JPS63179979A - Antifouling paint composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of retaining good storage stability as well as high antifouling performance for a long period, for application on ships shell, marine structures, etc., by blending an organotin-contg. copolymer as the vehicle, a copper compound as the antifouling agent and metallic powder as part of the pigment. CONSTITUTION:The objective composition can be obtained by blending (A) (i) a polymer of bis(tri)organotin salt of dibasic unsaturated carboxylic acid or (ii) a copolymer from said salt and another polymerizable unsaturated compound (pref. containing 10-22wt.% of tin) (B) a copper compound, and (C) metallic powder, i.e. a kind of, or a mixture of at least two kind of metal selected from Cu, Ag, Mg, Ca, Ba, Zn, Cd, Hg and Mn. This composition has been improved in terms of thickening during the storage, cobwebbing caused by its gelling and nonuniformity of the coating film therefrom, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antifouling paint composition that is applied to the outer panels of ships, marine structures, seawater inlet pipes, etc. to prevent the adhesion of marine organisms.

(Prior Art) When marine organisms adhere to the outer shell of a ship, marine structures, seawater inlet pipes, etc., the operating energy of the ship is extremely increased and the service life of these structures is significantly shortened.

Therefore, in recent years, high-molecular organotin compounds having organotin groups in their molecules have been used as excellent antifouling agents to prevent marine organisms from adhering to ships, marine structures, etc. It is also known that a copper compound (for example, cuprous oxide, copper rhodan) is used in combination with this polymeric organotin compound to produce a ship bottom paint having a fairly high level of antifouling performance.

(Problems to be Solved by the Invention) However, the antifouling paint, which is a mixture of a polymeric organotin compound and a copper compound, gradually increases in viscosity during storage, and in severe cases gels, resulting in stringiness.

This causes deviations in the designed coating thickness, uneven coating thickness, and inability to paint, which reduces the value of the product. Paints that have thickened or gelled in this way often show a decline in antifouling performance.

Therefore, an object of the present invention is to provide an antifouling paint composition that can maintain excellent storage stability and antifouling performance for a long period of time.

(Means and effects for solving the problem) The feature of the invention for solving the above object is that the main components are an organic tin-containing copolymer and a copper compound, and metal powder is included as a part of the pigment. .

The above-mentioned organotin-containing copolymers include (1) copolymers of bis(1-organotin) salts of dibasic unsaturated carboxylic acids and other polymerizable unsaturated compounds; ) dibasic unsaturated carboxylic acid bis(triorganotin)
a copolymer of a salt polymer and another polymerizable unsaturated compound; a mixture of a copolymer of a triorganotin salt of a monobasic unsaturated carboxylic acid and another polymerizable unsaturated compound; (3) Copolymers of polymers of organic tin salts of basic unsaturated carboxylic acids and other polymerizable unsaturated compounds are mentioned.

Examples of the dibasic unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and acid anhydrides thereof.

In addition, examples of the monobasic unsaturated carboxylic acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid,
These include vinylbenzoic acid and vinylbenzoic acid.

In the bis(triorganotin) salt or triorganotin salt of the acid, examples of the organotin group include a trialkyltin group, a tricycloalkyltin group, and a triphenyltin group.

Trialalkyl tin group. These alkyl groups have 3 to 10 carbon atoms.

Examples of the other polymerizable unsaturated compounds mentioned above include methyl methacrylate and butyl methacrylate-1.

Cyclohegyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate-1~, dodecyl acrylate, cyclohexyl acrylate-1~, phenyl acrylate-1~, hydroxyethyl acrylate, acrylic acid, methacrylic acid, etc. Acrylic compounds, vinyl chloride, vinylidene chloride, acryloni-1-lyl.

Methacrylic acid [・Ryl, acrylamide, vinyl acetate,
Vinyl butyrate, methyl vinyl ether.

Butyl vinyl ether, octyl vinyl ether.

Vinyl compounds with functional groups such as dodecyl vinyl ether and lauryl vinyl ether, and styrene.

Examples include vinyl hydrocarbons such as α-methylstyrene, butadiene, and vinyl 1-toluene.

Moreover, the tin content in the organic tin-containing polymer is 10 to 22
% is appropriate.

Further, as the copper compound as the antifouling agent, copper alloy,
Common antifouling agents such as cuprous oxide, copper rhodan, copper phosphide, copper rosinate, copper naphthenate, copper polyacrylate can be used, especially copper alloys, cuprous oxide.

Rodan copper is preferred.

As other antifouling agents, triorganotin monomers such as triphenyltin hydroxide, 1-rifenyltin chloride, 1-helibutyltin mesodibrom succinate, etc. can also be used.

Further, the metal powder mentioned above is Cu, which belongs to group Ib of the periodic table.
, Act, MCI belonging to the Ha family, Ca, Ba, ■
Zn, Cd, HCI belonging to group b, Mn belonging to group Wa
can be given. These may be used alone or as a mixture of two or more. Ca powder and Zn powder are particularly preferred in terms of price, toxicity to painting workers, and the like.

These metal powders have a particle size of 3 to 20 microns, preferably about 4 to 8 microns, in the form of powder, granules, or flakes. Further, the amount of metal powder mixed in the paint is preferably 0.1 to 20% by weight. These metal powders are highly active and are used as pigments and color vehicles in paints.

