JP2747459B2 - Self-polishing antifouling paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a self-polishing type (self-po
lish type) antifouling coating composition
composition), especially polymerizable fatty acid metal soap (met
al soap).

[0002]

2. Description of the Related Art Antifouling marine paints are mainly of the self-polishing and insoluble matrix type.
Are classified into two types. The self-polishing antifouling paint is gradually hydrolyzed and polished by seawater, forming a smooth and fresh surface that reduces friction between the ship surface and water,
Decrease sailing energy. The fresh surface exposes the antifouling toxins contained in the paint until it is used up.

[0003] Self-polishing coatings generally contain a resin containing hydrolyzable groups such as organic acid groups. The rate of hydrolysis of such paints depends on the type of cation and acid, and the percentage of acid groups contained in the resin.

[0004] The self-polishing antifouling paint may be a type containing or not containing a toxin. Paints containing toxins such as organotins are tin-substituted polyacrylates, which are renowned for having very good antifouling and self-polishing properties. However, such paints are extremely toxic and are therefore subject to legal restrictions. Antifouling paints containing copper are less toxic and may optionally contain additional toxins. An example of such a paint is disclosed in Japanese Patent Publication No. 6,284,1.
Nos. 68, 6,094,471 and European Patent Applications 26,958 and 204,456. The toxin-free antifouling paint itself is non-toxic and requires additional toxins. Examples of such non-toxic paints are disclosed in Japanese Patent Publication Nos. 01,131,285, 63,314,280 and 61,218,668.

US Pat. No. 4,774,080 discloses a hydrolyzable antifouling coating composition having very good film-forming properties and its resin being hydrolyzed to a side chain site. Having specific groups capable of forming hydrophilic groups, and being hydrolyzed and dissolved at an appropriate rate in seawater and prepared without the need for expensive and toxic triorganotin compounds There is disclosed a hydrolyzable antifouling paint composition characterized by the ability to do so. The specific group of the side chain includes a cation of a metal selected from zinc, copper and tellurium. The resin is a linear polymer and forms a non-crosslinked thermoplastic film.

[0006]

SUMMARY OF THE INVENTION The present invention comprises a film-forming, low viscosity, unsaturated fatty acid metal soap and, despite the fact that it does not require the use of expensive tin metal compounds, its low viscosity. As a result, it is an object of the present invention to provide a hydrolyzable or self-polishing antifouling paint composition which can be effectively stained because a large amount of an antifouling agent or a toxic agent can be incorporated.

[0007]

SUMMARY OF THE INVENTION A highly hydrophobic saturated acid such as a fatty acid or naphthenic acid and Co, Mn, Zn, Cu,
Soaps prepared from compounds of polyvalent metals such as Ca, etc. are well-known commodities in the paint industry, such as driers and catalysts. These soaps are water-insoluble, but are slowly hydrolyzed. The rate of hydrolysis depends on the type of acid and cation contained in the soap. This means that the hydrolysis rate can be adjusted by changing the acid and cation. These metal soaps cannot be used as binders in coating compositions. However, metal soaps made from unsaturated fatty acids such as linolenic acid, according to the present invention, can form a film when exposed to air at normal room temperature in the presence of a dryer.

