JPS6239672A - Anti-fouling coating material - Google Patents

Abstract

PURPOSE:To provide the titled material containing a specific polyalkylene oxide unsaturated carboxylic acid ester resin and an antifouling component at specific ratios, effective to inhibit the adhesion of various fouling life including adhesive algae and adhesive animal for a long period and useful for the treatment of ships, etc. CONSTITUTION:The titled material contains (A) 10-95(wt)% (based on the whole solid content) polyalkylene oxide unsaturated carboxylic acid ester resin consisting of a copolymer of (i) 5-75% monomer of formula [R1 is H, CH3 of CH2COO(CmH2mO)nR<2>, R<2> is H or 1-28C hydrocarbon group; CmH2mO is oxyalkylene; m is 2-4; n is 1-200), (ii) 3-55% polymerizable unsaturated carboxylic acid or its salt and (iii) 15-80% hydrophobic polymerizable unsaturated monomer and (B) 5-85% 2-amino-3-chloro-1,4-naphthoquinone and/or N- fluorodichloromethyl thiophthalimide.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention effectively prevents staining caused by adherent algae, adherent animals, etc. on the surfaces of submerged parts of various structures such as ship bottoms over a long period of time. Related to antifouling coating material.

[Conventional technology]

Currently related to ship bottoms, undersea communication cables, transportation pipelines, observation buoys, buoys, oil fences, silt protector-1 piers, thermal or nuclear power plant cooling channels, aquaculture fishing nets, fixed fishing nets, and marine development and marine civil engineering works. When various types of equipment and structures are immersed in the sea for a long period of time, they become mussels.

Adhering animals such as fujibo, serpura, oysters, hydrozoans, bryozoans, sea squirts, and sponges, and algae such as sea lettuce, blue laver, shiomidoro, hibimidoguchi, shiogusa, and miru can cause problems in ship operations, decreases in lumber strength, and structures. In addition to deterioration of seawater, decrease in seawater inflow, and decrease in cooling efficiency, aquaculture fishing nets have various other negative effects due to mesh clogging.

Conventionally, in order to prevent such damage due to biofouling in the sea, heavy metal compounds such as cuprous oxide and mercury oxide, carbamic acid compounds such as tetramethylthiuram disulfide and zinc dimethyldithiocarbamate, and phenarsazine chloride are generally used. Arsenic compounds such as bis(
Contains organic tin compounds such as tri-n-butyltin) oxide, and uses linseed oil, soybean oil, and hempseed oil as vehicles.

Tung oil, vinyl chloride resin, chlorinated rubber resin, acrylic resin,
Antifouling paints or fishing net anti-teta agents containing alkyd resin, urethane resin, polyester resin, coumaron resin, pine resin, tar pitch, etc. are used, and in power plants and industrial cooling waterways, chlorine and formalin are poured directly into waterways. This prevents the attachment of the above-mentioned sessile organisms.

In addition, a technology for an antifouling composition for fishing nets using 2-amino-3-chloro-1,4-naphthoquinone as an active ingredient and a rosin-based resin, a coumaron-based resin, or a cellulose-based resin as a vehicle was disclosed in JP-A-54-129126. In this issue, a technology for an antifouling agent for fishing nets using N-fluorodichloromethylthiophthalimide as an active ingredient and vehicles such as rosin, shellac, ester gum, alkyd resin, acrylic resin, vinyl chloride resin, and chloride rubber resin was disclosed. 1986-28
No. 904.

Further, the polyalkylene oxide unsaturated carboxylic acid ester resin used in the present invention is disclosed in Japanese Patent Application No. 59-25907 as a coating agent for materials that come into contact with water, and as a water-soluble coating composition in Japanese Patent Application No. 59-72904. has been disclosed.

[Problem that the invention seeks to solve]

However, (a) compositions containing the above-mentioned heavy metal compounds, namely cuprous oxide, mercury compounds, arsenic compounds such as phenarsazine chloride, and organotin compounds such as bis(tri-n-butyltin) oxide as active ingredients; Although an antifouling effect has been recognized, questions have been raised regarding safety and health or environmental conservation. Due to selectivity, such as a small amount, sufficient effects cannot be obtained.

