KR950011501B1 - Antifouling paint composition - Google Patents

Abstract

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Description

Anti-pollution antifouling paint composition

The present invention relates to a self-wearing antifouling coating composition, particularly a self-wearing antifouling coating having the highest quality as an antifouling coating, and an organic tin compound, which is legally regulated as a hazardous substance, is not only an additive but also a binder. The present invention relates to a self-wearing pollution-free antifouling coating composition that is not contained.

Antifouling paint is a paint for preventing or minimizing the growth of marine pollutant organisms attached to the seawater immersion area of various objects. Generally, it is applied to seawater immersion parts such as ships, fishing nets, marine structures, and cooling ports of power plants. Marine pollutant organisms such as barnacles, moss insects, phantoms, greens, green algae, etc. grow and attach, causing problems such as slowing down the ship's operating speed and increasing fuel consumption. As the eyes become clogged, various problems occur, such as the killing of fish due to poor seawater distribution. Various antifouling paints are currently used to control the growth of these marine pollutant organisms.

Organic tin compounds such as TriButyltin (TBT) or Triphenyltin (TPT) have been used worldwide for many years as antifouling factors required for these antifouling paints. By creating anti-fouling paints of the `` Opgarnotin copolymer '' type, it has been introduced as the anti-fouling factor that can exhibit the most effective and long-term antifouling effect.

Antifouling paints using such copolymers as binders have been referred to as self-polishing or self-wearing antifouling paints, which release antifouling agents as the coating film dissolves in seawater to provide antifouling properties continuously to the coating film. The biggest advantage of using self-polishing antifouling paint as propagating paint is that even if the paint is unevenly coated on the bottom, the roughness of the paint film is gradually reduced in seawater, thereby reducing the frictional resistance of the hull.

By painting in each repair dock, even if the thickness of the remaining paint film is increased and the surface roughness of the paint film is increased, this problem can be avoided as a self-polishing antifouling paint and the hull resistance of the hull can be prevented.

Conventional self-polishing antifouling coatings are homopolymers of organotin compounds having the general formula as described in British Patent Nos. 145, 790 and Japanese Patent Nos. 214 26/1965, 9579/1969 or such compounds and others. And a copolymer with an unsaturated monomer.

These polymers are slowly hydrolyzed in weakly alkaline (pH8 to 9.5) seawater to favor trialkyltin compounds, with the carboxyl groups being formed in the polymer. Free trialkyltin compounds inhibit biofouling as antifouling agents. By the formation of carboxyl groups in the polymer, the polymer becomes hydrophilic. When a large number of carboxyl groups are formed in the polymer due to hydrolysis, the polymer gradually dissolves in seawater. With this mechanism, the self-polishing antifouling paint continuously provides the active paint coating surface to the paint, thereby steadily releasing the poison over the paint life.

However, the trialkyl tin compound released in this way has a high antifouling effect due to its toxic effect, which has a fatal effect on marine organisms and has a huge impact on marine ecosystems. In addition to the regulations on trade, various regulations on ships coated with these paints are being tightened.

Accordingly, an object of the present invention is to provide a new type of self-polishing type antifouling coating composition in which no organic tin compound, which is a hazardous substance, is bonded to the binder used as the self-polishing antifouling paint, and not used as an additive at all.

In order to achieve the above object, a new pollution-free antifouling coating composition of the present invention is a binder, and Korean Patent Application No. 91-14360 filed on August 21, 1991 by the present applicant, and an application number of a domestic priority claim based on the same. No. 91-14360 and the binder specified in Korean Patent Application No. 91-25743 filed on the basis of the claim of domestic priority, and there are additives such as known antifouling agents, various pigments, rainy seasoning agents and anti-settling agents. It was made by adding more.

The binder specified in the above applications is a polymer composed of a monomer of formula (2) or copolymerized with another photopolymerizable radical monomer to the monomer.

In formula (2), R and R 'are the same, -H, -CH ₃ or -Cl, M is IB, II A, II B, III A, III B, IV A, IV B, VA, on the periodic table VB, VI A, VII A, VIII is one of the divalent or higher metals, n is the corresponding metal ion number, and Y is , Q ¹ and Q ² are the same or different, -C ₆ H ₅ , -CN or -NO ₂ , R ¹ to R ¹⁰ are the same or different, hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, X is or And X 'is , or ego,

R ¹¹ to R ¹⁴ are the same or different and are hydrogen or a linear or branched alkyl group of 1 to 10 carbon atoms, and Z ¹ and Z ² are the same or different and are linear or branched alkyl groups of 1 to 6 carbon atoms.

The binder used for the composition of this invention can be manufactured as a homopolymer by homopolymerizing the monomer represented by the said Structural formula (2), or can be manufactured as a copolymer which copolymerized the said monomer and the well-known photopolymerizable radical monomer.

