CN1069505A - Self-grinding antifouling coating composition - Google Patents

Abstract

A self-polishing antifouling paint composition comprising a metal soap resin prepared by reacting a metal compound containing at least a divalent metal with an unsaturated fatty acid, a mixture of unsaturated fatty acids, or a mixture containing an unsaturated fatty acid and other saturated organic acids.

Description

The invention relates to a self-grinding antifouling paint composition, in particular to a paint composition containing a polymerizable fatty acid metal soap.

Antifouling marine paints are mainly divided into two types, self-grinding and insoluble block. Self-abrasive antifouling paint will be gradually hydrolyzed and polished by seawater, resulting in a smooth, fresh surface that reduces friction between the ship's surface and water, thereby reducing sailing resistance. Fresh surfaces contain the paint's antifouling toxins until they are used up.

Self-grinding coatings generally contain a resin containing hydrolyzable groups, such as organic acid groups. The hydrolysis rate of this coating depends on the type of organic acid groups and cations, and the percentage of acid groups in the resin.

Self-abrasive antifouling coatings can be either toxin-containing or non-toxin-free. For example, poison coatings containing organotins are tin-substituted polyacrylates, which have been widely used due to their superior antifouling and self-abrasive properties. However, this paint is very toxic and therefore restricted by law. Copper-containing antifouling paints are less toxic and can be combined with additives when required.

It is an object of the present invention to provide a hydrolyzable or self-abrasive antifouling coating composition which forms a film capable of forming unsaturated Acid metal soap, because of its low viscosity, can easily carry a large amount of poison and achieve a good antifouling effect.

It is well known in the paint industry to make soaps from highly hydrophobic saturated acids (e.g. fatty acids, acids) and polyvalent metal (e.g. Co, Mn, Zn, Cu, Ca, etc.) compounds, such as driers and catalysts. These soaps are insoluble in water but hydrolyze slowly. The speed of hydrolysis depends on the type of acid and the cations contained in the soap. This means that the rate of hydrolysis can be adjusted by changing the acid and cation. These metallic soaps cannot act as binders for coating compositions. However, in accordance with the present invention, metal soaps prepared from unsaturated fatty acids such as linoleic acid can form films when present at normal room temperature with a desiccant and exposed to air.

A hydrolyzable coating composition comprising a metal soap resin having the following general structure: R1-A1-M-A2-R2, wherein R1 is an unsaturated fatty acid or a residue of a fatty acid; M is a metal having at least a divalent ; A1 and A2 are independent functional groups of hydroxy acid, sulfuric acid or phosphoric acid, R2 is unsaturated or saturated organic acid, alicyclic monovalent organic acid or alcohol, or the residue of acrylic acid oligomer.

Metallic soaps of unsaturated fatty acids or oils have a linear structure that hardens the interlinked film by exposure to oxygen present in the air in the presence of a desiccant. Because unsaturated metal soaps have a very low viscosity, large amounts of antifouling agents such as CuO can be added. For antifouling coatings that do not use any expensive and highly toxic agents such as tin compounds, it is important to be able to easily load high quantities of agents in order to achieve a long lasting antifouling effect.

By varying the amount and type of unsaturated fatty acids, the cross-linking density of the films formed according to the present invention can be adjusted. Incorporation of a saturated fatty acid reduces crosslink density and affects membrane properties. In turn, crosslink density and membrane properties affect the rate of hydrolysis.

The metal soap resin described above can be prepared by reacting a metal compound with an unsaturated fatty acid, a mixture of unsaturated fatty acids, or a mixture comprising one or more unsaturated fatty acids and a saturated organic acid. In addition, other polymers can be blended with the metal soap resin to modify the properties of the metal soap resin.

The unsaturated fatty acid available in the present invention has oleic acid, linseed oleic acid, linseed oleic acid, oleostearic acid, galactobionic acid, ricinoleic acid, erucic acid. Other usable fatty acids are those derived from castor oil, soybean oil, corn oil, cottonseed oil, linseed oil, auburn oil, perilla oil, poppy seed oil, rapeseed oil, safflower oil, sunflower oil, pine oil, tung oil , walnut oil, herring oil, herring oil and sardine oil; in addition, unsaturated organic acids can also be used, which can be converted into a fatty alcohol, which, in turn, can be used to make a Phosphoric or sulfonic acids containing unsaturated aliphatic groups.

