JPH06211941A - Underwater antifouling coating composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of giving a coating film which can keep a suitable solubility in seawater for a long time by copolymerizing a specified crosslinking monomer with an ethylenically unsaturated monomer in the presence of a polymerization modifier. CONSTITUTION:100 pts.wt. monomer mixture comprising a cross-linking monomer of formula I (wherein X and Y are groups of formulas II-VI; R is H or methyl; (m) is 1-5; and (n) is 0-2) and other copolymerizable and ethylenically unsaturated monomers in the presence of 1-20 pts.wt. polymerization modifier to obtain a hydrolyzable resin composition of a weight-average molecular weight of 10000-100000. 5-200wt.% antifouling component is added to this composition to obtain the objective composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having good hydrolyzability and an antifouling coating composition for preventing marine organisms from adhering to underwater structures such as ships and fish nets.

[0002]

2. Description of the Related Art Submarine antifouling paints using a triorganotin-containing copolymer are gradually hydrolyzed in seawater, and the triorganotin portion of the side chain of the copolymer gradually elutes from the surface of the coating film. It has been widely used since it has an antifouling effect.

[0003]

However, the use of marine antifouling paints using a triorganotin-containing copolymer has been restricted in recent years due to the problem of marine pollution. Therefore, attempts have been made to develop antifouling paints that do not worry about environmental pollution, but the present situation is that the antifouling performance of marine antifouling paints cannot be sufficiently hydrolyzed in seawater, so that they cannot exhibit antifouling performance for a long time. .

[0004]

[Means for Solving the Problems] Therefore, as a result of earnest research, the inventors of the present invention maintained an appropriate solubility of a coating film in natural seawater for a long period of time, and exhibited good coating properties as an underwater antifouling coating. The present invention has been completed, and the present invention has been completed.

That is, the present invention has the general formula [4]

[Chemical 4] And a hydrolyzable resin composition obtained by copolymerizing a crosslinkable monomer represented by the above with another copolymerizable ethylenically unsaturated monomer in the presence of a polymerization modifier, and the resin composition An undersea antifouling coating composition, characterized in that an antifouling component is added to the composition.

The hydrolyzable resin composition of the present invention has the general formula [5]

[Chemical 5] (In the formula, X and Y have the same meanings as described above) One or more crosslinkable unsaturated monomers represented by another copolymerizable ethylenic group in the presence of a polymerization regulator are used. It is obtained by copolymerizing with one or more unsaturated monomers.

The polymerization modifier is used in such a copolymerization reaction, because the unsaturated monomer represented by the general formula [5] is crosslinkable, the resulting copolymer becomes a purine-like gel substance, The purpose is to prevent the hydrolyzable coating resin composition from becoming unusable.

The crosslinkable unsaturated monomer represented by the general formula [5] is not particularly limited as long as it is an oxalic acid ester or an oxalic acid amide which can serve as a crosslinking agent. For example, oxalic acid divinyl ester, Oxalic acid diallyl ester, oxalic acid diacryloyloxyethyl ester,
Oxalic acid dimethacryloyloxyethyl ester, oxalic acid divinyloxyethyl ester, oxalic acid divinyloxybutyl ester, oxalic acid diacryloyloxypropyl ester, oxalic acid dimethacryloyloxypropyl ester, oxalic acid di (2'-vinylphenyl)
Ester, oxalic acid di (3′-vinylphenyl) ester, oxalic acid di (4′-vinylphenyl) ester,
N, N′-diacryloyloxyethyl oxalic acid amide, N, N′-dimethacryloyloxyethyl oxalic acid amide, vinyl oxalate (vinyloxyethyl) ester, vinyl oxalate (vinyloxybutyl) ester,
Vinyl oxalate (acryloyloxyethyl) ester, vinyl oxalate (methacryloyloxyethyl) ester, vinyl oxalate (2′-vinylphenyl) ester, vinyl oxalate (3′-vinylphenyl) ester, vinyl oxalate (4 ′) -Vinylphenyl) ester, acryloyloxyethyl oxalate (vinyloxyethyl) ester, methacryloyloxyethyl oxalate (vinyloxyethyl) ester, acryloyloxyethyl oxalate (vinyloxybutyl) ester, methacryloyloxyethyl oxalate (vinyloxy) Butyl) ester, acryloyloxyethyl oxalate (2'-vinylphenyl) ester, methacryloyloxyethyl oxalate (2'-vinylphenyl) ester, acryloyl oxalate Ciethyl (3'-vinylphenyl) ester, methacryloyloxyethyl oxalate (3'-vinylphenyl) ester, acryloyloxyethyl oxalate (4'-vinylphenyl) ester, methacryloyloxyethyl oxalate (4'-vinylphenyl) Ester, vinyl (allyl) oxalate, acryloyloxyethyl (methacryloyloxyethyl) oxalate, oxalic acid (2'-vinylphenyl) (3'-vinylphenyl) ester, oxalic acid (2'-vinylphenyl) ( 4'-vinylphenyl)
Ester, oxalic acid (3'-vinylphenyl) (4'-
Vinyl phenyl) ester etc. are mentioned.

