JPS59227959A - Underwater antifouling paint - Google Patents

Abstract

PURPOSE:To provide an underwater antifouling paint which is highly safe and excellent in an antifouling effect, can maintain its effect over a long period of time and is suitable for use in coating vessels, by mixing an active antifouling component composed of a specified halogen-contg. alcohol compd. with a paint vehicle. CONSTITUTION:An active antifouling component composed of a compd. of the formula (wherein X1, is H, halogen; X2 is halogen; n is 1-3) such as 2,3,3-triiodoallyl alcohol or 2,3,3-tribromoallyl alcohol is mixed with a paint vehicle in such a quantity that the antifouling agent of the formula accounts for 0.5-50wt% of the entire paint compsn., thus obtaining the desired underwater antifouling paint. Examples of the vehicles are vinyl chloride resin, rosin ester resin, etc. If desired, other inorg. or org. antifouling agent such as cuprous oxide or tributyltin fluoride may be incorporated in the paint of the present invention.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifouling paint for the purpose of preventing the attachment of harmful aquatic organisms to ships and underwater structures.

Plants such as green algae and brown algae, animals such as Fujibbo, Serpura, Kasane Kanzaki, sea squirts, mussels, and oysters, and aquatic organisms such as various bacteria called slime, molds, and diatoms are found on the bottom of ships, in the water line, Inner surfaces of power plant water intakes and cooling pipes,
If it adheres to aquaculture fishing nets, facilities, and other various coastal structures, it will cause significant losses in terms of conservation and maintenance of these structures. If it adheres to a ship, it increases the frictional resistance between the ship and the seawater, causing economic losses such as a decrease in ship speed and an increase in fuel costs. Removal of the above-mentioned deposits requires a great deal of effort, and there is also a large economic loss in this respect.

Conventionally, T'5, cuprous oxide, copper rhodanide, organic tin compounds, organic tin polymers, thiocarbamates, etc. have been used as anti-TLJ agents for underwater anti-F'I paints. These compounds tend to be effective against the above-mentioned nσ habitats, plants, slimes, etc., and are widely used for fire purposes, but the metals and organic metals they contain are not desirable from a public health or ecological standpoint. There is an urgent need to develop highly safe antifouling agents.

Prevention: /1'5 One of the characteristics required of the slag is that the effect lasts for a long time, for example, one year or more.

This is because ships and the like are used for long periods of time, and once they have set sail, it is impossible to reapply the anti-β paint on the bottom of the ship at the next port of call. Applying antifouling paint to 114 structures also requires skill, and it is disadvantageous to repaint them frequently, so those that have a long lifespan are often destroyed.

Therefore, the present inventors have developed a method that is highly safe and has excellent antifouling effects.
In addition, we have endeavored to find an antifouling agent that can be incorporated into the underwater antifouling coating O1 and maintain its effectiveness for a long period of time, and have finally completed the present invention.

The present invention provides a paint vehicle and an antifouling property J component of the formula % (1) (wherein X1 is a hydrogen atom or a halogen atom, X2 is a halogen atom, and n represents an integer from 1 to 3). The present invention relates to an underwater antifouling paint characterized by containing a compound.

As the halogen atom in the binary formula (1), chlorine, bromine and iodine are preferred, and the molecule may contain different halogen atoms. When the number exceeds 11 or 3, the compound of formula (1) hardly dissolves in seawater, so there is no longer any T grade.

Specific examples of the compound of formula (1) include 2.3.3-)I
J Iodoallylic alcohol Allyl alcohol, 3,4-dichloro-3-butene alcohol, 4,5-dibromo-4-pentene alcohol/1/
etc. are shamed.

In addition, the compound of the formula (l) has no adverse effect on the storage stability of the paint, such as thickening of the paint or interstitium, during coating 1,
It is highly safe, improves work efficiency, and causes less environmental pollution.

Furthermore, the compound of formula (1) exhibits almost no causticity or skin irritation during manufacturing and coating.

The underwater antifouling paint of the present invention has low bioselectivity, has a high antifouling effect against almost all water (↓) attached organisms, has the advantage of lasting for a long time, and is corrosion resistant to materials. Because it has no vulnerabilities, it can be used with confidence especially on ships and underwater structures made of steel, light alloys, and concrete.

As the paint vehicle used in the underwater antifouling paint of the present invention, commonly used resin vehicles can be used. For example, vinyl chloride) V-based resins, chlorinated rubber-based resins, chlorinated polyethylene resins, chlorinated polypropylene resins, acrylic resins, nutylene-butadiene-based resins, borie ether-based resins, epoxy-based resins, petroleum-based resins, and oils. Examples include resins based on Rosin, Rosin Nute/1/1 Resin, Rosin Stone!Gin, and Rosin.

As a vehicle with extremely antifouling properties, (meth)acrylic acid and bis(triphytylmethane)oxide, 1-
A tin compound salt such as liphenyltin hydroxide (σ, β-unsaturated 2 unsaturated 20 monomers obtained by condensation reaction of base tin compounds is a dicarboxylic acid) and a tin compound salt Ii
) Acrylic copolymer containing as J acid unit (GIJ) j.
It is also possible to use f&F1 compound oxides. However, polyacrylate, polyvinyl alcohol, C! MO$
When an O water-soluble resin is used as a paint vehicle, although the initial antifouling effect is excellent, the antifouling effect does not last for a long time, and it is not preferable to use a large amount of these water-soluble resins.