Metal compounds can be oxides, hydroxides, or chlorides. Most metals having a valence of at least two in the periodic table are useful in the present invention. These are metals belonging to groups Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIIa and VIII. The metal used to make the metal soap affects the rate of hydrolysis. Alkali metal soaps are immediately soluble in water. Soaps of alkaline earth metals are insoluble in water but hydrolyze in water. Different alkaline earth metals can cause different hydrolysis rates of soaps. For example, alkaline earth metals with higher quantum weights, such as barium, have a slower rate of hydrolysis than other alkaline earth metals with lower molecular weights, such as magnesium. When using Group III, IV metals and transition metals (such as Al, Co, Zn, Mn, Ca, etc.), the hydrolysis rate will also change.

Saturated organic acids useful in the present _invention include -COOH, _-OSO3H or -O- _PO3H3 acids. These acids can be aliphatic, aromatic, alicyclic monovalent organic acids or natural acids, the natural acids referred to here can be from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, capric acid, Diacid, myristic acid, palmitic acid, octadecanoic acid, benzoic acid, phthalic acid, toluic acid, o-hydroxybenzoic acid, nitric acid, chlorobenzoic acid, toluenesulfonic acid, naphthenic acid, abietic acid and various Selected from natural fatty acids.

Other saturated acids useful in the present invention are polymers with acids such as acrylic acid copolymers, acrylic-methacrylic acid copolymers, polyesters with -COOH, _-OSO3H- or _-O - _PO3H3 . Examples of acrylic copolymers are those made from acrylic and/or methacrylic acid, styrene sulfonic acid and/or vinyl monomers. Examples of polyesters are made from polyfunctional alcohols and polyfunctional acids. The function of the functional group of the polymer is not to form a film, but to improve the self-grinding property of the cross-linked film, so oligomers or low molecular weight polymers can be used.

Polymers that can be blended with the metal soap resins of this invention are water soluble (such as rosin resins and acrylamides), contain hydrophilic groups (such as hydroxyl groups) and polyacrylamides. Other useful polymers include polyacrylics, polyesters and polyurethanes with hydroxy acid groups, sulfonic acid groups, phosphoric acid groups, amine groups or amide groups.

The present invention will be described in further detail below with the aid of embodiment:

Example 1

In a four-necked reactor, mix 280 grams of linseed oil fatty acid, 50 grams of Cu(OH) ₂ and 200 grams of xylene, slowly heat to 140°C and maintain the temperature at 140°C for two hours to complete the reaction A clear solution with a solids content of 60% was obtained.

Example 2

In a four-necked reactor, mix 150 grams of oleic acid fatty acid, 120 grams of stearic acid, 50 grams of Cu(OH) ₂ 200 grams of xylene, slowly heat to 140°C and maintain the temperature at 140°C for two hours , to complete the reaction. A clear solution with a solids content of 57% was obtained.

Example 3

In a four-necked reactor, 60 grams of methyl methacrylate, 80 grams of butyl acrylate, 60 grams of acrylic acid, 3 grams of butylmercaptan, 50 grams of n-butanol and 200 grams of xylene were reacted at 120 ° C for three hours to form a polymer. Then 50 grams of linseed oil fatty acid and 50 grams of Ca(OH) _₂ were added to the polymer and heated to 140°C. The reactor was maintained at 140°C for two hours to allow the reaction to complete.

Example 4

To the same extent as Example 1, a resin was made from soybean oil fatty acid and Cu(OH) ₂ . An acrylic copolymer was made by using 80 grams of methyl methacrylate, 50 grams of butyl acrylate, 70 grams of acrylic acid, 3 grams of azobisisobutyronitrile and 200 grams of xylene. 50 grams of acrylic copolymer and 50 grams of the above resin were blended.

Examples 5 to 8

Adopt the resin prepared by embodiment 1 to 4, make antifouling paint according to following formula:

Ingredient Quantity (grams)

Resin 25

CuO 40

Swelling±#34 1.5

Talc 10

CaCO ₃ 5

Xylene 20

The physical and antifouling properties of the antifouling paints are summarized in Table 1. Control 1 was made from a chlororubber rosin, while Control 2 was made from a self-grinding organotin resin.

