JPH04252209A - Hydrolyzable resin composition and marine antifoulant - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific structural unit, having excellent coating film stability and antifouling property to marine life and useful as marine antifoulant, etc. CONSTITUTION:The objective composition contains the structural unit of formula I (A is H or methyl; R<1> is H, alkyl, aryl, aralkyl, alkoxy, etc.; R<2> and R<3> are alkyl, aryl, aralkyl, etc.) and having a weight-average molecular weight of preferably 5,000-300,000. The composition can be produced by the polymerization of one or more kinds of unsaturated monomers of formula II. A marine antifoulant is produced by adding an antifouling component such as cuprous oxide to the above composition.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition with good hydrolyzability and a marine antifouling agent for preventing the adhesion of marine organisms.

0002

[Prior Art] Marine antifouling agents using tri-organotin-containing copolymers undergo gradual hydrolysis in seawater, and the tri-organotin portion of the side chain of the copolymer is gradually eluted from the coating surface, resulting in long-term It has been widely used since it exhibits antifouling effects.

By the way, the use of marine antifouling agents using tri-organotin-containing copolymers has been restricted in recent years due to the problem of marine pollution.

In order to deal with this situation, instead of the tri-organotin compound, a hydrolyzable ester moiety is introduced into the polymer side chain to gradually release a drug with antifouling power into seawater. Special publication 60-50 that exhibits antifouling effect
A marine antifouling agent was proposed as seen in patent applications No. 0452 and JP-A No. 61-261374.

[0005]

[Problems to be Solved by the Invention] However, the ester moieties in the copolymers disclosed in these patent applications are not sufficiently hydrolyzed in weakly alkaline water such as natural seawater (pH 8.0-8.4). Therefore, the current situation is that it cannot exhibit an antifouling effect that can withstand practical use.

[0006]

[Means for Solving the Problems] As a result of intensive research, the present inventors have discovered a resin composition that can maintain appropriate solubility of a coating film in natural seawater for a long period of time, and have arrived at the present invention.

That is, the present invention provides the general formula [3] in the polymer.
]

[Formula 3] (wherein A is a hydrogen atom or a methyl group, R1 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an allyloxy group, an acyloxy group, a nitro group, a cyano group, or -COR4) , R2, R3 and R4 represent an alkyl group, an aryl group, an aralkyl group, an alkoxy group or an allyloxy group, and R2, R3, R4
may be the same or different), and an underwater antifouling agent prepared by adding an antifouling component to the resin composition.

The hydrolyzable resin composition of the present invention having a structural unit represented by the general formula [1] has a structural unit represented by the general formula [4]

[
By polymerizing one or more unsaturated monomers represented by formula 4 (wherein A, R1, R2, R3 and R4 have the same meanings as above), or by polymerizing one or more unsaturated monomers represented by the general formula [
4] by copolymerizing one or more unsaturated monomers with one or more other ethylenically unsaturated monomers.

Examples of the unsaturated monomer represented by the general formula [4] include:

[C5] Examples include.

These unsaturated monomers [4] are obtained by combining an unsaturated monomer having a free carboxyl group (for example, acrylic acid, methacrylic acid, etc.) and a halide represented by the general formula [6] with triethylamine and water. Obtained by reaction in the presence of a base such as sodium oxide or sodium carbonate.

[Formula 6] (wherein X represents a chlorine atom, a bromine atom or an iodine atom, and R1, R2, R3 and R4 have the same meanings as above)

Examples of the halides represented by the general formula [6] include bromodibenzoylmethane, acetylbromodibenzoylmethane, 1-bromoacetylacetone,
Methyl 2-bromoacetoacetate, ethyl 2-bromoacetoacetate, dimethyl 2-bromomalonate, diethyl 2-bromomalonate, dibutyl 2-bromomalonate, diethyl 2-bromo-2-benzoylmalonate, 2-acetyl-2
Examples include brominated compounds such as diethyl-bromomalonate, 1-bromo-1-benzoylacetylacetone, and bromotribenzoylmethane, and chlorinated compounds in which the bromine atom of the above compound is replaced with a chlorine atom.