These crosslinkable unsaturated monomers [5] are obtained by transesterification of oxalic acid and vinyl acetate (when preparing vinyl ester) or oxalic acid dichloride and the corresponding alcohol with triethylamine and pyridine. It can be easily obtained by reacting in the presence of a base such as sodium hydroxide, sodium carbonate or the like.

When the crosslinkable unsaturated monomer represented by the general formula [5] is copolymerized, the other ethylenically unsaturated monomer is limited as long as it is a copolymerizable monomer. However, acrylic (meth) acrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, vinylidene chloride, acrylonitrile, acrylamide, vinyl acetate, N- Examples thereof include vinyl-based monomers having a functional group such as vinylpyrrolidone, vinyl-based hydrocarbons such as styrene and butadiene, and unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl itaconate.

Examples of the polymerization regulator used in the present invention include butyl mercaptan, lauryl mercaptan, dodecyl mercaptan, organic sulfur compounds such as thioglycolic acid, 2,4-diphenyl-4-methyl-1-pentene (α-methyl). Examples thereof include styrene derivatives such as styrene dimer) and 1-methyl-4-isopropylidene-cyclohexene (ta-binolene).

The amount of the crosslinkable unsaturated monomer represented by the general formula [5] used in the present invention is preferably 1 to 20 parts by weight based on 100 parts by weight of all the polymerizable monomers. If it is used in an amount of less than 1 part by weight, the resin composition has a low hydrolyzability in seawater and cannot exhibit a sufficient antifouling effect.
This is because if the amount used exceeds 20 parts by weight, a large amount of polymerization regulator, polymerization initiator, etc. are required to prevent gelation, which is not preferable from the economical viewpoint.

The amount of the polymerization modifier used in the present invention is preferably 1-10 parts by weight based on 100 parts by weight of the total polymerizable monomers. This is because if the amount is less than 1 part by weight, the effect of adjusting the polymerization reaction is insufficient, and if the amount is more than 10 parts by weight, the progress of the polymerization reaction is excessively hindered.

The weight average molecular weight of the resin composition of the present invention is 1
It is preferably 0000-100,000. If the molecular weight is less than 10,000, the coating film becomes brittle and easily peels off. On the other hand, if the molecular weight exceeds 100,000, the viscosity of the polymerization solution will increase and handling will be difficult.

Next, the marine antifouling coating composition of the present invention comprises an antifouling component added to a hydrolyzable resin composition obtained by polymerizing a crosslinkable unsaturated monomer represented by the general formula [5]. An antifouling coating composition characterized by the following.

The antifouling component is not limited as long as it is a substance having a killing or repelling action on marine fouling organisms,
For example, copper compounds such as cuprous oxide, copper rhodanide, and copper powder, organic compounds such as tetrachloroisophthalonitrile, 3,4-dichlorophenylisothiocyanate, zinc dithiocarbamate, and 2-mercaptopyridine N-oxide zinc. Examples thereof include zinc compounds, thiuram-based compounds, maleimide-based compounds, and the like, and these can be used alone or in a mixture.

The amount of the antifouling component of the marine antifouling coating composition of the present invention is not limited, but a hydrolyzable resin obtained by polymerizing a crosslinkable unsaturated monomer represented by the general formula [5]. 5-200% by weight of the composition is preferred.

Further, in the marine antifouling paint of the present invention, dyes, pigments, plasticizers, rosin, chlorinated rubber, acrylic resins, vinyl chloride-vinyl acetate copolymer (VYH) may be added, if necessary.
Natural or synthetic resin vehicles such as H) can also be used in combination.

[0019]

EXAMPLES Next, the present invention will be described with reference to examples. In each example,% is% by weight, viscosity is the measured value at 25 ° C., and molecular weight is the weight average molecular weight by GPC (polystyrene conversion).
Indicates. The synthetic monomer was identified to be the target compound by IR and NMR.