Table 1

Embodiment 5 6 7 8 Control 1 Control 2

Hardness H H H H H H H B H H H

Viscosity (ku) 70 65 85 93 85 93

Shock Resistant Can Can Can Can Be Good Good Good Good

(500g*50cm)

Antifouling (%)

1 month 0 0 0 0 0 0 0

3 months 15 10 10 5 30 2

6 months 45 40 40 30 70 20

9 months 90 90 70 70 100 60

Note: The implementation of the antifouling test is to immerse the test piece in the sea, and the antifouling ability is expressed by the percentage of the dirty area.

Claims (17)

1, a kind of self-abrasion anti-foul paint compound, it is characterized in that: described composition comprises the metallic soap resin with following general formula: R1-A1-M-A2-R2, described R1 is a kind of aliphatic unsaturated hydrocarbon, described M is a kind of metal of divalence at least that has, described A1 and A2 are the functional groups of hydroxy acid, and described R2 is a kind of unit price organic acid of aliphatic series; Described metallic soap resin is to comprise the metallic compound and the product that comprises the reaction constituent interreaction of unsaturated organic acid of the above metal of divalence.

2, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described composition comprises a kind of unsaturated organic acid, and described unsaturated organic acid is selected for use from hydroxy acid, organic sulfonic acid and organic phosphoric acid.

3, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described metallic soap resin combination comprises low-molecular-weight polymeric acid, and described polymeric acid is selected for use from polyacrylic and polyester.

4, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described composition comprises the polymkeric substance that has hydrophilic group, the polymkeric substance of described hydrophilic group and described metallic soap resinous blending.

5, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described metal is to be subordinated in the metal of periodictable I b, II a, II b, III a, III b, IV a, IV b, V a, V b, VII a and VIII class to select for use.

6, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described unsaturated organic acid is a kind of unsaturated fatty acids, and described unsaturated fatty acids is selected for use from oleic acid, linolic acid, linolenic acid, oil-stearic acid, galactosonic acid, castor oil acid, erucic acid.

7, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described unsaturated organic acid is a kind of unsaturated fatty acids, described unsaturated fatty acids is obtained from a kind of oil, and described oil is selected for use from castor oil, soybean oil, oil of maize, oleum gossypii seminis, Semen Lini oil, oiticica oil, perilla oil, poppyseed oil, rape seed oil, safflower oil, Trisun Oil R 80, pine tar, tung oil, walnut oil, pilchardine, big menhaden fish oil and sardine oil.

8, according to the described self-abrasion anti-foul paint compound of claim 2, it is characterized in that: described unsaturated organic acid is selected for use from acetate, propionic acid, butyric acid, valeric acid, caproic acid, sad, capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, phenylformic acid, phthalandione, toluic acid, O-hydroxybenzoic acid, nitre phenylformic acid, chloro-benzoic acid, toluenesulphonic acids, naphthenic acid, sylvic acid and natural acid.

9, according to the described self-abrasion anti-foul paint compound of claim 2, it is characterized in that: described unsaturated organic acid comprises the polymeric acid of polyradical, described polymeric acid be from acrylic copolymer, vinylformic acid-Sipacril 2739OF, comprise the ethylene copolymer of styrene sulfonic acid and the polyester made by multi-group alcohol and polyfunctional group acid select for use.

10, according to the described self-abrasion anti-foul paint compound of claim 4, it is characterized in that: described to comprise the polymkeric substance that has hydrophilic group be from rosin, polyacrylamide, polyacrylic acid, polyester and contain the polyurethane of hydrophilic group and select for use.

11, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described R2 is a kind of aromatic unit price organic acid.

12, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described R2 is a kind of unit price organic acid of alicyclic ring.

13, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described R2 is a kind of alcohol.

14, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described R2 is the unsaturated resistates of acrylated oligomer.

15, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described R2 is the saturated resistates of acrylated oligomer.

16, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described A1 and A2 are the functional groups of sulfonic acid.

17, according to the described self-abrasion anti-foul paint compound of claim 1, it is characterized in that: described A1 and A2 are the functional groups of phosphoric acid.