At this time, the known weight part radical monomer is used for the purpose of providing flexibility of binder, controlling solubility and controlling self polishing property. Examples of such monomer include methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate and styrene. , Lauryl methacrylate, acrylonitrile, vinyl acetate, vinyl chloride, phenyl methacrylate, cyclohexyl acrylate, N, N'-dimethylaminoethyl methacrylate, 2-ethylhexyl acrylate, 2- Hydroxyethyl methacrylate and the like, but these examples do not limit the scope of the present invention.

In the preparation of the binder, the content of the hydrolyzable monomer is preferably used at least 20 parts by weight or more, based on 100 parts by weight of the polymer.

In order to prepare the binder, the hydrolyzable monomer may be substituted with a radical initiator such as benzoyl peroxide, azobisisobutyronitrile under the same solvent as xylene, toluene, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and n-butane. To polymerize at 50-120 ° C. in a known solution polymerization manner.

The above-mentioned binder is hydrolyzed by a mechanism similar to that of the polymer of the conventional organotin compound, wherein the free metal compound itself has antifouling properties, and copper dioxide, which is an antifouling agent of commonly used antifouling paints, is used as a coating composition. When used together, they elute together on the surface of the coating and have excellent antifouling properties.

In other words, when the binder on the surface of the coating film is dissolved in seawater by hydrolysis, the antifouling agent is separated at the same time. As such a state is repeated, the coating film always maintains a new surface layer, thereby becoming a perfect self-wear coating material.

When describing the advantages of the antifouling coating composition according to the present invention, firstly, it is possible to prevent marine environmental pollution by organotin compounds that have been a problem in the meantime; For example, the raw material cost of the paint can be lowered by using an inexpensive new wear type resin instead of the existing binder containing the expensive tributyltin compound; And thirdly, it is possible to reduce fuel costs when operating a ship by reducing surface friction with a magnetic wear type.

The self-wearing antifouling paint composition of the present invention is a binder which is a polymer of the monomer represented by the formula (2) or a copolymer of a photopolymerizable radical monomer and additives such as known antifouling agents, various pigments, organic solvents and antisettling agents. It consists of, the binder may be used 20 to 70% by weight based on the final composition, if the content is less than 20% by weight paint abrasion does not show the effect as a self-wear coating, antifouling or inferior, 70 weight If it contains more than%, there is a drawback that the antifouling period is shortened due to too much paint wear.

As the antifouling agent, well-known copper dioxide can be used, and can also be used in combination with a derivative of isociazoline. An appropriate amount is 20 to 60% by weight with respect to the final composition. In use, problems of adhesion of the coating film and sedimentation in the production of the paint are caused.

As a pigment, metal oxides, such as iron oxide and zinc oxide, can be used, and 1-20 weight% can be used with respect to coating composition.

Xylene and methyl isobutyl ketone may be used as the organic solvent, and antisettling agents such as polyamide wax may be used as other additives.

As the coating composition, a self-polishing type pollution-free antifouling paint free of organotin compounds can be obtained by a conventional antifouling paint production method, and an appropriate amount of wear required according to the content of the coating composition can be obtained.

In the following Preparation Examples, Examples, Comparative Examples, Experimental Examples will be described in detail the manufacturing method of the pollution-free coating composition according to the present invention and its effect. However, the following examples do not limit the scope of the present invention.

[Production Example of Monomer]

47.0 parts by weight of zinc dimethacrylate, 117.0 parts by weight of toluene, and 0.3 parts by weight of hydroquinone are added to a 1 L four-necked flask and heated to 30 ° C. while adding nitrogen. 74.0 parts by weight of dioctylphosphate monoexoxide is added dropwise to the zinc dimethacrylate solution over 2 hours. When the solution became clear, it heated up at 80 degreeC, stirred for 1 hour, and toluene was removed by distillation under reduced pressure, and 79.9 weight part of semisolid colorless monomers were obtained. Yield 90%.

1R; 1950, 2875, 2680, 1650, 1596, 1575, 1461, 1378, 1247, 1189.9, 1099, 1034, 985, 885, 830, 619, 527.8, 490.

NMR (CDLl ₃ ); 6.48, 6.43, 6.20, 6.17, 6.14, 5.80, 3.85, 1.70, 1.65, 1.49, 1.45-1.30, 0.95-0.80.

[Manufacture Example 1 of Binder (Manufacture of E-1)]

75 weight part of xylene and 75 weight part of methyl isobutyl ketones are put into a 4 neck flask, and it heats up at 80 degreeC, injecting nitrogen. A mixed solution of 60 parts by weight of the monomer, 30 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, and 0.75 parts by weight of azobisisobutyronitrile was added dropwise uniformly over 5 hours, followed by maintaining for 1 hour, and then raising the temperature. After maintaining for 30 minutes at 100 ℃ to cool to room temperature to prepare a binder E-1.

