JPH0885767A - Antifouling coating material - Google Patents

Abstract

PURPOSE: To obtain an antifouling coating material which forms a biojelly layer on the surface of an underwater structure to protect it from the deposition of fouling aquatic life without using any antifouling agent by using a specified compound as the component. CONSTITUTION: This material comprises a biojelly-forming compound having a benzylideneaniline skeleton or styryl or cinnamyl groups and a binder. The compound having a benzylidene skeleton is represented by formula I (wherein n and m are each 0-5; X and Y are each a halogeno, a 1-20C hydrocarbon group, a 1-2 C alkoxy, nitro, amino, hydroxy, carboxyl, ester, cyano, azo or azomethine), and the compound having styryl or cinnamyl groups is represented by formula II (wherein X<1> is H, carboxyl, hydroxymetyl, aldehydo, carbonyl or amido, and Y is a halogeno, a (halo)alkyl, nitro an alkoxy, carboxyl, ester, cyano, azo, azomethine or amino, or the like).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing aquatic fouling organisms from adhering to the surface of ships, bridges and the like. In the present specification, the aquatic fouling organism refers to an adhering organism that attaches to an artificial structure in water and causes industrial and economic disadvantages, and an adhering organism that grows to a size that an individual can visually observe, For example, it refers to animals such as barnacles, mussels, oysters, hydroids, bryophytes, ascidians, serpras, and plants such as Ulva.

[0002]

BACKGROUND ART When aquatic organisms such as barnacles, serpra, squirts, bryozoans, oysters, and oysters adhere to the bottom of ships, problems such as increased weight, increased water flow resistance, and reduced cruising speed will occur, resulting in reduced ship life. It causes industrial problems such as increased fuel consumption. Methods for preventing adhesion of these aquatic organisms have been studied for a long time, and biological methods using natural enemies of organisms causing adhesion, use of structural materials that are difficult to attach (e.g. use of copper alloys, silicone-based materials) Paint, fluorine-based paint, etc.), prevention of larva inflow (for example, a method of shielding with a screen), extermination of larvae (for example,
Use of light, ultraviolet rays, color, ultrasonic waves, etc., temperature rise, oxygen deficiency and other difficult environments to survive), mechanical removal of adhering organisms (for example, cleaning,
(Jet cleaning, brushing, suction, etc.), chemical or biochemical methods (for example, shellfish killing, repelling, use of antifouling agents, etc.) are being considered. Recently, because of its wide application range, high effect, and easy processing, the method of applying ship bottom paints containing shellfish killers, repellents, antifouling agents, etc. has been widely adopted and studied. Came. However, paints containing these chemicals are designed so that the drug in the coating film gradually elutes into the water, or the paint containing this is gradually scraped and dissipated into the water, and new paint surfaces are always exposed. Therefore, it has been pointed out that there is a concern that it will have an adverse effect on the marine environment. In particular, when it was pointed out that the tin compounds, which are the most representative antifouling agents in the 1980s, were contaminated by fish and shellfish, various regulations were added to tin-containing ship bottom paints in European countries and the United States, and they replaced the aquatic organisms. The development of a method for preventing biological pollution has emerged as an urgent issue. However, at present, no promising method has been developed as an alternative to the paint for contaminating ship bottoms, which contains antifouling agents. The focus of the research is on the development of low toxicity antifouling agents that replace tin compounds.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a paint which does not use an antifouling agent and which prevents the attachment of aquatic fouling organisms.

[0004]

The present invention relates to an aquatic fouling organism adhesion preventing paint, which comprises forming a biojelly layer on the surface of a structure in water.

In the present invention, the structure means a ship bottom, a fishing net, a water conduit, a bridge and the like. Conventionally, slime was attached to the underwater structure.

