JPS60188478A - Antifouling paint composition - Google Patents

Abstract

PURPOSE:To provide an underwater antifouling paint compsn. which has excellent storage stability and gives a coating film capable of retaining an excellent antifouling effect over a long period of time, consisting of a vehicle and a copper alloy powder contg. a plurality of specified metals. CONSTITUTION:An underwater antifouling compsn. is obtd. by incorporating 100-950pts.wt. copper alloy powder contg. 3-25wt% Ni and/or Mn and 0.1- 5wt% Zn and/or Sn in 100pts.wt. (on a solid basis) vehicle (e.g. PVC, silicone rubber, oil varnish or a polymer contg. an organotin compd.). The paint compsn. has excellent storage stability and antifouling performance and gives a coating film capable of retaining an excellent antifouling effect over a long period of time. The compsn. is particularly suitable for use in coating vessels, underwater structures or seawater introducing pipes which have much difficulty in repainting work.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an underwater antifouling coating composition. More specifically, the present invention relates to an antifouling paint composition containing copper alloy powder that can be applied to ship bottoms, marine structures, seawater introduction pipes, and the like.

In general, it is known that when marine organisms adhere to the bottom shell of a ship, it results in a waste of propulsion energy and causes trouble in the operation of the ship. Furthermore, it has been found that organisms adhere to the surface of marine structures, damaging the anticorrosion coating layer, and as a result, the service life of the structure is significantly shortened. Furthermore, there have been problems such as the accumulation of attached organisms on seawater inlet pipes, etc., which significantly deteriorates their original functions.

In this way, the adhesion of marine organisms causes extremely great damage industrially, so it is necessary to avoid such adhesion as much as possible. As a countermeasure, anti-ice paint compositions containing various antifouling agents are used. There is.

By the way, conventional antifouling paint compositions use a water-resistant resin capable of forming a film, such as vinyl chloride resin, as a color vehicle, and add a copper compound or metal such as cuprous oxide or copper rhodan, or an organic tin compound, etc. It consists of a composition to which an antifouling agent is added, or a coating composition to which an elution aid for the antifouling agent is added. However, the antifouling property of the paint film obtained from this type of paint composition is achieved by the gradual elution and diffusion of the antifouling agent contained in the paint or its decomposition products from the paint film into seawater, etc. It is something that

Furthermore, in recent years, organic tin polymer type antifouling paint compositions, which contain as a main component an antifouling component chemically bonded to a film-forming resin, have come into use. However, the paint film formed from this type of paint composition gradually undergoes a hydrolysis reaction in seawater, and the antifouling agent is released into the seawater and exhibits an antifouling effect. The mechanism is that the forming resin also becomes water-soluble, and the coating itself gradually dissolves in seawater and peels off along with the attached organisms.

Furthermore, in recent years, it has become extremely difficult to repaint vessels, offshore structures, or seawater inlet pipes, so once applied, antifouling paints can form a film that can be expected to have a long-term antifouling effect. The demands on compositions are becoming very strong.

In addition, conventional antifouling paint compositions often tend to thicken during storage, and in severe cases, there is a problem in that coating becomes almost impossible. Therefore, it has been strongly desired to improve the various drawbacks of such coating compositions.

In view of these circumstances, the present inventors have developed an antifouling paint that has excellent storage stability and antifouling performance, and is capable of forming a coating film that can maintain its antifouling effect for a longer period of time. As a result of extensive research into compositions, we have arrived at the present invention.

In other words, an object of the present invention is to provide an antifouling paint composition that has extremely good storage stability and excellent antifouling performance, and is capable of forming a coating film that can maintain its antifouling effect for a long period of time. It's about doing.

That is, the present invention uses (a) a color vehicle (2), (n) a small amount of a metal selected from di-Nokel and manganese (both of which contain 3 to 2
5% by weight and a small amount of a metal selected from zinc and tin (both 1
Copper alloy powder containing 0.1 to 5% by weight of seeds, and in another embodiment, in addition to the above (a) and (b), an antifouling agent containing (c) another antifouling agent. The present invention relates to coating compositions.

As the "color vehicle" used in the antifouling paint composition of the present invention, all those commonly used as color vehicles in antifouling paint compositions can be used without any problem. For example, vinyl resin (vinyl chloride resin, vinyl chloride-isobutyl ether copolymer resin, vinyl chloride-vinyl acetate copolymer resin, etc.), chlorinated rubber resin, chlorinated polyethylene, chlorinated polypropylene, acrylic resin, styrene-butadiene copolymer resin, etc. Polymer resins, epoxy resins, maleated dicyclopentadiene resins, oil varnishes, rosins, organic tin-containing polymers such as tributyltin-containing acrylic copolymers and triphenyltin-containing acrylic copolymers, or silicone rubber can be suitably used. .

These may be used singly or as a mixture of two or more, if necessary.

