl type 89% and 1.4
-) Lance type 11% structure, number average molecular weight 1050) 1
00 parts by weight, 20 parts by weight of maleic anhydride, and 0.2 parts by weight of 2,6-ditertiary-butyl-4-methylphenol as a polymerization inhibitor were placed in a flask, the atmosphere was replaced with nitrogen gas, and the mixture was heated to 180-190" while stirring. After heating at 100-120°C for 6 hours, the content temperature was lowered to 80°C to fully heat the maleic anhydride.Then, the content temperature was lowered to 80-100°C. Excess water was removed under reduced pressure while maintaining the temperature at C. 65 parts by weight of soybean oil fatty acid glycidyl ester was added to 100 parts by weight of the maleated polybutadiene thus obtained, and the mixture was heated at 130 to 140°C with stirring. After esterification for an hour, the contents were cooled to 70''C and diluted by adding 20 parts by weight of isopropyl alcohol and 16 parts by weight of butyl cellosolve to obtain an esterified product with a solid content of 80% after 4 days of oxidation.

Cobalt naphthenate, lead naphthenate, and calcium naphthenate were added to 100 parts by weight of the obtained esterified product so that the metal equivalent values were 0.06 part by weight, 0.6 part by weight, and 0.2 part by weight, and further. Triethylamine 6 sufficient to neutralize 95% mole of carboxyl groups of the esterified product
．． Add 6 parts by weight, mix thoroughly, and add 1 part by weight of deionized water.
It was diluted with 75 parts by weight to obtain a coating composition with a solid content of 28%.

The resulting composition was applied to a 0.8×100×150+ms steel plate to a thickness of 0.3 mm and left at room temperature for 10 days to form a dry and cured coating. When this steel plate was suspended below the sea surface under the same conditions as in Example 1 and the state of adhesion of marine organisms was observed, it was found that Fujitbo and sea cucumbers were attached, and the thickness was 0.5 ann at the most common place.

〔Effect of the invention〕

The coating composition of the present invention forms a cured coating film in a short period of time, and the formed cured coating film has an excellent effect of preventing attachment of aquatic organisms, such as marine organisms, and prevents attachment of marine organisms etc. for a long period of time. . Furthermore, there is no danger in handling and it is highly safe. Furthermore, it has excellent waterproof and rust-proof properties.

Therefore, the present invention is applicable to ship bottom paints, underwater/submarine piping paints,
It can be effectively used as an anti-algae paint.

Claims (1)

[Claims] (1) A coating composition prepared by blending a reaction product of a hydroxyl group-containing liquid diene polymer with maleic acid or maleic anhydride into a coating material.