[0006] The slime layer is a slimy thin film layer formed mainly by metabolites of organisms in water.
Conventionally, thin slime layers have been studied as a type of contaminants on the bottom of ships. Therefore, there was no idea to positively use this to prevent the attachment of large-scale aquatic fouling organisms that substantially affect the life and operation of ships such as barnacles, sea lions, oysters, cellulas and mussels. The present invention is a method of positively forming this slime layer on the surface of an underwater structure, thereby preventing the attachment of aquatic fouling organisms, and the method of preventing the attachment of aquatic fouling organisms by such a method has never been known. unknown. As a slime layer used for such a purpose, a jelly-like layer having a thickness of 0.3 mm or more, more preferably 0.5 mm to 6 mm, and particularly 1 mm to 5 mm is suitable. Therefore, in the present invention, a slime layer having a thickness of about 0.3 mm or more is particularly called bio jelly. In the present invention, the thickness of the slime layer was determined by measuring the film thickness after allowing the test plate to be flat and leaving it at room temperature for 1 hour. As mentioned above, this slime layer or biojelly layer is a metabolite of mainly aquatic organisms, especially microorganisms, but it is a layer in which organisms such as bacteria and diatoms can live, and those organisms are actually observed. . Chemically, various sugars,
It contains polysaccharides, lipids, glycoproteins and phospholipids.
A jelly-like slime layer having a thickness of 0.3 mm or more is particularly useful for preventing the attachment of large aquatic fouling organisms.

The slime layer can be positively formed on the underwater structure by applying a paint containing a certain compound. Examples of such slime layer-forming substances include various benzylideneaniline derivatives. When these compounds are used, it is possible to easily form a thick slime layer, that is, biojelly, on the surface of a structure in water. Therefore, in the present specification, a compound having such properties is particularly referred to as a biojelly forming agent. To tell.

The present invention relates to an antifouling paint containing such a biojelly-forming compound and a binder. The biojelly-forming compound is preferably a compound having a benzylideneaniline skeleton or a compound having a styryl group or a cinnamyl group. The compound having a benzylidene aniline skeleton is a compound represented by the following formula I.

[Chemical 3] In the formula, n and m are each a number of 0-5, X is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or 1 to 20 carbon atoms.
A group selected from an alkoxy group, a nitro group, an amino group, a hydroxyl group, a carboxyl group, an ester group, a cyano group, an azo group, and an azomethine group (provided that when n is 2 or more, X represents 2 or more types of groups). Y may be a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a nitro group, an amino group, a hydroxyl group, a carboxyl group, an ester group, a cyano group, an azo group, and A group selected from azomethine groups (provided that when m is 2 or more, Y may represent 2 or more types of groups).

N and m are preferably 0 or 1 respectively
Is. X is preferably a halogen atom, particularly chlorine or bromine; a hydrocarbon group, more preferably 2-18 carbon atoms.
An aliphatic hydrocarbon group which may have a saturated or unsaturated side chain of, for example, ethyl, isopropyl, n-propyl, t-
Groups such as butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, lauryl, stearyl, oleyl; alkoxy groups, especially saturated or unsaturated alkoxy groups having 1-18 carbon atoms, such as ethoxy, butoxy, hexyloxy, octoxy. , Nonyloxy, octoxy, nonyloxy, stearyloxy, benzyloxy, naphthyloxy group, hydroxyl group; nitro group and the like.

Y is preferably a halogen atom, especially chlorine,
Or bromine; hydrocarbon group, more preferably 1-carbon
An aliphatic hydrocarbon group which may have 18 saturated or unsaturated side chains, for example, ethyl, isopropyl, n-propyl, t-butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, lauryl, stearyl, Groups such as oleyl; alkoxy groups, especially saturated or unsaturated alkoxy groups having 1-18 carbon atoms, such as ethoxy, butoxy, hexyloxy, octoxy, nonyloxy, octoxy, nonyloxy, stearyloxy, benzyloxy, naphthyloxy groups, hydroxyl groups. Such as a nitro group.

Among the compounds having a benzylideneaniline skeleton, particularly preferred biojelly-forming compounds are:
4'-ethylbenzylidene-4-ethylaniline, 2'-
Isopropylbenzylidene-4-butoxyaniline, 4
-Nonylbenzylideneaniline, 4'-stearylbenzylidene-4-butoxyaniline, benzylidene-4-
Nonyloxyaniline, 4'-ethylbenzylidene-4
-Hexylaniline, 4'-ethoxybenzylidene-4
-N-octylaniline, 2'-butoxybenzylidene-2-ethylaniline, 4'-naphthyloxybenzylideneaniline, 4'-ethylbenzylidene-4-nitroaniline, 3 ', 4'-diethylbenzylidene-4-butylaniline, Terephthalidene-di-4-butoxyaniline, di-4-butoxybenzylidene-p-penylenediamine, benzylidene-4-n-octylaniline, 4 '
-Nonylbenzylidene-4-methoxyaniline, 4'-
Ethylhexylbenzylideneaniline, 4 ', 4-oleyloxybenzylideneaniline, 2'-ethoxy-4'-
Examples include bromobenzylideneaniline, 4'-hexylbenzylidene-4-octoxyaniline, 4'-nonyloxybenzylidene-4-nonylaniline, 4'-nonylbenzylidene-2-butoxyaniline.