1. Production of unsaturated monomer 1 equipped with thermometer, reflux condenser, stirrer and dropping funnel
In a nitrogen gas stream, 156.2 g (1.2 mol) of 2-hydroxyethyl methacrylate, 94.9 g (1.2 mol) of pyridine and 400 ml of tetrahydrofuran (THF) were placed in a four-necked flask of 1 l and stirred under ice cooling. Meanwhile, 76.2 g (0.6 mol) of oxalic acid chloride was added dropwise over 1 hour. After returning to room temperature and stirring for 2 hours,
The reaction solution was filtered to remove pyridine hydrochloride, and the filtrate was concentrated under reduced pressure. The obtained crude crystals were recrystallized from ethanol to obtain 142.6 g of dimethacryloyloxyethyl oxalate ester. The yield was 76%. By the same operation, oxalic acid diacryloyloxyethyl ester was obtained in a yield of 46%, N, N′-dimethacryloyloxyethyl oxalic acid amide was obtained in a yield of 78%, and N, N′-diacryloyloxyethyl oxalic acid amide was obtained. Yield 35%
Thus, oxalic acid di (4'-vinylphenyl) ester was obtained with a yield of 54%.

2. Preparation of Copolymer Example 1 4 g of methacrylic acid dimethacryloyloxyethyl ester 4 g, methyl methacrylate 92 g, butyl acrylate 100 g, α-methylstyrene were placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer. Dimer-4 g, xylene 200 g and azobisisobutyronitrile (AI
2 g of BN) was added, and polymerization was carried out at 85-90 ° C. for 6 hours in a nitrogen atmosphere. The obtained copolymer solution (copolymer solution A) had a viscosity of 180 cps, a heating residue of 47.4%, and a molecular weight of 30,000.

Example 2 In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 10 g of oxalic acid diacryloyloxyethyl ester, 86 g of methyl methacrylate, 104 g of ethyl acrylate and α-methylstyrene dimer were added. 10g,
200 g of xylene and azobisisobutyronitrile (A
IBN) (4 g) was added, and polymerization was performed at 85-90 ° C. for 6 hours in a nitrogen atmosphere. The obtained copolymer solution (copolymer solution B) had a viscosity of 150 cps, a heating residue of 49.0%, and a molecular weight of 28,000.

Example 3 In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 4 g of methacrylic acid dimethacryloyloxyethyl ester, 66 g of methyl methacrylate, 130 g of 2-methoxyethyl acrylate, and α-methyl were used. Styrene dimer-4 g, xylene 200 g, and azobisisobutyronitrile (AIBN) 2 g were put therein, and under a nitrogen atmosphere 85-9
Polymerization was carried out at 0 ° C. for 6 hours. The resulting copolymer solution (Copolymer solution C) had a viscosity of 120 cps and a heating residue of 49.
The molecular weight was 28,000 at 6%.

Example 4 In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 20 g of N, N'-dimethacryloyloxyethyl oxalic acid amide and 11 of isobutyl methacrylate were used.
0 g, butyl acrylate 50 g, 2-methoxyethyl acrylate 20 g, thioglycolic acid 20 g, xylene 2
00g and azobisisobutyronitrile (AIBN) 6
g was added and polymerization was carried out at 85-90 ° C. for 6 hours in a nitrogen atmosphere. The obtained copolymer solution (Copolymer solution D) had a viscosity of 100 cps, a heating residue of 48.3%, and a molecular weight of 220.
It was 00.

Example 5 In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2 g of N, N'-diacryloyloxyethyl oxalic acid amide, 78 g of methyl methacrylate and 2-ethoxyethyl methacrylate were used. 20 g, methyl acrylate 100 g, dodecyl mercaptan 2 g, xylene 200
g and azobisisobutyronitrile (AIBN) (2 g) were added, and polymerization was carried out at 85-90 ° C. for 6 hours under a nitrogen atmosphere. The obtained copolymer solution (Copolymer solution E) had a viscosity of 190 cps, a heating residue of 46.5%, and a molecular weight of 1500.
It was 0.

Example 6 In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 14 g of oxalic acid di (4'-vinylphenyl) ester, 60 g of dibutyl maleate, 126 g of vinyl acetate and α-methyl were used. Styrene dimer-10 g, xylene 200 g and azobisisobutyronitrile (AIB
N) (3 g) was added, and polymerization was carried out at 85-90 ° C. for 6 hours in a nitrogen atmosphere. Obtained copolymer solution (copolymer solution F)
Had a viscosity of 150 cps, a heating residue of 47.3%, and a molecular weight of 30,000.

Comparative Example 1 100 g of methyl methacrylate, 100 g of butyl acrylate, 200 g of xylene and 2 g of azobisisobutyronitrile (AIBN) were placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer. Polymerization was carried out at 85-90 ° C. for 6 hours under a nitrogen atmosphere. The obtained copolymer solution (Copolymer solution G) had a viscosity of 780 cps, a heating residue of 50.4% and a molecular weight of 40,000.

Comparative Example 2 120 g of isobutyl methacrylate, 60 g of butyl acrylate, 2-methoxyethyl acrylate 2 were placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer.
0 g, xylene 200 g and azobisisobutyronitrile (AIBN) 2 g were put, and the temperature was 85-90 ° C under a nitrogen atmosphere.
Polymerization was carried out for 6 hours. The resulting copolymer solution (copolymer solution H) had a viscosity of 630 cps and a heating residue of 49.8%.
And the molecular weight was 54,000.