[0012] Other ethylenically unsaturated monomers to be used when copolymerizing the unsaturated monomer represented by general formula [4] are not limited as long as they are copolymerizable monomers. However, for example, methyl methacrylate, ethyl methacrylate
Acrylic (methacrylic) acid esters such as butyl acrylate and 2-ethylhexyl acrylate, vinyl monomers having functional groups such as vinylidene chloride, acrylonitrile, acrylamide, vinyl acetate, and N-vinylpyrrolidone, styrene, Examples include vinyl hydrocarbons such as butadiene, and unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl itaconate.

The resin composition of the present invention preferably contains 30% by weight or more of the monomer represented by the general formula [4] as a structural unit in the polymer. This is because if the amount is less than 30% by weight, the hydrolyzability of the resin composition in seawater is low and a sufficient antifouling effect cannot be exhibited.

The weight average molecular weight of the resin composition of the present invention is 5
000-300,000 is desirable. If the molecular weight is less than 5,000, the coating film becomes brittle and easily peels off, while if it exceeds 300,000, the viscosity of the polymerization solution increases and becomes difficult to handle.

Next, the marine antifouling agent of the present invention has the general formula [2
] This is an underwater antifouling agent characterized by adding an antifouling component to a resin composition having a structural unit represented by the following. The antifouling component is not limited as long as it has a killing or repellent effect on marine fouling organisms, but examples include copper compounds such as cuprous oxide, copper rhodan, copper powder, tetrachloroisophthalonitrile, 3,4 -Dichlorophenylisothiocyanate-
Zinc compounds such as zinc dithiocarbamate, zinc 2-mercaptopyridine N-oxide,
Examples include thiuram compounds and maleimide compounds.

Although the amount of the antifouling component present in the marine antifouling agent of the present invention is not limited, it is preferably 3 to 150% by weight of the resin composition having the structural unit represented by the general formula [2]. Furthermore, the marine antifouling agent of the present invention may contain dyes, pigments,
Plasticizers and natural or synthetic resin vehicles such as rosin, chlorinated rubber, vinyl chloride-vinyl acetate copolymer (VYHH) may also be used.

[0017]

[Example] Next, the present invention will be explained with reference to examples. In each example, % is weight %, viscosity is a value measured at 25°C, and molecular weight is a weight average molecular weight by GPC (polystyrene conversion).
shows. Furthermore, the synthesized monomer was identified as the target compound by IR and NMR.

1. Production of unsaturated monomer Production example 1 2 equipped with a thermometer, reflux condenser, stirrer and dropping funnel
Bromodibenzoylmethane 303 in a four-necked flask
．． 2g (1 mol), acrylic acid monomer 72.1g (
1 mol) and 500 ml of ethyl acetate were added thereto, and while stirring, a solution prepared by diluting 101.2 g (1 mol) of triethylamine with 100 ml of ethyl acetate was added dropwise over about 5 minutes while keeping the temperature at room temperature. After further stirring at room temperature for 6 hours, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtrate was concentrated at about 30°C under reduced pressure to obtain 241 g (liquid) of dibenzoylmethyl acrylate. Ta. The yield was 82%.

Production Example 2 72.1 g (1 mol) of the acrylic acid monomer of Production Example 1
Instead of methacrylic acid monomer 86.1g (1 mol
), 247 g of dibenzoylmethyl methacrylate (pale yellow crystals, mp77
．． 5-79.0°C, yield 80%).

Production Example 3 Bromodibenzoylmethane 303.2g (1
150 mol) of methyl 2-chloroacetoacetate instead of
．． Acetyl methoxycarbonyl methyl acrylate 1 was obtained by the same operation as in Production Example 1 using 5 g (1 mol).
20 g (liquid, yield 65%) was obtained.