The compound having a styryl group or cinnamyl group suitable for the present invention is a compound represented by the following formula. Formula I:

[Chemical 4] The compound represented by the formula I used in the present invention is typically a styrene compound in which X is hydrogen, X is a carboxyl group (cinnamic acid type), a hydroxymethyl group (cinnamic alcohol type), an aldehyde group ( Cinnamyl compounds such as cinnamic aldehyde) and amide (cinnamic amide). The aromatic group or carbon directly connected to the aromatic group may have a substituent.

The aromatic group is, like divinylbenzene,
It may have another ethylenically unsaturated group such as a vinyl group (when m = 1). Further, it may have another substituent (Y), for example, the groups described above. When n is 0, the substituent (Y) represents a state without a substituent, that is, a hydrogen atom. The number of substituents (Y) is preferably 2 or less. When Y is a halogen atom, it may be any of F, Cl, Br and I.
Cl or Br is preferred. When Y is an alkyl group, it has 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, such as a saturated or unsaturated alkyl group which may have a branch, a cycloalkyl group and an aralkyl group. . If the number of carbon atoms and the number of substituents are too large, the molecular weight per styryl or cinnamyl group (simply referred to as equivalent) becomes too large, which is not preferable. The alkyl group may be substituted with halogen. Other preferable examples of Y include a nitro group, a cyano group, an azomethine group, an azo group, an alkoxy group and an alkoxysilyl group. The alkoxy group and the alkoxysilyl group are particularly preferably an alkoxy group having 1 to 2 carbon atoms. The alkoxysilyl group may be an alkoxysilylalkyl group. In this case, the alkyl group preferably has 1 to 2 carbon atoms. The substituent (Y) is a reactive group itself,
For example, it may be a hydroxyl group, a carboxyl group, an amino group, an ammonium group, a sulfonic acid group, a phosphonium group, a sulfonium group, etc., and the carboxyl group may be an organic or inorganic salt or an ester. In addition, the onium group and carboxyl group control the ionicity of the biojelly forming agent, taking into consideration the compatibility with the blended coating components, the affinity for the base material, the water properties of the system used, the solubility, etc. , Is important in adjusting paint properties. Similarly, the length of the alkyl group when Y is an alkyl group or an alkoxy group and the length of the ester residue when it is an ester adjusts the affinity and lipophilicity of the biojelly-forming agent component, and It is useful for controlling compatibility, controlling transferability from paint to water, and controlling release.

R'represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom and the like. The alkyl group, which is typically a hydrogen atom, has 1 to 18 carbon atoms, preferably 1 to 9 carbon atoms,
Particularly, it is 1 to 3, and it may be a cycloalkyl group or an aralkyl group. It is better not to have a branch or an unsaturated bond.
Typically it is methyl or ethyl. The halogen atom is chlorine or bromine. The number of substituents is 2 or less, preferably 0 or 1. m is 0 or 1, especially 0.

The compound having a styryl group or a cinnamyl group used in the present invention has a molecular weight of about 100 to 800,
Particularly, about 100 to 600 is preferable. If the molecular weight is too large, the formation of biojelly becomes insufficient and the layer thickness does not grow. Further, it is preferable that not only the molecular weight but also the styryl equivalent or the cinnamyl equivalent is in the range of about 100 to about 600.

When the compound used in the present invention is cinnamic acid, its ester or salt may be used. In particular, cinnamic acid ester is extremely effective in growing biojelly. The ester is an ester with a branched or straight-chain saturated or unsaturated C 1-18, more preferably 1-12, especially 1-8 alcohol.