[0008] The hydrolyzable coating composition of the present invention
Is represented by the general formula (R1-A1)_n-M- (A2-R2)_m  [Wherein R1 represents a residue of an unsaturated fatty acid or a fatty alcohol.
Wherein M represents a metal having at least two valences,
A1 and A2 each independently represent a carboxylic acid, a sulfonic acid
Or a functional group of phosphoric acid, and R2 is an unsaturated or saturated organic
Acid, alicyclic monovalent organic acid or alcohol, or acrylic acid
Ligomer residues, n and m each represent 1 or 2
And n + m is 2 or 3. ] The metal represented by
Contains soap resin. More particularly, the present invention relates to a ship surface
, Immersed in seawater and gradually hydrolyzed
Prevents the continuous production of smooth and fresh surfaces
Used to form a fouling coating, by crosslinking
A hydrolyzable antifouling paint composition comprising:
(A) General formula (R1-A1)_n-M- (A2-R2)_m  [Wherein R1 represents an alkenyl group derived from an unsaturated fatty acid;
M represents a metal having a valence of 2 or more, and A1 and A2
Is independently carboxylic acid, sulfonic acid or phosphoric acid
Wherein R2 is an aliphatic, aromatic, or alicyclic monovalent
Unsaturated or saturated residues of mechanical acids or alcohols, or acrylic
OligomerResidueAnd n and m are each 1 or 2
And n + m is 2 or 3. ]
A metal soap film-forming binder and (b) stains on the coated surface of a ship immersed in seawater
An effective amount of an antifouling agent to prevent the metal soap film-forming binder,
And metal compounds containing metals having a valence of 2 or more
Reaction composition containing at least unsaturated fatty acid (reactio
n composition).
In addition, the metal soap film-forming binder is used as the antifouling agent.
As a film-forming binder forfunctionTo do
Providing a hydrolyzable antifouling paint composition characterized by the following
It is. Here, the reaction composition is reacted with a metal.
Refers to a reactant or a mixture of reactants, wherein the composition is unsaturated
Organic acids, mixtures of unsaturated organic acids or saturated with unsaturated organic acids
It is a mixture with an organic acid.

The metal soap of an unsaturated fatty acid or oil has a linear structure, and when exposed to oxygen in the air in the presence of a dryer, cures to form a crosslinked film. Since unsaturated metal soap has a very low viscosity, a large amount of an antifouling agent such as CuO can be added. The ability to add a large amount of toxin
In order for the antifouling effect to be exerted continuously for a long period of time, it is important for an antifouling paint which does not use any expensive and powerful toxic substances such as tin compounds.

[0010] The crosslink density of the film formed according to the present invention can be adjusted by changing the amount and type of unsaturated fatty acid. The incorporation of saturated fatty acids reduces the crosslink density and affects the properties of the film. On the other hand, the crosslink density and the properties of the coating affect the rate of hydrolysis.

The above-mentioned metal soap resin comprises a metal compound,
It can be prepared by reacting an unsaturated fatty acid, a mixture of unsaturated fatty acids, or a mixture containing at least one unsaturated fatty acid and a saturated organic acid. In addition, other polymers can be blended with the metal soap resin to change the properties of the soap resin.

Unsaturated fatty acids useful in the present invention include oleic, linoleic, linolenic, eleostearic, ricanoic, ricinoleic and erucic acids. Other useful fatty acids are castor oil, soybean oil, corn oil, cottonseed oil, linseed oil, deer oil, eno oil, poppy oil, rapeseed oil, safflower oil, sunflower oil, tall oil, tung oil,
Mention may be made of those obtained from walnut oil, herring oil, menhaden oil and sardine oil. Other unsaturated organic acids can also be used. The unsaturated acids can be converted to fatty alcohols, which can be used to prepare phosphoric or sulfonic acids containing unsaturated aliphatic groups.

The metal compound may be an oxide, a hydroxide, or a chloride. Most of the metals having at least two valences in the periodic table can be used in the present invention.
Ib, IIa, IIb, IIIa, IIIb, IV
Any metal belonging to the groups a, IVb, Va, Vb, VIIa and VIII may be used. The metal used to prepare the metal soap affects the rate of hydrolysis. Alkali metal soaps are readily soluble in water. Alkaline earth metal soaps are insoluble in water but are hydrolysable in water. The rate of soap hydrolysis varies depending on the type of alkaline earth metal. For example, the rate of hydrolysis of a high molecular weight alkaline earth metal such as barium is higher than that of other low molecular weight alkaline earth metals such as magnesium.
slow. The hydrolysis rates are Al, Co, Zn, Mn, C
The use of Group III and IV metals, such as o, and transition metals also changes.

[0014] Useful saturated organic acids in the present invention, -COOH, is -OSO ₂ H or may be a saturated organic acid containing the _{-O-PO 3 H} 3. The acid is an aliphatic, aromatic, alicyclic monovalent organic acid, or a natural acid such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,
Caprylic acid, capric acid, lauric acid, myristic acid,
Palmitic acid, stearic acid, benzoic acid, naphthoic acid,
Toluic acid, salicylic acid, nitrobenzoic acid, chlorobenzoic acid, chloroacetic acid, bromoacetic acid, benzenesulfonic acid,
Examples include naphthalenesulfonic acid, toluenesulfonic acid, naphthenic acid, rosin, and various natural fatty acids.