(c) The above-mentioned compounds that have been conventionally considered effective against biological fouling, i.e., heavy metal compounds, carbamic acid compounds,
Arsenic compounds, organotin compounds, 2-amino-3-chloro-
1,4-naphthoquinone, N-fluorodichloromethylthiophthalimide and vehicles such as linseed oil, soybean oil, hempseed oil, tung oil, vinyl chloride resin, chlorinated rubber resin, acrylic resin, alkyd resin, urethane resin, polyester resin, coumaron resin Compositions containing pine resin, tar pitch, etc. do not have a long-lasting antifouling effect, and (d) the use of chlorine or formalin causes corrosion to the cooling device, and the antifouling effect is not sufficient. In addition, (e) a method in which only polyalkylene oxide unsaturated carboxylic acid ester resin is gradually eluted in water without using an antifouling active ingredient to prevent aquatic organisms from adhering to materials that come into contact with water, Because there are various conditions such as regional differences in growth rate of seawater and seawater current speed, and differences in navigation speed and sea area for ships, in sea areas where sessile organisms are actively breeding, it is necessary to apply a coating large enough to prevent their adhesion. A high rate of film dissolution is required, and if the rate of dissolution is high on the bottom of a ship where the voyage speed is high, the coating will dissolve and be exhausted in a short period of time, resulting in fouling caused by marine organisms. If the dissolution rate is reduced to achieve long-term antifouling properties, the reproductive ability of the adherent organisms exceeds the dissolution rate of the paint film, so it will not be possible to completely prevent the adherent fouling by marine organisms. There were problems such as:

[Means for solving problems]

The present invention is intended to solve the above-mentioned problems.
The object of the present invention is to provide an antifouling coating material that exhibits a non-selective fouling organism inhibiting effect against a wide range of fouling organisms, from periphyton algae to periphyton animals, over a long period of time.

The present invention provides (A) monomers 5 to 2 represented by general formula (1).
75% by weight.

H2C=CCOO(CmH2mO)nR2-(1) (wherein R1 is H, C11, or C)I, COO(C,
,R2,,,0)nR”.

R2 is 1 (or a hydrocarbon group having 1 to 28 carbon atoms, C, n
112□0 is an oxyalkylene group, m is an integer of 2 to 4,
n is an integer from 1 to 200. ) (B): Polymerizable unsaturated carboxylic acid or its salt 3-55
% by weight, and (C): 15 to 80% by weight of hydrophobic polymerizable unsaturated monomer
Polyalkylene oxyto unsaturated carboxylic acid ester resin consisting of a copolymer of 10 to 95% per total solid content of the coating material.
% by weight, and 5 to 85% by weight of at least one compound selected from the group consisting of 2-amino-3-chloro-1.4-naphthoquinone and N-fluorodichloromethylthiophthalimide based on the total solid content of the coating material. It is a stain-resistant coating material.

The polyalkylene oxide unsaturated carboxylic acid ester resin used in the present invention is a film-forming component of the antifouling coating material of the present invention.

In general formula (1), the hydrocarbon group represented by R2 includes methyl group, ethyl group, allyl group, propyl group, isopropyl group, butyl group, inbutyl group, tert-butyl group, amyl group, isoamyl group, hexyl group, group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group,
Decyl group, undecyl group, lauryl group, tridecyl group,
myristyl group, cetyl group, isocetyl group, stearyl group, instearyl group, oleyl group, octyldodecyl group, behenyl group, decyltetradecyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonyl Examples include alkyl groups, alkenyl groups, and alkylphenyl groups such as phenyl group, lauryl phenyl group, dioctylphenyl group, dinonylphenyl group, and styrenated phenyl group.

Examples of the oxyalkylene group represented by C, 11□10 include oxyethylene group, oxypropylene group, oxybutylene group, and oxytetramethylene group.

Component (A) is a water-soluble monomer, which includes acrylic acid, methacrylic acid, or itaconic acid, ethylene oxide, propylene oxide, which is an alkylene oxide having 2 to 4 carbon atoms,
1 to 200 moles of butylene oxide or tetrahydrofuran per carboxyl group.

Preferably, there are compounds added in an amount of 1 to 30 moles, or alkyl ethers, alkenyl ethers, or alkylphenyl ethers having 1 to 28 carbon atoms, preferably 1 to 22 carbon atoms.

When the number of moles of alkylene oxide added exceeds 200 moles, copolymerization reaction becomes difficult to occur, and alkyl ether,
When the number of carbon atoms in the hydrocarbon group of the alkenyl ether or alkylphenyl ether exceeds 28, water solubility decreases.