3. Preparation of underwater antifouling paint (1) Preparation of undersea antifouling paint for ship bottoms Copolymer solutions AF obtained in Examples 1-6 and Comparative Example 1
Using the copolymer solutions G and H obtained in 2 above, the compounding ingredients shown in Table 1 below were added to obtain a marine antifouling paint for ship bottoms of the present invention. The compounding results are shown in Table 1. The numbers in the table represent weight (g).

[Table 1]

(2) Preparation of undersea antifouling paint for fishnets Copolymer solutions AF obtained in Examples 1-6 and Comparative Example 1
Using the copolymer solutions G and H obtained in 2 above, the compounding ingredients shown in Table 2 below were added to obtain the undersea antifouling paint for fishnets of the present invention. The compounding results are shown in Table 2. The numbers in the table represent weight (g).

[Table 2]

4. Solubility test of coating film A rotating drum having a diameter of 318 mm and a height of 440 mm was attached to the center of a water tank so that it could be rotated by a motor. Next, a heating device and a cooling device were attached to keep the temperature of the seawater constant, and a PH automatic controller was attached to keep the PH of the seawater constant. 1 m of each of the copolymers obtained in Example 1-12 and Comparative Example 1-4 and the marine antifouling paint
It was coated on a hard vinyl chloride plate having a thickness of m so that the dry film thickness was about 100 microns, and then dried at 50 ° C. for 24 hours.
The test plate coated with the undersea antifouling paint was fixed to the rotating drum of the above rotating device so as to come into contact with seawater, and 37 km /
It was spun in seawater for 3 months at a speed of hr. During that period, the temperature of seawater was kept at 25 ° C and the pH was kept at 8.0-8.2, and the seawater was replaced every week. The initial film thickness of each coating test plate and the remaining film thickness after 3 months were measured with 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) Ship bottom antifouling test Example 7-1 which is the undersea antifouling coating composition for ship bottoms of the present invention
2 and Comparative Examples 3 and 4 were coated on both sides of a hard vinyl chloride plate so that the dry film thickness would be 200 microns. The test plate was immersed 1.5 m below the sea surface in Owase Bay, Mie Prefecture, and the test plate was observed for contamination for 18 months. The results are shown in Table 4. The numbers in the table are the areas where the fouling organisms are attached.
Represents cents.

[Table 4]

(2) Fishnet Antifouling Test Example 13- which is the undersea antifouling coating composition for fishnets of the present invention
18 and Comparative Examples 5 and 6 include polyethylene fish net pieces (20c
m × 20 cm) for 5 minutes, then dry at room temperature for 1 day,
The test plate was immersed in 1.5 m below the sea level in Owase Bay, Mie Prefecture, and the test plate was observed for contamination for 5 months. The results are evaluated based on the following evaluation criteria and summarized in Table 5. ⊚: No organism attached or only slime attached. ◯: A small amount of organisms adhere, but there is no problem as a culture net. Δ: The degree of being unusable as a culture net due to adhesion of organisms. X: A large amount of organisms are attached.

[Table 5]

[0034]

[Effect] The hydrolyzable resin composition according to the present invention obtained by polymerizing a crosslinkable unsaturated monomer in the presence of a polymerization regulator is capable of appropriately disintegrating the crosslinked site in the resin in natural seawater. Therefore, as is clear from the results of the coating film solubility test shown in Table 3, the coating film exhibits an appropriate hydrolyzability so that it can be stably dissolved for a long period of time. In addition, the resin composition of the present invention has excellent adhesion to substrates such as ship bottoms and fish nets, and its coating film is tough. Therefore, the underwater antifouling coating composition of the present invention obtained by adding an antifouling component to the resin composition can maintain the antifouling effect for a long period of time, is excellent in the storage stability of the coating, and is a conventional antifouling agent. There is no worry of marine pollution as seen.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C09D 5/14 PQJ 6904-4J 125/00 PFB 9166-4J 129/10 PFP 6904-4J 131/04 PDT 6904- 4J 133/00 PPHY 7921-4J

Claims (2)

[Claims] 1. A general formula [2]: A hydrolyzable resin composition obtained by copolymerizing the crosslinkable monomer represented by the above with another copolymerizable ethylenically unsaturated monomer in the presence of a polymerization modifier. 2. A general formula [3]: In the presence of a polymerization modifier, a crosslinkable monomer represented by a hydrolyzable resin composition obtained by copolymerizing with another copolymerizable ethylenically unsaturated monomer, an antifouling component. An underwater antifouling coating composition characterized by being added.