Production Example 4 Bromodibenzoylmethane 303.2g (1
diethyl 2-bromomalonate 239 instead of mol)
．． 157 g of diethoxycarbonylmethyl acrylate was obtained by the same operation as in Production Example 1 using 0 g (1 mol).
(liquid, yield 68%).

2. Copolymer Production Example 1 5 equipped with a thermometer, reflux condenser, stirrer and dropping funnel
In a 00ml four-necked flask, add 45g of dibenzoyl methyl acrylate, 45g of methyl methacrylate, 10g of butyl acrylate, 60g of xylene, and 40g of ethyl acetate.
and 1 g of azobisisobutyronitrile (AIBN) were added thereto, and polymerization was carried out at 75-80° C. for 6 hours under a nitrogen atmosphere. The obtained dibenzoyl methyl ester-containing copolymer solution (copolymer solution A) had a viscosity of 450 cps and a heating residue of 4.
The molecular weight was 41,000 at 8.9%.

Example 2 A 5-unit refrigerator equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
In a 00 ml four-necked flask, add 60 g of dibenzoyl methyl acrylate, 35 g of methyl methacrylate, 5 g of 2-ethylhexyl acrylate, 60 g of xylene, 40 g of ethyl acetate, and azobisisobutyronitrile (AIBN).
), and polymerization was carried out at 75-80°C for 6 hours under a nitrogen atmosphere. The obtained dibenzoyl methyl ester-containing copolymer solution (copolymer solution B) had a viscosity of 380 cps,
The heating residue was 49.9% and the molecular weight was 42,000.

EXAMPLE 3 A 5-unit refrigerator equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
Put 40 g of dibenzoyl methyl methacrylate, 40 g of methyl methacrylate, 20 g of methyl acrylate, 100 g of xylene, and 1 g of azobisisobutyronitrile (AIBN) into a 00 ml four-necked flask, and add 75-80 g of azobisisobutyronitrile (AIBN) under a nitrogen atmosphere. Polymerization was carried out at ℃ for 6 hours. The obtained dibenzoyl methyl ester-containing copolymer solution (copolymer solution C) had a viscosity of 1300 cps, a heating residue of 49.2%, and a molecular weight of 45,000.

EXAMPLE 4 A 5-unit tank equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
70 g of dibenzoyl methyl methacrylate, 30 g of ethyl acrylate, 100 g of xylene, and azobisisobutyronitrile (AIBN) in a 00 ml four-necked flask.
1 g was added, and polymerization was carried out at 75-80° C. for 6 hours under a nitrogen atmosphere. The obtained dibenzoyl methyl ester-containing copolymer solution (copolymer solution D) had a viscosity of 750 cps, a heating residue of 49.9%, and a molecular weight of 40,000.

EXAMPLE 5 A 5-unit machine equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
45 g of acetyl methoxycarbonyl methyl acrylate, 4 g of methyl methacrylate in a 00 ml four-necked flask.
5g, butyl acrylate 10g, xylene 60g, ethyl acetate 40g and azobisisobutyronitrile (AI
BN) was added, and polymerization was carried out at 75-80°C for 6 hours under a nitrogen atmosphere. The obtained acetylmethoxycarbonylmethyl ester-containing copolymer solution (copolymer solution E) is
Viscosity 540 cps, heating residue 48.9%, molecular weight 37
,000.

EXAMPLE 6 A 5-unit machine equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
55 g of acetyl methoxycarbonyl methyl acrylate and 4 methyl methacrylate in a 00 ml four-necked flask.
0g of styrene, 5g of styrene, 60g of xylene, and 1g of azobisisobutyronitrile (AIBN) were added, and polymerization was carried out at 75-80°C for 6 hours under a nitrogen atmosphere. The obtained acetylmethoxycarbonylmethyl ester-containing copolymer solution (
Copolymer solution F) had a viscosity of 400 cps and a heating residue of 49
．． At 3%, the molecular weight was 35,000.