Component (B) is also a water-soluble monomer, including monobasic acids such as acrylic acid, methacrylic acid, and chloric acid, dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and carbon atoms of these dibasic acids. Number 1
In addition to ~22 alkyl or alkenyl monoesters, lithium salts, sodium salts, potassium salts, ammonium salts, alkylamine salts having 1 to 4 carbon atoms, monoethanolamine salts, jetanolamine salts, and triethanol of their carboxylic acids. There are also amine salts.

Component (C) is a hydrophobic monomer such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate-1-, octyl (meth)
Acrylate, nonyl(meth)acrylate-1~, decyl(meth)acrylate, 14-decyl(meth)arylate, tetradecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, oleyl(meth)acrylate, cyclohexyl Acrylic esters and methacrylic esters such as (meth)acrylate, vinyl acetate, styrene,
α-methylstyrene, acrylonitrile, vinyl chloride,
Examples include butadiene and chloroprene. In the present invention, "(meth)acrylate" means both acrylate and methacrylate.

The polyalkylene oxide unsaturated carboxylic acid ester resin contains 5 to 75% by weight of component (A), 3 to 55% by weight of component (B), and 15 to 80% by weight of component (C), by weight or component (A). It is a weight combination of 10 to 70% by weight of component (B), 5 to 55% by weight of component (B), and 20 to 75% by weight of component (C).

Each of the components (A) to (C) may be used alone or in combination of two or more of those exemplified above or those other than those exemplified. The water solubility, strength, flexibility, etc. of the copolymer can be adjusted by appropriately selecting the types and proportions of each component and the molecular weight of the copolymer.

Both components (A) and (B) are necessary to impart an appropriate affinity for water to the polyalkyleneoxy 1-unsaturated carboxylic acid ester resin, and to ensure that the antifouling active ingredient is efficiently eluted into water. It is necessary for both components (A) and (B) to be present in a certain proportion. (A)
(B) If both components are larger than the above range, the affinity for water will be too large, and the antifouling active ingredient will elute excessively, making it difficult to maintain the antifouling activity for a long period of time. If it is smaller than this range, the affinity for water will decrease, the amount of elution of the antifouling active ingredient will decrease, and the effectiveness of the antifouling active ingredient on the surface of the coating material in water will not be maintained, resulting in increased lη loss due to adhesion by marine organisms. happen.

Component (C) is necessary for imparting strength and flexibility, and for controlling the amount of the antifouling active ingredient in the coating material eluted into the sea. If the blending ratio is larger than the above range, the affinity for water will decrease and the elution amount of the antifouling active ingredient will decrease, and if it is smaller than the above range, the strength and flexibility will decrease and the affinity for water will increase. If too much, the elution amount of the antifouling active ingredient becomes excessive, making it difficult to maintain the antifouling effect for a long period of time.

The polyalkylene oxide unsaturated carboxylic acid ester resin is a mixture of each component (A), (B) and (C).
It can be easily obtained by solution polymerization, emulsion polymerization, or suspension polymerization in the presence of a radical catalyst.

The smaller the molecular weight of polyalkylene oxide unsaturated carboxylic acid ester resin, the greater the affinity for water, but in order to have a suitable affinity, the weight average molecular weight must be 5000 to 5000.
It is desirable to adjust it to 5oooooo, preferably 10,000 to 300,000.

The polyalkylene oxide unsaturated carboxylic acid ester resin used in the present invention is blended in a range of 10 to 95% by weight of the total solid content of the coating material, but if it is less than 10% by weight, it will not affect the surface of the material after application of the coating material. Physical property defects such as cracks and peeling due to poor adhesion of the coating material to the workpiece occur.

Moreover, if it exceeds 95% by weight, the consistency becomes too high, making it inconvenient to handle during construction.

2-Amino-3-chloro-1,4-naph 1-quinone, which is another component in the present invention, is represented by the following formula (2), and N
-Fluorodichloromethylthiophthalimide is expressed by the following formula (
3). All of these are antifouling active ingredients, and one or two of these compounds can be used in the present invention.

These antifouling active ingredients contain 5 to 50% of the total solid content in the coating material.
It is blended in a range of 85% by weight, but if it is less than 5% by weight, the antifouling effect will be insufficient, and if it exceeds 85% by weight, the physical properties of the coating material will deteriorate significantly.