Further, the copper alloy powder as an antifouling agent used in the antifouling paint composition of the present invention contains 3 to 25% by weight of at least one metal selected from nickel and manganese, and at least one metal selected from zinc and tin. It contains 0.1 to 5% by weight of at least one kind of metal, and the remaining composition is mainly copper.

The shape of the copper alloy powder referred to in the present invention includes all types of powder such as granular, fibrous, and flat.

If the content of at least one metal selected from nickel and manganese is less than 3% by weight in the copper alloy powder, the tendency of the copper alloy powder to oxidize becomes large, and therefore the sustainability of the antifouling effect is reduced. I can't wait anymore. Furthermore, at the initial stage of immersion in the sea, the amount of copper ions eluted becomes excessive, resulting in a decrease in the durability of the antifouling effect of the coating film.

On the other hand, if the content of at least one metal selected from zinc and tin in the copper alloy powder is less than 0.1% by weight, the uniform dissolution of copper ions due to the homogenization of the structure of the copper alloy will be impaired. This leads to wastage of copper alloy, and as a result, the durability of the antifouling effect of the coating film decreases.

Conversely, if the content of at least one metal selected from nickel and manganese exceeds 25% by weight, the copper content as an antifouling agent will inevitably decrease, and the content of at least one metal selected from nickel and manganese will inevitably decrease. If the content of at least one type exceeds 5% by weight, the bactericidal effect due to copper elution effect will be suppressed, and the antifouling effect will decrease in either case.

In addition, the copper alloy powder is selected by considering the surface condition of the coating film, etc.
Granular with an average particle diameter of 10μ or less, or an average length of 10 to 20
They are preferably flat particles with an average thickness of 2 to 10 microns, or fibrous particles with an average diameter of 2 to 15 microns and a length of 10 to 200 microns.

In any case, by making the copper alloy powder in the present invention have a specific composition as described above, the elution of copper ions can be controlled and the antifouling effect can be maintained for a long time.

In the first aspect of the present invention, the copper alloy powder is 100 to 950 parts by weight based on 100 parts by weight of the solid content of the vehicle,
Preferably, it is used in a ratio of 200 to 900.

In the above range, if the amount of copper alloy powder used is less than 100 parts by weight, the desired antifouling effect is unlikely to be exhibited. On the other hand, if it is used in excess of 950 areas, the strength of the coating film tends to decrease and defects such as peeling tend to occur, which is not very preferable.

The antifouling paint composition of the present invention can form a coating film having sufficient antifouling properties by itself, but if necessary, other antifouling agents,
For example, cuprous oxide, cuprous rhodan, tributyltin fluoride, bistributyltin oxide, tributyltin chloride, bis(tributyltin)-α,α′-dibrom succinate, triphenyltin hydroxide, triphenyltin acetate, Triphenyltin chloride, triphenyltin fluoride, bis(triphenyltin)-
One or a mixture of two or more antifouling agents commonly used in antifouling paint compositions, such as α,α′-dibromsuccinate, organotin compounds such as triphenyltinnicotinic acid, thiurams, dithiocarbamates, etc. may be used together.

That is, the composition of the second aspect of the present invention has a vehicle solid content of 1
00 parts by weight, 100 to 800 parts by weight of the copper alloy powder and 250 parts by weight or less of the other antifouling agents.

When the other antifouling agents are used in an amount exceeding 250 parts by weight, the strength of the coating film tends to decrease, which is not preferable.

In the antifouling paint composition of the present invention, in addition to the above components,
If necessary, color pigments; extender pigments; plasticizers; elution aids for antifouling agents (rosin, etc.); solvents; and other harmful additives (anti-foaming agents, anti-settling agents, leveling agents), etc. that are normally used in paints. Various components can be added and mixed.

The antifouling paint composition of the present invention can be made into a one-component paint by mixing and dispersing the color vehicle, copper alloy powder, and other components in a common paint manufacturing device (ball mill, disper, etc.) all at once or in parts. It can be prepared.

Alternatively, the coating components may be prepared by dividing them into a two-component type and mixing and dispersing them immediately before use.

The antifouling paint composition of the present invention thus prepared can be applied to ships and marine structures, either as is or after adjusting the viscosity with a solvent, usually by airless spray coating, but in some cases by roller coating, brush coating, or double gun coating. Approximately 3 for things etc.
Applied at dry film thickness of 0μ to 300μ.

The coating film obtained from the antifouling paint composition of the present invention having the above-mentioned structure has excellent antifouling properties and can maintain the same antifouling performance for a long period of time.

The details of the present invention will be explained below using Examples and Comparative Examples.

"Part" or "%" means "1 part by weight" or "% by weight."