EXAMPLE 7 A 500 liter cell equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
In a 00ml four-necked flask, add 30g of diethoxycarbonylmethyl acrylate, 45g of methyl methacrylate,
25g of methoxyethyl acrylate, 100g of xylene
and 1 g of azobisisobutyronitrile (AIBN) were added thereto, and polymerization was carried out at 75-80° C. for 6 hours under a nitrogen atmosphere. The obtained diethoxycarbonyl methyl ester-containing copolymer solution (copolymer solution G) had a viscosity of 650 cps, a heating residue of 48.7%, and a molecular weight of 39,000.

Example 8 5 equipped with a thermometer, reflux condenser, stirrer and dropping funnel
In a 00ml four-necked flask, add 50g of diethoxycarbonyl methyl acrylate, 40g of methyl methacrylate,
10 g of butyl acrylate, 100 g of xylene, and 1 g of azobisisobutyronitrile (AIBN) were added, and polymerization was carried out at 75-80° C. for 6 hours under a nitrogen atmosphere. The obtained diethoxycarbonyl methyl ester-containing copolymer solution (copolymer solution H) had a viscosity of 600 cps and a heating residue of 4
The molecular weight was 41,000 at 9.2%.

EXAMPLE 9 5-50 equipped with a thermometer, reflux condenser, stirrer and dropping funnel
11.0 g of acrylic acid, 45 g of methyl methacrylate, and 10 g of butyl acrylate in a 00 ml four-necked flask.
, 200 g of methyl isobutyl ketone and 1 g of azobisisobutyronitrile (AIBN) were added, and the mixture was heated under a nitrogen atmosphere for 7 hours.
Polymerization was carried out at 5-80°C for 6 hours. After cooling to room temperature, 46.3 g of bromodibenzoylmethane was added and thoroughly stirred, and then a solution prepared by diluting 15.6 g of triethylamine with 50 g of xylene was added dropwise over about 5 minutes while keeping the temperature at room temperature. After further reaction at 55-60°C for 5 hours, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtrate was concentrated at 50°C to adjust to a solution with a solid content of 50%. The resulting copolymer solution (copolymer solution I) containing dibenzoylmethyl acrylate as a structural unit had a viscosity of 620 cps and a heating residue of 5
At 0.2%, the molecular weight was 45,000.

Comparative Example 1 Example 1 was prepared by using 45 g of phenacyl acrylate in place of 45 g of dibenzoyl methyl acrylate in Example 1.
Polymerization was carried out in a nitrogen atmosphere at 75-80°C for 6 hours in the same manner as above. The obtained phenacyl ester-containing copolymer solution (comparative copolymer solution 1) had a viscosity of 700 cps,
The heating residue was 49.5% and the molecular weight was 37,000.

Thermometer, reflux condenser, stirrer and dropping funnel
70 g of p-chlorobenzyl methacrylate, 30 g of methoxyethyl acrylate, 100 g of xylene, and 1 g of azobisisobutyronitrile (AIBN) were placed in a 500 ml four-necked flask equipped with a nitrogen atmosphere.
Polymerization was carried out at 80°C for 6 hours. The obtained benzyl ester-containing copolymer solution (comparative copolymer solution 2) had a viscosity of 1
200 cps, heating residue 49.2%, molecular weight 42.0
It was 00.

3. Preparation of underwater antifouling agent (1) Preparation of underwater antifouling agent for ship bottom Copolymer solution A- obtained in Example 1-9 and Comparative Examples 1 and 2
Using Copolymer I and Comparative Copolymer Solutions 1 and 2, the ingredients listed in Table 1 below were added to obtain an underwater antifouling agent for ship bottoms of the present invention. The blending results are shown in Table 1. Note that the numbers in the table represent weight (g).