It reacts with trace amounts of water contained in solvents, etc. and generates hydrogen gas, which may cause blistering and expansion of paint containers. In order to prevent this container from expanding, it is effective to use a water absorbing agent in combination.

Examples of water absorbing agents include anhydrite and zeolite.

Silica gel, activated alumina, etc. can be used, but anhydrite and zeolite are particularly effective. The mixing amount is preferably 0.5 to 20% by weight in the paint for anhydrite, and 0.1 to 5% by weight in the paint for zeolite.

Additionally seawater inert pigments such as Bengara, Titanium White.

Talc, silica, calcium carbonate, barium sulfate and seawater-reactive pigments such as zinc oxide, magnesium oxide,
It is also possible to mix calcium oxide.

In addition, to add flexibility to the coating film, a plasticizer may be added as needed.
For example, it is also possible to mix together chlorinated paraffin, chlorinated diphenyl, methylphenyl silicone, low molecular weight polybutene, di-2-ethylhexyl phthalate, dibutyl phthalate, and the like.

(Example) Production example of tri-organotin-containing copolymer Production example 1 8.5 parts of maleic anhydride (parts by weight, same hereinafter) and 37.3 parts of methyl methacrylate were placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer. parts, 2 parts of octyl acrylate, 0.5 parts of benzoyl peroxide and 6 parts of xylene.
After mixing 0 parts and polymerizing at 95 to 100°C for 3 hours, bis(
51.7 parts of tributyltin) oxide and 22 parts of xylene were added and reacted at the same temperature for 1 hour to obtain a copolymer (hereinafter referred to as copolymer A).

Production Example 2 In a reaction vessel similar to Production Example 1, 65 parts of tributyltin methacrylate, 2 parts of octyl acrylate, 32.5 parts of methyl methacrylate, 0.5 parts of benzoyl peroxide, and 82 parts of xylene were charged and heated at 90 to 95°C for 6 hours. Polymerization was carried out to obtain a copolymer (hereinafter referred to as copolymer B).

Production Example 3 50 parts of copolymer A and 50 parts of copolymer B were mixed to obtain a copolymer (hereinafter referred to as copolymer C).

Production Example 4 57 parts of tributyltin methacrylate, 2 parts of octyl acrylate, 41 parts of methyl methacrylate, 0.5 part of benzoyl peroxide and 82 parts of xylene were charged.
Polymerization was carried out at 90 to 95°C for 6 hours to obtain a copolymer (hereinafter referred to as copolymer).

Examples 1 to 13 and Comparative Example 1 Part 4 The compositions shown in Attached Table 1 were mixed and dispersed in a paint conditioner to a particle size of 50 microns or less to produce antifouling paints.

Performance evaluation test Tar epoxy paint on steel plate (our product name: Viscon AC)
was coated in two coats to give a dry film thickness of 200 microns, and then a vinyl tar-based paint (our company's trade name: SILPAX SQ) was applied to give a dry film thickness of 40 microns.

The test plates were overcoated with the antifouling paints produced in Examples 1 to 10 and Comparative Examples 1 to 3 to a dry film thickness of 100 microns, and the following tests were conducted.

(2) Antifouling test The test plates were immersed for 12 months at the Nagasaki part of the test site, and the presence or absence of adhesion of marine organisms was examined.

(2) Storage Stability Test Examples 1 to 10 180 d of the paints of Comparative Examples 1 to 3 were placed in a 200 d container, sealed, and stored at 50'C for 3 months to examine storage stability.

The above test results are listed in Attached Table-2.

(Effect of the invention) As can be seen from the comparative test results in Attached Table 2, the antifouling paint of the present invention clearly has better storage stability than the conventional antifouling paint made of an organic tin-containing copolymer, a copper compound, and a general pigment. The antifouling properties of the paint film were also excellent.

that's all

Claims (1)

[Scope of Claims] 1. An antifouling paint composition comprising an organic tin-containing copolymer as a color vehicle, a copper compound as an antifouling agent, and metal powder as part of the pigment. 2. The organotin-containing copolymer in claim 1 is a copolymer of a bis(triorganotin) salt of a dibasic unsaturated carboxylic acid and another polymerizable unsaturated compound. An antifouling paint composition characterized by containing. 3. The organotin-containing polymer in claim 1 is a copolymer of a bis(triorganotin) salt of a dibasic unsaturated carboxylic acid and another polymerizable unsaturated compound; An antifouling paint composition comprising a mixture of a polymer of a triorganotin salt of a monobasic unsaturated carboxylic acid and a copolymer of another polymerizable unsaturated compound. 4. The organotin-containing polymer in claim 1 contains a copolymer of a triorganotin salt of a monobasic unsaturated carboxylic acid and another polymerizable unsaturated compound. Characteristic antifouling paint composition. 5. The metal powder in claim 1 includes Cu, Ag, which belongs to Group Ib of the Periodic Table, Mg, which belongs to Group IIa,
Ca, Ba, Zn belonging to group IIb, Cd, Hg, VIIa
An antifouling paint composition characterized in that it is one type or a mixture of two or more types selected from the Mn group. 6. The antifouling paint composition according to claim 1,
An antifouling paint composition characterized by containing a water absorbing agent.