The salt may be either an inorganic salt or an organic salt. Inorganic salts include alkali metals such as Na,
Examples thereof include alkaline earth metal salts such as K, such as Ca and Mg, ammonium and other Mn, Zr (0), Al, Zn, Fe and the like. Examples of the organic salt include amines, alkanolamines, polyamines, N-heterocyclic compounds such as imidazoline.

In the present invention, the biojelly-forming agent is blended in a suitable coating composition and dipped in water to coat the surface of the structure to be used. It can be used as a paint for fishing nets by dissolving or dispersing it in an appropriate solvent and adding a polymer if necessary. The binder suitable for the present invention includes a glass transition temperature (Tg) of 15 to 120 ° C., more preferably 25 to 100 ° C., a number average molecular weight of 1,000 to 50,000,
More preferably 5000 to 30000, hydroxyl value 0 to 1
00, more preferably 0 to 80. Further, the Tg value in the above range is suitable for achieving film strength as an antifouling paint and appropriate film consumption.

When the glass transition temperature is lower than 15 ° C., the coating film becomes too soft and, for example, peeling or the like occurs during navigation of a ship. When the temperature is higher than 120 ° C, cracks and the like occur in the coating film. When the number average molecular weight is less than 1000, a tough coating film cannot be obtained. When the number average molecular weight is more than 50,000, the viscosity of the coating composition is high, and more solvent than necessary must be used to maintain a constant viscosity. When the hydroxyl value is greater than 100, seawater enters the membrane and elutes more biojelly agent than necessary, so that the stainproof property cannot be maintained for a long time. Examples of the binder resin that can be used in the present invention are acrylic resin, polyester resin, alkyd resin, vinyl resin, epoxy resin, urethane resin, urea resin and the like.

The biojelly-forming compound of the present invention is preferably blended in an amount of 15 to 75% by weight, more preferably 20 to 60% by weight, based on the coating solid content. The binder resin is preferably added in an amount of 20 to 70% by weight, more preferably 30 to 60% by weight, based on the total weight of the coating material.

In the antifouling paint of the present invention, for example, in addition to the above-mentioned biojelly-forming compound and the binder resin, a suitable diluent, for example, water, alcohol, alkyl glycol, cellosolve, acetic ester, xylene, toluene, ketone or the like extender pigment. For example, talc, a coloring pigment, a curing agent, etc. may be mixed. Further, in the present invention, known antifouling agents, pesticides, and herbicides can be used within the range that does not inhibit biojelly formation.

The coating method for coating the antifouling coating composition of the present invention on a structure may be any method such as coating, dipping,
A spray or the like can be used. After a certain amount of time, the bio jelly is peeled off by a mechanical action due to waves and the progress of a ship, and a new jelly layer is formed.
In order to facilitate this formation, it is preferable that the paint itself is gradually scraped away by the waves and the operation of the ship so that a new painted surface appears. The new coated surface grows better with biojelly than the old coated surface, and a thick biojelly layer is formed in a short time. Such properties are evaluated by the degree of wear of the film thickness. In the present specification, the degree of film thickness consumption is measured by the following method. The coating material is applied on an acrylic resin disk so that the dry film thickness is about 200 μm, and dried at room temperature for one day and night, and the initial film thickness (d ₀ ) is measured by a surface roughness meter. Next, this coating disk was rotated in seawater at a peripheral speed of 30 knots for one month, and the film thickness (d ₁ ) was measured with a surface roughness meter. The difference (d ₁₎
-D ₀ ) is defined as the degree of wear. The coating material used in the present application has particularly favorable results when the degree of wear is 2 to 40 μm.

The slime layer, in particular, the biojelly layer is formed by immersing the structure, which has been treated by coating, impregnating, or kneading a coating containing a biojelly-forming agent, in water. Just do it. Less than,
The present invention will be described with reference to examples.

Production of Binder Resin : Binder Resin Production Example A 69 parts of xylene and 8 parts of n-butanol were added to a four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, and 110 parts were added.
Keep at ℃ to 120 ℃. 67 parts of styrene in this solution,
A mixed solution of 21 parts of 2-ethylhexyl acrylate, 12 parts of 2-hydroxyethyl methacrylate and 2 parts of azobisisobutyronitrile was added dropwise at a constant rate over 3 hours, and the temperature was kept for 2 hours after the addition. As a result, the solid content of the resin solution 53.
Varnish A having 0% and a resin number average molecular weight of 9,900 was obtained.
The obtained binder resin had a Tg of 40 ° C. and an OH value of 5
It had 0 mg kOH. Tg is JIS K7121-
The value measured in 1987 is used.