The antifouling coating material of the present invention includes the above-mentioned polyalkylene oxide unsaturated carboxylic acid ester resin, 2-amino-3-
In addition to chloro-1,4-naphthoquinone and N-fluorodichloromethylthiophthalimide, if necessary, pigments and dyes such as titanium white, lithopone, baryta, Bengara, zinc white, and phthalocyanine, or to maintain good physical properties. Additives such as surfactants, thixotropic agents, anti-color fading agents, and ultraviolet light inhibitors, and solvents for adjusting consistency, such as xylene, toluene, n-butanol, inpropatol, methyl isobutyl ketone, etc., are added in a conventional manner. It can be kneaded and used. Furthermore, the antifouling coating material of the present invention also includes:
Conventional antifouling active ingredients such as cuprous oxide and organic tin can also be used in combination.

[For production]

The antifouling coating material of the present invention can be used by coating a workpiece by a conventional method such as spray coating, brush coating, flow coating, or the like.

The surface of the resulting coating material can maintain a uniform surface that elutes the antifouling active ingredient that prevents the attachment of marine organisms over a long period of time into the sea with which it comes in contact.

In the antifouling coating material coated on the workpiece, the polyoxyalkylene oxide unsaturated carboxylic acid ester resin gradually dissolves, and along with this, the antifouling active ingredient also elutes, so the surface of the coating material is always maintained. A new surface is exposed, and the antifouling active ingredient comes into contact with seawater to prevent the attachment of organisms, and the growth of a small amount of attached organisms is suppressed by the antifouling active ingredient exposed on the surface, and as the resin elutes, The antifouling active ingredient that is peeled off and further eluted into the water maintains a high concentration near the surface of the coating material and suppresses the growth of living organisms. In this way, the polyoxyalkylene oxide unsaturated carboxylic acid ester resin and the antifouling active ingredient mutually utilize their properties to prevent biofouling.

The antifouling coating material of the present invention can be applied not only to seawater, but also to objects to be coated that may come into contact with fresh water, ports, and the like.

〔Effect of the invention〕

According to this invention, since a specific polyoxyalkylene oxide unsaturated carboxylic acid ester resin and an antifouling active ingredient are combined, it can be used non-selectively against a wide range of fouling organisms, from attached algae to attached animals. It inhibits adhesion over a long period of time and exhibits excellent antifouling effects.

〔Example〕

The present invention will be explained in detail below using production examples, working examples, and comparative examples. Unless otherwise specified, parts and % are parts by weight, respectively.
Indicates weight %.

Production Example Production of Polyalkylene Oxide Unsaturated Carboxylic Acid Ester Resin In a 4-tubular flask equipped with a stirrer, nitrogen blowing line, condenser and exhaust line, the compound (A) represented by the general formula (1) was prepared using polyoxypropylene ( n
=5) 50 parts of glycol monomethacrylate, 5 parts of methacrylic acid as a polymerizable unsaturated acid (B), 45 parts of methyl methacrylate as another polymerizable unsaturated monomer (C), and N as a polymerization initiator.

0.5 part of N'-azobisisobutyronitrile (hereinafter abbreviated as AIBN), and isopropanol (hereinafter referred to as IP
Add 400 parts of IPA (abbreviated as A) and add IPA under nitrogen gas flow.
The temperature was raised to the reflux temperature of , and the polymerization reaction was carried out by stirring at the same temperature for 16 hours. The resulting polymer solution was a transparent liquid. The polymer solution was concentrated to a solid content of 50% to obtain a polymer solution A. The viscosity of polymer solution A is determined by a bubble viscometer.
(X), and the average molecular weight determined by gel permeation chromatography is 13,500 on the number average and 5,290 on the weight average.
It was 0.

Similarly, (A), (B), (
C) Each component was reacted in the proportions shown in Table 1 to obtain polyalkylene oxide unsaturated carboxylic acid ester resin B-K. The obtained resin A-K was applied to both sides of a 10100 mm x 50 aluminum plate, weighed precisely in advance.
The aluminum plate was coated with a relative humidity of 0%,
It was attached to the hook of a microbalance in a chamber adjusted to an air temperature of 25°C, and its weight was continuously measured. After the solvent in the resin evaporated and weight loss stopped, the relative humidity in the chamber was set to 100%. Set.

A water affinity test was conducted by measuring the weight increase rate after 72 hours using the following formula.

The results obtained are shown in Table 1. Other properties of Resin A- are also listed in Table 1.

Note 1 ■: Pentaoxypropylene glycolmo・
Nomethacrylate ■: Tetradeoxypropylene glycol monomethacrylate ■: Methoxy nonaoxyethylene methacrylate ■: Methoxytricosaoxyethylene methacrylate
” Note 2 MAA: Methacrylic acid AA Niacrylic acid Note 3 MMA: Methyl methacrylate St: Styrene VAc: Vinyl acetate BA Butyl Niacrylate Note 4 Viscosity is isopropyl alcohol at 25°C 5
This is the value measured using a bubble viscometer for a 0% solution.

