JPS60188477A - 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 specified metal. CONSTITUTION:An underwater antifouling paint compsn. is obtd. by incorporating 100-950pts.wt. copper alloy powder contg. 3-25wt% Ni and/or Mn 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 must be avoided as much as possible, and as a countermeasure, underwater antifouling paint compositions containing various antifouling agents are used. .

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, it becomes almost impossible to apply. 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 provides (a) a color vehicle (ii), (II+) a copper alloy powder containing 3 to 25% by weight of nickel and/or manganese; In addition, the present invention relates to an antifouling paint composition containing (c) another antifouling agent.

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, maleic cyclobentadiene 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 the remaining composition contains copper. It is the main ingredient.

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. Moreover, at the initial stage of immersion in the sea, the amount of copper ions eluted becomes excessive, resulting in wasted copper alloy, and as a result, the durability of the antifouling effect of the coating film decreases.

On the other hand, if the amount of nickel and/or manganese exceeds 25% by weight, the copper content as an antifouling agent will inevitably decrease, resulting in a decrease in the antifouling effect of the coating film.

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 1.0 μ or less, or an average length of 10 to 2
It is preferable that the particles be flat particles with an average thickness of about 2 to 10 microns, or fibrous particles with an average diameter of about 2 to 15 microns and an average length of about 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 proportion of 200 to 900 parts by weight.

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 more than 950 parts by weight is used, the strength of the coating film tends to decrease and defects such as peeling tend to occur, which is not so preferred.

The antifouling coating composition of the present invention is sufficient in itself to contain butyltin fluoride, bistributyltin oxide, tributyltin chloride, bis(tributyltin)-α,α′-dibrom succinate, triphenyltin hydroxide, and tributyltin fluoride. Organic tin compounds such as phenyltin acetate, triphenyltin chloride, triphenyltin fluoride, bis(triphenyltin)-α,α′-dibromsuccinate, triphenyltinnicotinic acid, thiurams, dithiocarbamates, etc. One or a mixture of two or more of the antifouling agents used in the antifouling paint composition may be used in combination.

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 weight9, it is not preferable because the strength of the coating film tends to decrease.

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 its antifouling properties for a long period of time.

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

"Parts" or "%" are "parts by weight" or "% by weight."

Examples 1 to 10 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 10 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.

0 Note 1) Antifouling properties: On a vinyl chloride resin board (300 x 100 x 2 inches), 50μ of the antifouling paint compositions of Examples 1 to 10 and Comparative Examples 1 to 10 were spray-coated twice, and dried at room temperature for 4 days. After that (dry film thickness was about 100 μm), it was suspended on a triple-layered Toba raft at a depth of 1.5 m, and the state of biofouling was observed after 6, 9, and 12 months. Evaluation is based on the biofouling area (
χ)

Note 2) Storage stability: After each antifouling paint composition obtained with the formulations in Tables 1 and 2 above was placed in a 200 mA glass bottle and stored in a sealed state at 50 ° C. for 20 days. The viscosity of

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°C) than the paint composition of the comparative example. It can be seen that the results (days) are significantly superior.

2 Procedural amendment Manabu Shiga, Commissioner of the Patent Office1, Indication of the case Patent Application No. 44907 of 19822,
Title of the invention: Antifouling paint composition 3, Relationship with the case of the person making the amendments: Applicant: Name of person (332): Dainippon Toyo Co., Ltd., Mitsubishi Metals Co., Ltd.: 4, Agent: 5, Date of amendment order: Proprietor: 7, Amendment Contents: 1. The scope of claims in the specification is amended as shown in the attached sheet.

2. “Marine structure” on page 2, line 9 of the specification is changed to “underwater structure (
(Structures used in seawater or freshwater, such as port facilities, oil drilling equipment, wire mesh and supports for fish and shellfish culture cages, and bridge piers).

3. Insert the following sentence between lines 9 and 10 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.

5. Table 1 between pages 10 and 11 of the specification is corrected as follows.

Claim +11: An underwater antifouling paint composition comprising (a) a color vehicle and (b) a copper alloy powder containing 3 to 25% by weight of nickel and/or manganese.

(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 composition 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 content). thing.

(4) An underwater antifouling paint composition comprising (a) a color vehicle, (b) a copper alloy powder containing 3 to 25% by weight of nickel and/or manganese, and other antifouling agents such as C9.

(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) Color vehicle (solid content) 100! 100 to 800 parts by weight of copper alloy powder and 250 parts by weight of other antifouling agents
The underwater antifouling coating composition according to claim (4) or (5), comprising a proportion of not more than parts by weight.

Claims (1)

[Scope of Claims] (1) An antifouling paint composition comprising (a) a color vehicle and (n) a copper alloy powder containing 3 to 25% by weight of nickel and/or manganese. (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 in item 2. (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. (An antifouling paint composition consisting of (41) (a) color vehicle (2), (rl) copper alloy powder containing 3 to 25% by weight of nickel and/or manganese, and (c) other antifouling agents. ( 5) The color vehicle is made of at least one polymer or polymer selected from vinyl resin, chlorinated rubber resin, silicone rubber, oil-based resin, rosin, and organic tin compound-containing polymer. The antifouling coating composition described in Section 6. (6) 100 parts by weight of a color vehicle to 100 parts by weight of a copper alloy powder.
Claims (4) or (5) consisting of ~800 parts by weight and 250 parts by weight or less of other antifouling agents
The antifouling paint composition described in Section 1.