[Manufacture Example 2 of Binder (Manufacture of E-2)]

75 weight part of xylene and 75 weight part of methyl isobutyl ketones are put into a 4 neck flask, and it heats up at 80 degreeC, injecting nitrogen. A mixture of 70 parts by weight of the monomer, 20 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, and 0.75 parts by weight of azobisisobutyronitrile was added dropwise and uniformly over 5 hours, followed by maintaining for 1 hour, and then raising the temperature. After maintaining for 30 minutes at 100 ℃ to cool to room temperature to prepare a binder E-2.

EXAMPLE

In the manufacturing examples of Tables 1 and 2, one-third of the binder was mixed with 1/2 of xylene, iron oxide, zinc oxide and methyl isobutyl ketone, and stirred for 30 minutes with a high speed dissolver of 1500 RPM. Or dispersed twice using a sand mill. Put the remaining binder and xylene into the dispersed mixture, add copper dioxide, dichloro octyl isociazoline and polyamide wax, and then stir for 30 minutes with a high speed dissolver of 1500 RPM and self-polishing type without organotin compound of the present invention. An antifouling coating composition is prepared.

TABLE 1

TABLE 2

Next, as a comparative paint of the self-polishing antifouling paint of the present invention, a resin in which an existing organic tin compound is bound to a binder was used.

[Comparative Example]

The production method of this example is the same as that of the above embodiment except that tributyltin copolymer is used instead of the binder in the above embodiment.

TABLE 3

The following is a detailed test method of the antifouling properties of the paint according to the nine examples and two comparative examples and a comparative test of the wear property as a wear-resistant paint.

Experimental Example 1

The test paints prepared according to the above Examples and Comparative Examples were subjected to the antifouling test in the following manner.

By using one kind of rolled steel plate of KSD35 with width × length × thickness of 300 × 300 × 3.2mm, pre-treat it with sandblasting in accordance with KSM5569 method and paint rust-preventive paint twice by type. Then, the antifouling paints prepared by the above Examples and Comparative Examples were sprayed twice so that the dry film thickness was 200 μm, respectively, and then dried for about 1 week.

The above test specimens were deposited in a depth of about 1m in the antifouling paint test site installed near the Ulsan city to confirm the antifouling condition for 12 months.

Experimental Example 2

The paint abrasion test of the paints prepared in Examples and Comparative Examples was carried out in the following manner.

An antirust coating is applied to a tin plate having a width × length × thickness of 150 × 75 × 1 mm, and then the test paint is spray-coated to a dry coating thickness of 100 μm and then sufficiently dried for about 1 week.

The tank is then kept at 25 ° C with a heater in a tank of width x length x height of 3 x 2 x 1.5 mm, and fresh sea water is automatically introduced and discharged more than about 100 tons per day, and the test specimen is taken from the sea water in the tank. It was set to move at 16 knots, similar to the operating speed. That is, after each test specimen was moved to 16 knots in the real seawater, the test results of the wear amount of the paint were obtained as shown below.

TABLE 4

Antifouling test was observed after 12 months of curing.

TABLE 5

As can be seen from Tables 4 and 5, the antifouling properties of the coating compositions according to Examples 1 to 9 were found to be very good, and even in the wear test, various wear rates can be obtained according to the content of the coating composition, and it can be seen that the wear is very constant for a long time. have. That is, the excellentness of the new pollution-free antifouling paint is demonstrated by the above table.

Claims (5)

One or more of a binder consisting of a polymer composed of a monomer of the following structural formula (2) or a copolymer of the monomer and another photopolymerizable radical monomer copolymerized with a known antifouling agent, various pigments, an organic solvent and an antisettling agent. A self-wearing pollution-free antifouling coating composition comprising: In formula (2), R and R 'are the same, -H, -CH ₃ or -Cl, M is IB, II A, II B, III A, III B, IV A, IV B, VA, on the periodic table VB, VI A, VII A, is one of the divalent metals of the group VIII, n is the number of metal ions of interest, Y is Q ¹ and Q ² are the same or different, , -C ₆ H ₅ , -CN or -NO ₂ , R ¹ to R ¹⁰ are the same or different, hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms, X is or And X 'is or ego, R ¹¹ to R ¹⁴ are the same or different and are hydrogen or a linear or branched alkyl group of 1 to 10 carbon atoms, and Z ¹ and Z ² are the same or different and are linear or branched alkyl groups of 1 to 6 carbon atoms. The anti-wear antifouling coating composition according to claim 1, wherein the binder is used in an amount of 20 to 70% by weight based on the final composition. The anti-fouling antifouling coating composition according to claim 1, wherein the antifouling agent is used alone or in combination with a derivative of isocyazoline. The anti-wear antifouling coating composition according to claim 1, wherein the antifouling agent is 20 to 60% by weight based on the final composition. The anti-wear antifouling coating composition according to claim 1, wherein the pigment is used in an amount of 1 to 20% by weight based on the coating composition.