[Table 1]

(2) Preparation Example 1 of underwater antifouling agent for fish nets
Using copolymer solutions A-I and comparative copolymer solutions 1 and 2 obtained in 9 and Comparative Examples 1 and 2, the ingredients listed in Table 2 below were added to prepare marine defense for fish nets of the present invention. I got the stain. The blending results are shown in Table 2. Note that the numbers in the table represent weight (g).

[Table 2]

4. Test for Solubility of Paint Film A rotating drum with a diameter of 318 mm and a height of 440 mm was installed in the center of the water tank, and could be rotated by a motor. Next, a heating device and a cooling device were installed to keep the temperature of the seawater constant, and an automatic PH controller was installed to keep the pH of the seawater constant. 1 mm of each copolymer and marine antifouling agent obtained in Example 1-18 and Comparative Example 1-4
It was coated on a thick hard vinyl chloride plate to a dry film thickness of about 100 microns, and then dried at 50°C for 24 hours. The test plate coated with the underwater antifouling agent was fixed to the rotating drum of the rotating device of the above device so as to be in contact with seawater, and the test plate was heated at 37 km/h.
It was rotated in seawater for 3 months at a speed of hr. During this period, the seawater temperature is kept at 25℃ and the pH is kept at 8.0-8.2.
The seawater was replaced every week. The initial film thickness of each coated test plate and the remaining film thickness after 3 months were measured using a microscope, and the dissolved coating film thickness was calculated from the difference. The results are shown in Table 3.

[Table 3]

5. Antifouling test (1) Antifouling test for ship bottoms Examples 10-18 and Comparative Examples 3 and 4, which are marine antifouling agents for ship bottoms of the present invention, were applied to both sides of a hard vinyl chloride board with a dry film thickness of 2.
It was coated to a thickness of 0.00 microns. This test plate was immersed 1.5 m below the sea surface in Owase Bay, Mie Prefecture, and staining of the test plate by attached organisms was observed for 18 months. The results are shown in Table 4. Note that the numbers in the table represent the percent area of adhesion of fouling organisms.

[Table 4]

(2) Fish net antifouling test Examples 19 to 27 and Comparative Examples 5 and 6, which are underwater antifouling agents for fish nets of the present invention, were tested using polyethylene fish net pieces (20 c
20 cm) for 5 minutes, then dried at room temperature for 1 day.
The test board was immersed 1.5 m below the sea surface in Owase Bay, Mie Prefecture, and the staining of the test board due to attached organisms was observed for 5 months. The results were evaluated based on the following evaluation criteria and summarized in Table 5. ◎: There is no living organism attached or only slime is attached. ○: A small amount of organisms adhere to the net, but it does not pose any problem as aquaculture net. △: Due to the adhesion of organisms, the net cannot be used as an aquaculture net. ×: A large amount of living things are attached.

[Table 5]

[0038]

[Effect] As is clear from Table 3, the resin composition of the present invention is moderately hydrolyzed in natural seawater, so the coating film remains stable and dissolved for a long period of time. Therefore, the underwater antifouling agent of the present invention, which is composed of the resin composition and the antifouling component, can exhibit antifouling effects for a long period of time without polluting environments such as oceans and rivers.

Claims (2)

[Claims] Claim 1: A polymer having the general formula [1] [Formula 1] (where A is a hydrogen atom or a methyl group, and R1 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an allyloxy group) group, acyloxy group, nitro group, cyano group or -COR4, R2, R3 and R4 represent an alkyl group, aryl group, aralkyl group, alkoxy group or allyloxy group, R2, R3, R4
may be the same or different). Claim 2: A polymer containing a compound having the general formula [2] [Chemical formula 2] (where A is a hydrogen atom or a methyl group, and R1 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an allyloxy group, acyloxy group, nitro group, cyano group or -COR4, R2, R3 and R4 represent an alkyl group, aryl group, aralkyl group, alkoxy group or allyloxy group, R2, R3, R4
may be the same or different), and an antifouling component is added to a resin composition.