Binder Resin Production Example B 69 parts of xylene and 8 parts of n-butanol were added to a four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, and added to 110.
Keep at ℃ to 120 ℃. Methacrylic acid-2 in this solution
-Ethylhexyl 45 parts, styrene 30 parts, 2-ethylhexyl acrylate 6 parts, 2-hydroxyethyl methacrylate 16 parts, methacrylic acid 3 parts, azobisisobutyronitrile 2 parts mixed solution at a constant rate for 3 hours. After dropping, the temperature is kept for 2 hours after dropping. As a result, a varnish A having a resin solution solid content of 56.0% and a resin number average molecular weight of 8600 was obtained. The obtained binder resin has Tg: 25 ° C., OH
Value: had 70 mg kOH.

Binder Resin Production Examples C to N Varnish C shown in Table 1 in the same manner as Binder Production Example B
~ N was synthesized.

[Table 1]

Examples 1 to 42 Preparation of Antifouling Paints Using the varnishes prepared above, antifouling paints were prepared according to the formulations shown in Tables 2 to 5.

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

The bio-jelly-forming paint prepared as above was applied to a commercially available acrylic plate (300 mm × 100 mm × 2 m).
m) is applied to a dry coating film thickness of about 200 μm and left for one day to dry the test plate.
It was immersed in the sea at a depth of about 1 m, and visually observed as the adhered area% of the adhered amount of animals such as barnacles and cerpra, and plants such as Ulva and Aonouri. The results are shown in Table 6.

[0032]

[Table 6]

Comparative Examples 1 to 8 Preparation of Comparative Paint A paint containing no biojelly forming agent was prepared according to the formulation shown in Table 7.

[0034]

[Table 7]

Using this coating composition, formation of biojelly and antifouling property were evaluated, and the results are shown in Table 6.

[0036]

Industrial Applicability By intentionally forming a biojelly layer on an underwater structure, adhesion of aquatic fouling organisms such as barnacles, cellula, oysters and ascidians can be effectively prevented. When a benzylidene aniline compound is used, the biojelly layer can be formed thick and quickly. By increasing the thickness of the slime layer, the aquatic pollutant can be attached more effectively.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area A01N 37/10

Claims (5)

[Claims] 1. An antifouling paint comprising a biojelly-forming compound having a benzylideneaniline skeleton, a styryl group or a cinnamyl group, and a binder. 2. A compound having a benzylidene aniline skeleton has the general formula: In the formula, n and m are each a number of 0-5, X is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or 1 to 20 carbon atoms.
A group selected from an alkoxy group, a nitro group, an amino group, a hydroxyl group, a carboxyl group, an ester group, a cyano group, an azo group, and an azomethine group (provided that when n is 2 or more, X represents 2 or more types of groups). Y may be a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, a nitro group, an amino group, a hydroxyl group, a carboxyl group, an ester group, a cyano group, an azo group, and The antifouling paint according to claim 1, which is a benzylideneaniline derivative showing a group selected from azomethine groups (provided that when m is 2 or more, Y may represent two or more groups). 3. A compound having a styryl group or a cinnamyl group is represented by the formula: [In the formula, X is a hydrogen atom, a carboxyl group, a hydroxymethyl group, an aldehyde group, a carbonyl group, or an amide group.
(However, when X is a carboxyl group, it may be an ester or salt thereof); Y is a halogen atom, an alkyl group, a halogenated alkyl group, a nitro group, an alkoxy group,
Carboxyl group, ester group, cyano group, azo group, azomethine group, amino group, alkoxysilyl group, alkoxysilylalkyl group; R'is hydrogen atom, alkyl group, halogen atom; n is 0 to 2, m is 0 or 1 The biojelly forming agent according to claim 1, wherein 4. The antifouling paint according to claim 1, wherein the binder has a Tg of 15 to 120 ° C. 5. An antifouling paint having a film thickness consumption of 2 to 40 μm /
The antifouling paint according to claim 1, which is a month.