Examples 1 to 15 and Comparative Examples 1 to 10 Antifouling paint compositions of the present invention and comparative examples were obtained according to the formulations shown in Tables 1 and 2. First, in Examples 1 to 15 and Comparative Examples 8 to 10, the components except the copper alloy powder were mixed and kneaded in a bot mill all day and night, and then the copper alloy powder was stirred and mixed in a disper. In Comparative Examples 1 to 7, all the components were mixed and kneaded in a bot mill for a day and night to obtain coating compositions. Table 3 shows the comparative test results of the storage stability of each antifouling paint composition and the antifouling properties of the coating film obtained from each paint composition.

1 Note 1) Antifouling property: On a vinyl chloride resin board (300 x 100 x 2 m), 50μ of the antifouling paint compositions of Examples 1 to 15 and Comparative Examples 1 to 10 were spray-coated twice, and dried at room temperature for 4 days. rear(
The dry film thickness was 100 μm), and was suspended on a raft in Toba, Mie Prefecture at a depth of 1.5 m, and the state of biofouling was observed after 6, 9, and 12 months. The evaluation is based on the biofouling area (χ
).

Note 2) Storage stability: Viscosity after storing each antifouling paint composition obtained with the formulations in Tables 1 and 2 above in a 200 mJ+ glass bottle in a sealed state at 50°C for 20 days. I looked into it.

It is clear from the comparative test results in Table 3 above that in the seawater immersion test (for 12 months) of the paint film, almost no living organisms were observed on the paint film of the antifouling paint composition of the present invention. The antifouling paint composition has very excellent antifouling performance, and furthermore, the antifouling paint composition of the present invention has better storage stability (50°C, 20 days) was found to be significantly superior.

3 Procedural amendment band Commissioner of the Patent Office Manabu Shiga 3, Person making the amendment Relationship to the case Applicant Name (332) Dainippon Toyo Co., Ltd. Mitsubishi Metals Co., Ltd. 4, Agent 5, [Date of official order] Issue 7, Contents of amendment 1, the scope of claims in the specification is amended as shown in the attached sheet.

2. "Marine structures" on page 2 of the specification, line 14, are defined as "underwater structures (port facilities, oil drilling equipment, wire mesh and supports for fish and shellfish culture cages, bridge piers, etc., structures used in seawater or freshwater)" Correct to ``object)''.

3. Insert the following sentence between lines 17 and 18 on page 6 of the specification.

``Compositions containing unavoidable metal impurities normally derived from raw materials used in the production of copper alloy powder are also included within the technical scope of the present invention.'' 4. The specification is amended as follows.

Claims (1) (a) a color vehicle, (b) 3 to 25% by amount of at least one metal selected from nickel and manganese, and at least one metal selected from zinc and tin. An underwater antifouling paint composition comprising 0.1 to 5% by weight of copper alloy powder.

(2) The color vehicle is made of at least one polymer or polymer selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based varnish, rosin, and organic tin compound-containing polymer. ) The underwater antifouling paint composition described in item 2.

(3) The underwater antifouling paint according to claim 1 or 2, comprising 100 to 950 parts by weight of copper alloy powder to 100 parts by weight of color vehicle (solid). Composition.

(4) (a) a color vehicle; (b) 3 to 25% by weight of at least one metal selected from nickel and manganese;
0.1 of at least one metal selected from zinc and tin
-5% by weight of copper alloy powder, and P9 and other antifouling agents.

(5) The color vehicle is at least one polymer selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based varnish, rosin, and organic tin compound-containing polymer. ) The underwater antifouling paint composition described in item 2.

(6) Claim (4) consisting of 100 to 800 parts of copper alloy powder and 250 parts by weight or less of other antifouling agents to 100 parts by weight of color vehicle (solid content) Or the underwater antifouling paint composition described in item (5).

Claims (6)

[Claims] (1) (a) a color vehicle and (b) 3 to 25% by weight of at least one metal selected from nickel and manganese;
0.1 of at least one metal selected from zinc and tin
An antifouling paint composition comprising a copper alloy powder containing ~5% by weight. (2) The color vehicle is made of at least one polymer or polymer selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based varnish, rosin, and organic tin compound-containing polymer. The antifouling paint composition described. (3) Copper alloy powder 100~100 parts by weight of color vehicle
The antifouling coating composition according to claim (1) or (2), comprising 950 parts by weight. (4) (a) Color vehicle, (II+) 3 to 25% by weight of at least one metal selected from nickel and manganese, and 0.0% by weight of at least one metal selected from zinc and tin.
An antifouling paint composition comprising a copper alloy powder containing 1 to 5% by weight, and (iii) another antifouling agent. (5) The color vehicle is at least one polymer selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based varnish, rosin, and organic tin compound-containing polymer. ) The antifouling paint composition described in item 2. (6) 100 parts by weight of copper alloy powder to 100 parts by weight of color vehicle
The antifouling coating composition according to claim 4 or 5, comprising 800 parts by weight or less of other antifouling agents and 250 parts by weight or less.