Among resin A-, A with relatively high water affinity,
Using 51 insect resins of 'B, F which has medium affinity, and E and I which have low water affinity, the coating materials of Examples 1-10 were prepared by roll dispersion in the formulation shown in Table 2, and the coating materials were prepared in advance by roll dispersion. 1 painted with tar epoxy paint (JIs-5s6+-1 type)
0cm x 20cm mild steel plate (JIS-G-3310
) with a brush to a coating thickness of 1,000 μm, and after drying, it was removed from a raft under water in Yura Bay, Sumoto City, Hyogo Prefecture.
．． We surveyed five rice fields and observed the adhesion of fouling organisms. In addition, as Comparative Example 1, a test panel coated with tar epoxy paint was immersed in the sea at the same time, and the state of adhesion of fouling organisms was 12 m. Furthermore, as Comparative Example 2-9 with the formulation shown in Table 3, polyalkylene oxide unsaturated cartonic acid ester resin,
A coating material containing chlorinated rubber resin Alloprene R:0 (trade name: manufactured by Inverial Chemical Industries Ltd.) or pine resin and 2-amino-3-croc-1,4-naphthixine or N-fluorodicrocomethylthiophthalimide was prepared. A test plate prepared in the same manner as in the example was immersed in the sea and the state of adhesion of the organisms was observed from May 31, 1980 to June 1, 1986. The sea immersion test results are shown in Table 4. Of the comparative examples shown in Table 3, Comparative Examples 7 and 8 were not subjected to a sea immersion test because peeling and cracking occurred immediately after coating and the physical properties deteriorated.

Note to Table 4: The numbers in the table are expressed as numbers from 1 to 10 based on relative comparison of the degree of adhesion, with 1O being no adhesion and 1 being adhesion on the entire surface.

As is clear from Table 4, in all of Examples 1 to 10, the performance of Examples 1, 6, 8, and 9 using resins with low affinity for water is recognized to be slightly low; In comparison, Comparative Examples 2 to 6 showed excellent antifouling performance against an extremely wide range of marine fouling organisms such as sessile animals and algae over a period of 3 years, whereas Comparative Examples 2 to 6 showed excellent antifouling performance for a long period of 3 years. Only the antifouling effect was observed in Comparative Example 9 in which the antifouling active ingredient content was less than 5 parts by weight.

From the above results, it is clear that the antifouling coating material of the present invention has excellent antifouling performance for a long period of three years, which was difficult to achieve with conventional techniques.

Claims (4)

[Claims] (1) (A): Monomers 5 to 75 represented by general formula (1)
Weight%, ▲Mathematical formulas, chemical formulas, tables, etc.▼…(1) (In the formula, R^1 is H, CH_3 or CH_2COO(
C_mH_2_mO)_nR^2, R^2 is H or a hydrocarbon group having 1 to 28 carbon atoms, C_mH_2_mO is an oxyalkylene group, m is an integer of 2 to 4, and n is an integer of 1 to 200. ) (B): Polymerizable unsaturated carboxylic acid or its salt 3-55
% by weight, and (C): 15 to 80% by weight of hydrophobic polymerizable unsaturated monomer
Polyalkylene oxide unsaturated carboxylic acid ester resin consisting of a copolymer of 10 to 95% per total solid content of the coating material.
% by weight, and 5 to 85% by weight of at least one compound selected from the group consisting of 2-amino-3-chloro-1,4-naphthoquinone and N-fluorodichloromethylthiophthalimide based on the total solid content of the coating material. Fouling coating material. (2) Component (A) is acrylic acid, methacrylic acid or itaconic acid, ethylene oxide, propylene oxide,
The antifouling coating material according to claim 1, which is a compound to which butylene oxide or tetrahydrofuran is added, or an alkyl ether, alkenyl ether, or alkylphenyl ether thereof. (3) Patents in which component (B) is acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, monoesters thereof, lithium salts, sodium salts, potassium salts, ammonium salts, or amine salts thereof. The antifouling coating material according to claim 1 or 2. (4) Any of claims 1 to 3, wherein component (C) is an acrylic ester, a methacrylic ester, vinyl acetate, styrene, α-methylstyrene, acrylonitrile, vinyl chloride, butadiene, or chloroprene. The antifouling coating material described in Crab.