The antifouling agent in the formula used in the present invention is 05 to 50% by weight, preferably 1 to 30% by weight based on the entire coating composition.
It is convex and divided as if breaking the mold. The underwater antifouling paint of the present invention may further contain other known inorganic or organic antifouling agents, if necessary.

Examples of such compounds include cuprous oxide, copper rhodanide, copper hydroxide, metallic copper, various tin compounds such as bis(tributyltin) oxide, 1-liptylsnuchloride, tributyltin fluoride, tributyltin acetate, I -butylnununicotin-1-, triphthylnununicotin-1-, tributyltin-a, α'-sibrom succinate, triphenyltin hydroxide l-, triphenyltin nuchloride, l-lifconi Nilsnufluoride, 1-liphenylnus acetate, -1-, l-liphenylnunicotine-1., triphenyltindimethylcythiocarbame-1., triphenyltinperzachii-1-, bis-
(triphenyltin)-α,α′-sibrom succinate, bis-(+·liphenyltin) oxide, and dithiocarbamic acid derivatives, such as tetramethylnauram monozatvy-yy ITJ,!=llll
? i), tetraethylphthiuram cisulfide, bis-(dinotyldithiocarbamic acid) llj button (
Hereinafter referred to as IZf) #ICJtlt= ethylene-
Zinc bis(dithiocarbamate) (hereinafter referred to as [ZINIfB
J (abbreviated as 1-ru), ethylene-bis(dithiocarbamine [□1) mankan, bis-(dimethyldithiocarbamic acid) former ji (lsu, lower g '1.''TCu J) are present.

In addition, the underwater antifouling ◇i x:'t of the present invention is;
The crosspiece solvent /4', +; can be included.

The underwater protection l'Q system of the present invention can be prepared by methods known per se in the field of coating paint production.

For compounding, a known machine such as a ball mill, a pebble mill, etc. is used.

The underwater antifouling paint of the present invention described above provides antifouling properties and slime resistance for a very long period of time, and exhibits excellent effects in preventing the attachment of harmful underwater organisms to ships and underwater structures.

The present invention will be explained in more detail below by way of examples.

In the examples, it is written as "part" (by Yu Chong Kong).

1=Resin symbols and trade names used in the examples have the following meanings.

fP-45 West Germany 13 A Vinyl chloride-vinyl isopropyl ether prioritization manufactured by SF 1-8-5 B Styrene-bucdiene copolymer V A G II manufactured by Gutdeyer, USA U.S. UC. Polyvinyl chloride resin T 13 T manufactured by Company C
- Acrylic copolymer solution prepared as follows. That is, 40 parts of a mixture of 65 parts of triptyltin methacrylate and 135 parts of methyl methacrylate are dissolved in 60 parts of xylene in a reaction tank equipped with means for heating and cooling.
To this is added 0.35 parts of benzoyl peroxide. In order to control the temperature due to the exotherm, the temperature of the solution is gradually raised under reflux using a cooling means over a period of 10 hours to a final temperature of 1]0'C. The final solution viscosity was 4.5 voids at 25°C.

Example The antifouling component according to the present invention and other components were placed in a ball mill and dispersed for 24 hours to prepare an underwater antifouling paint of the present invention. The formulation is shown in Table 1.

One known antifouling paint was tested for size comparison. The formulation is shown in Table 2.

These antifouling paints were subjected to an antifouling test 15r9. The antifouling test was carried out using the antifouling paints shown in Tables 1 and 2.A commercially available ship bottom No. 1 coating based on anticorrosion coating (Coalcoo) v/vinyl chloride/I/based resin was applied beforehand. 100X300
% to a test steel plate with a dry film thickness of 60 to 80 microns, and after drying for 4 hours, it was placed in the sea at a depth of 1 m on a test raft off the coast of Ura, Tamano City, Okayama Prefecture. The samples were dipped in water and evaluated by visual observation of the amount of animals such as Fujibbo and Serpura and plants such as Ulva and Green Nori as attached area%.

The exam period was from January 1980 to January 1980. Changes in biofouling history are shown in Table 3, and changes in slime adhesion amount are shown in Table 4.

Slime is a general term for diatoms, a viscous film made of various underwater bacteria and bacterial metabolites,
If this adheres, spores of sea lettuce, blue seaweed, or fujibbo larvae will enter, encouraging the reproduction of contaminant organisms.
Antifouling paints must have excellent slime resistance.

As can be seen from the Examples in Table 4 and above, the underwater antifouling paint of the present invention shows significantly better results than the comparative examples. In particular, it exhibits a surprisingly excellent effect in preventing slime build-up, and the fact that it has such an outstanding effect in slime resistance is very significant.

Patent applicant: Nippon Paint Co., Ltd. Same Kurita Industries Co., Ltd. Agent: Patent Attorney Mitsuma’>13 Husband

Claims (2)

[Claims] (1)? as an antifouling active ingredient and a formula (in the formula
1 represents a hydrogen atom or a halogen atom, X2 represents a halogen atom, and n represents an integer of 1 to 3. ) An underwater antifouling paint whose 4'S signature is that it contains the compound. (2) Underwater antifouling according to item 1 of box j'y61 of the patent claim in which the compound of formula (I) is 2.8.8-triiodoallyl alcohol 7z=j', -1° (31 formula (1) 2.3.8-1-ribromoallyl alcohol.