[0015] Other unsaturated organic acids useful in the present invention, for example -COOH, as polyester copolymers and copolymers of acrylic acid or methacrylic acid containing -OSO ₂ H or _{-O-PO 3 H} 3 And acid-containing oligomers. Examples of the acrylic copolymer include a copolymer of acrylic acid (or methacrylic acid), styrene sulfonic acid, and / or a vinyl monomer. Examples of polyesters include polyfunctional (polyfunctional)
(ional) alcohols and polymers prepared from polyfunctional acids. The function of these polymers is not to form a film, but to modify the self-polishing properties of the crosslinked film. Therefore, the polymer is not required to have a film-forming property, and may be an oligomer.

The metal soap resin or metal soap film of the present invention
Polymers that can be blended with the forming binder include water-soluble polymers such as rosin resin and polyacrylamide, polymers containing hydrophilic groups such as carboxyl groups, and polyacrylamides. But it is good. Other useful polymers include polyurethanes and polyesters and polyacryls containing carboxylic, sulfonic, phosphoric, amino or amide groups.

[0017]

The present invention will be described in more detail in the following examples.

[0018]

Example 1 In a four-necked reaction vessel, 280 g of linseed oil fatty acid, 50 g of Cu (OH) ₂ and 200 g of xylene were mixed, gradually heated to 140 ° C., and maintained at the same temperature for 2 hours. The reaction was completed. A clear solution with 60% solids was obtained.

[0019]

Example 2 In a four-necked reaction vessel, 150 g of tung oil fatty acid, 120 g of stearic acid, 50 g of Cu (OH)
₂ and 200 g of xylene were mixed, gradually heated to 140 ° C., and maintained at the same temperature for 2 hours to complete the reaction.
A clear solution with a solid content of 57% was obtained.

[0020]

Example 3 In a four-necked reaction vessel, 60 g of methyl methacrylate, 80 g of butyl acrylate, 60 g of acrylic acid, 3 g of butyl mercaptan, 50 g of n-butanol and 200 g of xylene were brought to 120 ° C. And reacted for 3 hours to obtain an oligomer. Thereafter, 50 g of linseed oil fatty acid and 50 g of Ca (OH) ₂ were added to the oligomer and heated to 140 ° C. 140 ° C. for 2 hours
To complete the reaction.

[0021]

Example 4 According to the method of Example 1, a resin was prepared from soybean oil fatty acid and Cu (OH) ₂ . An acrylic copolymer is synthesized using 80 g of methyl methacrylate, 50 g of butyl acrylate, 70 g of acrylic acid, 3 g of azobisisobutyronitrile and 200 g of xylene.
50 g of the acrylic copolymer is blended with 50 g of the above resin.

[0022]

Examples 5-8 Antifouling paints were prepared from the resins of Examples 1-4 according to the following recipe. The physical properties and antifouling properties of the component amount (g) Resin 25 CuO 40 Bentone (Bentone) # 34 1.5 Talc 10 CaCO ₃ 5 Xylene 20 The above antifouling paint are summarized in Table 1. Control 1 is chloro rubber ros
In), Control 2 was prepared from a self-polishing organotin resin. In Table 1, the antifouling test was performed by immersing the test plate in the sea, and the antifouling ability was determined by the fouling area.
) As a percentage.

[Table 1]

Claims (12)

(57) [Claims] 1. On a surface of a ship, the ship is immersed in seawater.
Smooth and fresh due to gradual hydrolysis
An antifouling coating that creates a continuous surface
Antifouling paint composition used to form
Wherein the coating composition comprises: (a) a general formula (R1-A1)_n-M- (A2-R2)_m  [Wherein R1 represents an alkenyl group derived from an unsaturated fatty acid;
M represents a metal having a valence of 2 or more, and A1 and A2
Is independently carboxylic acid, sulfonic acid or phosphoric acid
Wherein R2 is an aliphatic, aromatic, or alicyclic monovalent
Unsaturated or saturated residues of mechanical acids or alcohols, or acrylic
OligomerResidueAnd n and m are each 1 or 2
And n + m is 2 or 3. ]
A metal soap film-forming binder and (b) stains on the coated surface of a ship immersed in seawater
An effective amount of an antifouling agent to prevent the metal soap film-forming binder,
And metal compounds containing metals having a valence of 2 or more
Reaction composition containing at least unsaturated fatty acid (reactio
n composition).
In addition, the metal soap film-forming binder is used as the antifouling agent.
As a film-forming binder forfunctionTo do
A hydrolyzable antifouling paint composition comprising: 2. The hydrolyzable antifouling paint composition according to claim 1, wherein the reaction composition further comprises a saturated organic acid selected from the group consisting of carboxylic acids, organic sulfonic acids, and organic phosphoric acids. 3. The hydrolyzable antifouling coating composition according to claim 1, wherein the reaction composition further comprises a low molecular weight polymeric acid selected from the group consisting of polyacrylic acid and polyester. . 4. The hydrolyzable antifouling paint composition according to claim 1, further comprising a hydrophilic group-containing polymer in addition to the unsaturated metal soap film-forming binder. 5. The method according to claim 1, wherein the metal is any of Ib, IIa, IIb,
IIIa, IIIb, IVa, IVb, Va, Vb, V
The hydrolyzable antifouling paint composition according to claim 1, which is a metal selected from the group consisting of metals belonging to groups IIa and VIII. 6. The method according to claim 1, wherein the unsaturated fatty acid is oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricanoic acid,
The hydrolyzable antifouling paint composition according to claim 1, which is an unsaturated fatty acid selected from the group consisting of ricinoleic acid and erucic acid. 7. The unsaturated fatty acid may be castor oil, soybean oil, corn oil, cottonseed oil, linseed oil, eucommia oil, eno oil, poppy oil, rapeseed oil, safflower oil, sunflower oil, tall oil, kiri oil, walnut oil. The hydrolyzable antifouling paint composition according to claim 1, which is an unsaturated fatty acid obtained from an oil selected from the group consisting of oil, herring oil, menhaden oil and sardine oil. 8. The method according to claim 1, wherein the saturated organic acid is acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, benzoic acid, naphthoic acid, toluic acid. The hydrolysis according to claim 2, wherein the hydrolysis is selected from the group consisting of salicylic acid, nitrobenzoic acid, chlorobenzoic acid, chloroacetic acid, bromoacetic acid, benzenesulfonic acid, naphthalenesulfonic acid, toluenesulfonic acid, naphthenic acid, rosin and natural fatty acids. Antifouling paint composition. 9. The method according to claim 9, wherein the saturated organic acid is an acrylic copolymer,
An oligomer group selected from a copolymer of a vinyl monomer and styrene sulfonic acid, and a polyester prepared from a polyfunctional alcohol and a polyfunctional acid.
3. The hydrolyzable antifouling paint composition according to claim 1. 10. The hydrophilic group-containing polymer is a rosin,
5. The composition of claim 4, wherein the polyacrylamide is selected from polyacrylamide, acrylic polymer, polyester and polyurethane containing hydrophilic groups.
3. The hydrolyzable antifouling paint composition according to 1.). 11. The antifouling agent is CuO.
3. The hydrolyzable antifouling paint composition according to 1.). 12. A method for protecting a hull, said method comprising:
Applies a hydrolyzable antifouling paint composition to the surface of the hull.
And smooth by being gradually hydrolyzed in seawater
Protective film that continuously produces a fresh and fresh surface
Forming a coating composition comprising: (a) a metal soap film-forming binder; and (b) an effective amount of an antifouling agent, wherein the metal soap film-forming binder is , A general formula (R1-A1)_n-M- (A2-R2)_m  [Wherein R1 represents an alkenyl group derived from an unsaturated fatty acid;
M represents a metal having a valence of 2 or more, and A1 and A2
Is independently carboxylic acid, sulfonic acid or phosphoric acid
Wherein R2 is an aliphatic, aromatic, or alicyclic monovalent
Unsaturated or saturated residues of mechanical acids or alcohols, or acrylic
OligomerResidueAnd n and m are each 1 or 2
And n + m is 2 or 3. ]
And the metal soap film-forming binder has a low content.
At least a metal compound containing a metal having a valence of 2 or more;
Reaction composition containing at least unsaturated fatty acid (react
(ion composition).
And a metal soap film-forming binder
But as a film-forming binder of the antifouling agentfunctionDo
A method comprising: