WO1992016570A1

WO1992016570A1 - Marine antifouling paint

Info

Publication number: WO1992016570A1
Application number: PCT/JP1992/000299
Authority: WO
Inventors: Kiyomi Mori; Takeshi Hamachi; Shigemi Kojima; Keiji Ueda; Hitoshi Tabuchi
Original assignee: Nitto Kasei Co., Ltd.
Priority date: 1991-03-15
Filing date: 1992-03-12
Publication date: 1992-10-01

Abstract

A polymer having repeating units represented by general formula (I); a marine antifouling paint comprising an antifouling component and a solvent and containing a resin containing the polymer as a binder; and a process for protecting ships or fishnets by applying the paint thereto. In the formula (I), A represents hydrogen or methyl; B represents -C(=O)OR'O-, -OR'O-, -C(=O)OCH2-, -C(=O)NHCH2O-, -C(=O)R'O-, -OC(=O)R'O-, -O- or -R'O-, wherein R' represents alkylene or phenylene; and R represents alkyl, cycloalkyl, aryl or aralkyl which may be arbitrarily substituted on the aryl group.

Description

Akira Hosoki

Marine antifouling paint

Technical field

The present invention relates to a marine antifouling paint for preventing marine organisms from adhering to underwater structures such as ships and fish nets, a method for protecting ships and fish nets using the paint, and a polymer used therefor.

Background art

Marine antifouling paint using an organotin-containing copolymer is gradually hydrolyzed in seawater, and the organotin portion of the copolymer side chain is appropriately eluted from the coating film surface, and can exhibit a long-term antifouling effect It has been widely used. However, the use of marine antifouling agents using organotin-containing copolymers has recently been restricted due to the problem of marine pollution.

In order to cope with such a situation, an antifouling agent is introduced into the side chain of the polymer instead of the organotin compound, and the antifouling agent is released into seawater to release the antifouling agent. A submarine antifouling agent has been proposed which is found in the patent applications of Japanese Patent Application Laid-Open No. 60-500452 and Japanese Patent Application Laid-Open No. 61-26374, which exhibit high performance.

However, the ester moieties in the copolymers disclosed in these patent applications are not sufficiently hydrolyzed under weak alkaline conditions such as natural seawater (pH 8.0 to 8.9), and are therefore practically resistant to antifouling. There was a major drawback in that it was not effective.

Disclosure of the invention

Accordingly, the present inventors have conducted intensive studies to solve the above-mentioned disadvantages of the prior art, and as a result, the antifouling coating film is appropriately hydrolyzed in natural seawater for a long time. The present inventors have found a marine antifouling paint and a polymer used therein, and have reached the present invention. That is, according to the present invention, a) an antifouling component b) a binder of the formula (I)

A

B

-CH ₂ -C- Hi ΟΞ (I)

Wherein R is an alkyl group, cycloalkyl group, aryl group or an aralkyl group which may be optionally substituted in the aryl group, A is a hydrogen atom or a methyl group, and B is a group ((= 0) 01 ^ 0—, Base 1 01 ^ 0—, Base 1 C (= 0) OCH ₂ —, Base 1 C (= 0) NHCH ₂₀ —, Base 1 C (= 0) R ¹⁰ 0. = 0) 1 ^ 0—, group 10— or group RiO—, and R ¹ represents an alkylene group or a phenylene group, respectively.] 3) A marine antifouling paint comprising: a) a solvent and, if necessary, d) an additive. According to the present invention, further, the formula (I)

Wherein A, B, and R have the above meanings. And a polymer having an appropriate hydrolyzability in seawater. Here, “appropriate hydrolyzability” means the degree of hydrolyzability of the copolymers A to Q of Examples 1 to 17 as shown in the data of the coating film solubility test (Table 3). It is said.

In a preferred embodiment of the present invention, in the repeating unit of the above formula (I)

Wherein Α, Β and R have the same meanings as described above, By polymerizing one or more unsaturated monomers represented by the general formula (1) or one or more unsaturated monomers represented by the general formula (（) and another ethylenically unsaturated monomer It can be obtained by copolymerizing one or more monomers.

Examples of the unsaturated monomer represented by the formula (1 ′) include the following:

o o = = o = =

o o = o =

A

CH ₂ = C-C00 (CH ₂ ) ₂ -0C-C-0C ₂ H ₅ (A: H, CH ₃ )

A

CH ₂ = C-C00 (CH ₂ ) 2-OC-C-OC4H9 (A: H, CH ₃ ) A

A 0 0

I II II

CH ₂ = C-C00 (CH ₂ ) 2-0C-C-0CH ₂ (A: H, CH ₃ )

A 0 0

A

CE ₂ = C-C00 (CH ₂ ) 3-0C-C-0C ₂ H ₅ (A: H, CH ₃ )

A CH ₃ 0 0

I I I! Il

(A: H, CH ₃ ) / s-dBfd 0 to Si9 OM

w m

. pq

(¾ w c td cxi

-<-<----■--

HV: A 0 0

(A: H, CH ₃ )

A O 0 0

I II II II

A O 0 0

I II II II CH ₂ = CC-CH ₂ 0C-C-0C ₂ H ₅ (A: H, CH ₃ )

A O 0 0

I II II II

CH2 = CC-0CH ₂ CH ₂ 0-C- C-0t-C ₄ H ₉ (A: B, CH ₃ ) The unsaturated monomer of the above formula (Ι ') is represented by the formula (II) It is obtained by reacting an unsaturated monomer having a free hydroxyl group with an acid halide represented by the formula (III) in the presence of a base such as triethylamine, pyridine, sodium hydroxide, or sodium carbonate. .

A

(CH ₂ = C CII)

B! -OH

Wherein A is a hydrogen atom or a methyl group, B ¹ is a group (= 0) 01 ^ —, a group OR ¹ —, a group C (=. 0) NHCH ₂ —, a group -〇 (= 0) 1 ^ —, group OCK-O)! ^ ¹ — or group R ¹ —, and R ¹ represents an alkylene group or a phenylene group, respectively.

00

II II-(III)

X-CC0B [In the formula, R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and X represents a chlorine atom, a bromine atom or an iodine atom.]

Here, unsaturated monomers having a free hydroxyl group represented by the formula (II) include, for example, aryl alcohol; 5-methallyl alcohol,

2—Hydroxyshetyl acrylate, 2—Hydroxyshetyl methacrylate, 2—Hydroxypropyl acrylate, 2—Hydroxypropyl methacrylate, 3—Hydroxypropyl acrylate, 3 —Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 41-hydroxybutyl methacrylate, N-methylol acrylamide, vinyl 4-hydroxybutyl ether, and the like.

Examples of the acid halide represented by the formula (III) include ethyl chloroglyoxylate, propyl bromoglyoxylate, butyl chloroglyoxylate, octyl chloroglyoxylate, phenyl chloroglyoxylate, benzyl chloroglyoxylate, Examples include acid chlorides such as cyclohexyl chloroglyoxylate and acid bromides obtained by substituting the bromo atom of the above compound with a bromo atom.

Further, the unsaturated monomer of the formula (1 ′) is obtained by converting an unsaturated monomer having a free carboxyl group (for example, acrylic acid or methacrylic acid) and a halide represented by the formula (IV) into triethylamine. It can also be obtained by reacting in the presence of a base such as pyridine, sodium hydroxide and sodium carbonate.

00

II I! (IV)

X-CHzCCOE [Wherein, R and X have the same meaning as described above]

Examples of the halide represented by the formula (IV) include methyl bromopyruvate, ethyl bromopyruvate, butyl bromopyruvate, octyl bromopyruvate, phenyl bromopyruvate, benzyl bromopyruvate, and cyclobromopyruvate. Brominated compounds such as xyl, and chlorinated compounds obtained by substituting the prom atom of the above compound with a ketone atom are included. On the other hand, the polymer according to the present invention having a repeating unit represented by the formula (I) further comprises one or more unsaturated monomers having a free hydroxyl group represented by the formula (II). After copolymerizing one or more of the other copolymerizable ethylenically unsaturated monomers, the resulting copolymer is mixed with an acid halide represented by the formula (III), triethylamine, pyridine It can also be obtained by reacting in the presence of a base such as sodium hydroxide, sodium carbonate and the like.

When the unsaturated monomer represented by the formula (Γ) is copolymerized, the other ethylenically unsaturated monomer is not limited as long as it is a copolymerizable monomer. For example, acrylate (methacrylic acid) esters such as methyl methacrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, vinylidene chloride, acrylonitrile, acrylamide, vinyl acetate, and vinyl pyrrolidone. Vinyl monomers having a group; vinyl hydrocarbons such as styrene and butadiene; and unsaturated dicarboxylic acid esters such as dimethyl maleate and dimethyl itaconate.

The antifouling component contained in the marine antifouling paint of the present invention is not limited as long as it has a killing or repelling effect on marine fouling organisms. Compounds such as zinc oxide, rodane, and powder; organic compounds such as tetrachloroisophthalonitrile; 3,4-cycle-mouth phenylisothiocynate; zinc dithiolbamate; 2-mercaptopyridine N —Zinc compounds such as zinc oxide, thiuram compounds, maleimide compounds, etc., which can be used alone or as a mixture.

The amount of the antifouling component in the marine antifouling paint of the present invention is not particularly limited, but is preferably from 10 to 200% by weight of the polymer having the repeating unit represented by the formula (I).

The marine antifouling paint of the present invention further comprises a polymer having a repeating unit of the formula (I) and, if necessary, a rosin, a rubber chloride, an acryl resin, a vinyl chloride-vinyl acid copolymer (VYHH). Natural or synthetic resins such as the above can also be used in combination.

The marine antifouling paint of the present invention can contain further additives as necessary. Examples of such additives include pigments, dyes, and plasticizers. Further, the marine antifouling paint of the present invention contains a solvent for the above polymer, but such a solvent is not particularly limited. For example, methyl ethyl ketone, methyl isobutyl ketone, xylene, propylene glycol Monomethyl ether acetate and the like can be mentioned.

Example

Next, the present invention will be described with reference to examples. In each example,% is% by weight, viscosity is a value measured at 25 ° C, and molecular weight is weight average molecular weight by GPC (in terms of polystyrene). Is shown. The synthetic monomer was identified as the target compound by IR and NMR, and the purity was measured by GLC analysis.

1. Production of unsaturated monomers Production Example 1

In 21 nitrogen flasks equipped with a thermometer, reflux condenser, stirrer and dropping funnel, put 2-hydroxyethyl acrylate 116.1 (1. While stirring, 136.5 g (1. Omol) of ethyl chloroglyoxylate was diluted with 100 ml of ethyl acetate and kept at room temperature, and added dropwise over about 1 hour. Next, a solution prepared by diluting 103.2 g (1.02 mol) of triethylamine into 100 ml of ethyl acetate was added dropwise over about 1 hour while maintaining the temperature at room temperature. After stirring at 30 to 40 for 4 hours, the reaction solution was filtered to remove the triethylamine hydrochloride, and then the concentrated solution was concentrated under reduced pressure to give 2-ethoxyoxalyloxethyla yellow liquid. There were obtained 217. Og of acrylate (purity: 91.0%, yield: 91.4%).

Production Example 2

Similar to Preparation Example 1 except that 144.1 g (1. Omol) of 2-hydroxypropyl methacrylate was used instead of 116.1 g (1.0 mo 1) of 2-hydroxyethyl acrylate of Preparation Example 1. By the operation, a brown viscous liquid, 2-ethoxyoxalyloxypropyl methacrylate, 225.δ3 (purity: 89.5%, yield: 90.2%) was obtained.

Production Example 3

Instead of 116.1 g (1.0 mo 1) of 2-hydroxyethyl acrylate in Production Example 1, 116.2 g (1. Omo 1) of vinyl-4-hydroxybutyl ether and 136.5 g of ethyl chloroglyoxylate were used. g (1. Omo 1) was replaced with chlorochloroglyoxylate 185.δ g (1. Omo l) to produce a brown liquid by the same operation as in Production Example 1. There was obtained 268.2 g (purity: 88.3%, yield: 89.3%) of a certain 4-phenoxoxalyloxybutyl vinyl ether.

Production Example 4

72.1 g (1. Omo I) of acrylic acid was used instead of 116.1 g (1.0 mo 1) of 2-hydroxylethyl acrylate of Production Example 1, and ethyl oxyglyoxylate 136. The same operation as in Production Example 1 was repeated, except that 257.0 g (1. Omo 1) of benzil bromopyruvate was used in place of 5 g (1. Omol), to obtain a dark brown liquid, 3-benzyloxy 2,3- Dioxopropyl acrylate 248.1 (purity 92.4%, yield 92.2%) was obtained.

Production Example 5

After charging 282.1 g (2.222mo1) of oxalyl chloride in 11 cellulosic flasks equipped with a thermometer, a calcium chloride tube, a stirrer, and a dropping funnel, benzyl alcohol 200. 2 g (1.852mo 1) was added dropwise, followed by stirring at room temperature for 30 minutes. Excess oxalyl chloride was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 297.9 g of oxalic acid monobenzyl ester chloride (1.50 mO1, yield 81%, bp 93 ~ 95 ° CZ3mmHg).

Next, 215.2 g (1.5 mol) of 2-hydroxyhydroxyl methacrylate and 118.7 of pyridine were placed in a 21-mL flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel in a nitrogen stream. g (1.5mo)) and tetrahydrofuran (THF) 11, then dilute 299.7g (1.5mol) of monobenzyl oxalate chloride in THF30Om] to 10 ° C or less. The solution was dropped. Return to room temperature, 2 o'clock After stirring for a while, the reaction solution was filtered to remove pyridine hydrochloride, and the concentrated solution was concentrated under reduced pressure to obtain 438.0 g of benzoyloxalyloxexyl methacrylate, a pale yellow liquid (yield 99%). %).

Production Example 6

Similar to Preparation Example 5 except that 175.2 g (1.5mo 1) of 2-hydroxyethyl acrylate was used instead of 195.2 g (1.5mo 1) of 2-hydroxyethyl methacrylate of Preparation Example 5. Through the operation, 417.0 g (yield: 99%) of benzoyloxalyloxhexyl atearylate as a pale yellow liquid was obtained.

Production Example 7

After charging 343.2 g (2.704mo1) of oxalyl chloride to 11 four-necked flask equipped with a thermometer, a calcium chloride tube, a stirrer, and a dropping funnel, t-butanol 167.0 g A solution obtained by diluting (2.254mo 1) in 200 ml of T HF was added dropwise at 10 ° C or lower, and then stirred at room temperature for 1 hour. Excess oxalyl chloride and THF were distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 263.3 g of mono-oxalic acid mono-t-butyl ester chloride (1.600 mol, yield 71%). Bp 44 ° C / 1 OmmHg).

Next, 215.2 g (1.5 mol) of 2-hydroxyethyl methacrylate and 118.7 g of pyridine were placed in a 21-mL flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel in a nitrogen stream. After charging (1.5 mol) and tetrahydrofuran (THF) 11, dilute 246.9 g (1.5 mol) of oxalic acid mono-t-butyl ester chloride to 30 ml of THF and reduce the temperature to 10 ° C or less. It was dropped while keeping it. Return to room temperature 2 After stirring for an hour, the reaction solution was filtered to remove pyridine hydrochloride, and the concentrated solution was concentrated under reduced pressure to obtain 383.5 g of t-butoxalyloxhetyl methacrylate as a pale yellow liquid (yield 99%).

Production Example 8

Production Example 7 using 174.2 g (1.5 mo 1) of 2-hydroxyl acrylate instead of 195.2 g (1.5 mol 1) of 2-hydroxyl methacrylate of Production Example 7 By the same operation as described above, 359.0 g (yield: 98%) of t-butoxalyloxshetyl acrylate as a pale yellow liquid was obtained.

2. Production of copolymer

Example 1

2-Ethoxalyloxhetyl acrylate 90 g, methyl methacrylate 10 g, methyl ethyl ketone in a 50 Om 1 four-necked flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel 100 g and 2 g of azobisisobutyronitrile (AIBN) were added, and the mixture was polymerized under a nitrogen atmosphere at 80 to 85 for 2 hours, and 0.5 g of AIBN and 50 g of methyl ethyl ketone were added, and the polymerization was further performed for 2 hours. The obtained yellow copolymer solution (copolymer solution A) had a viscosity of 630 cps, a heating residue of 38.9%, and a molecular weight of 140,000.

Example 2

In a 50-Om 1 four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 2-ethoxyhexyloxhexyl acrylate 80 g, methyl methacrylate 15 g, butyl acrylate 5 g , Xylene 60 g, methyl isobutyl ketone 40 g and azobisisobutyronitrile (AIB N) 2 g was added, polymerization was carried out at 80 to 85 ° C. for 2 hours in a nitrogen atmosphere, and 0.5 g of AIBN was added to carry out polymerization for 2 hours. The resulting yellow copolymer solution (copolymer solution B) had a viscosity of 220 cps, a heating residue of 49.1%, and a molecular weight of 42,000.

Example 3

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 70 g of 2-ethoxyxyloxypropyl methacrylate, 30 g of ethyl acrylate, 60 g of xylene, 40 g of methyl isobutyl ketone and 2 g of azobisisobutyronitrile (AI BN) was added, and the mixture was polymerized for 2 hours at 80 to 85 in a nitrogen atmosphere, and 0.5 g of AIBN and 50 g of methyl isobutyl ketone were added, and the polymerization was further performed for 2 hours. The resulting yellow copolymer solution (copolymer solution C) had a viscosity of 580 cps, a heating residue of 40.3%, and a molecular weight of 142,000.

Example 4

In a 500 ml four-necked flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 85 g of 2-ethoxyxyloxypropyl methacrylate, 15 g of methyl methacrylate, 60 g of xylene, 40 g of methyl isobutyl ketone g and azobisisobutyronitrile (AI BN) 2 g were added, polymerization was carried out at 80 to 85 for 2 hours in a nitrogen atmosphere, and 0.5 g of AI BN and 50 g of methyl isobutyl ketone were added to carry out polymerization for another 2 hours. The resulting yellow copolymer solution (copolymer solution D) had a viscosity of 595 cps, a heating residue of 41.2%, and a molecular weight of 120,000.

Example 5

500m1 four-hole equipped with thermometer, reflux condenser, stirrer and dropping funnel In a flask, put 75 g of 4-phenyloxyloxybutyl vinyl ether, 20 g of methyl methacrylate, 5 g of styrene, 60 g of xylene, 40 g of methyl isobutyl ketone and 2 g of azobisisobutyronitrile (AIBN), Polymerization was carried out under a nitrogen atmosphere at 80 to 85 for 2 hours, and 0.5 g of AIBN and 50 g of methyl isobutyl ketone were added to carry out polymerization for another 2 hours. The resulting yellow copolymer solution (Copolymer Solution E) had a viscosity of 300 cps, a heating residue of 40.2%, and a molecular weight of 63,000.

Example 6

In a 50-Om 1 four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 4-phenoxalyloxybutyl vinyl ether 65 g, methyl acrylate 35 g, styrene 5 g, xylene 60 g , 40 g of methyl isobutyl ketone and 2 g of azobisisobutyronitrile (AIBN), polymerize at 80-85 ° C under nitrogen atmosphere for 2 hours, add 5 g of AI BNO. And 50 g of methyl isobutyl ketone. Polymerization was further performed for 2 hours. The obtained yellow copolymer solution (copolymer solution F) had a viscosity of 250 cps, a heating residue of 39.1%, and a molecular weight of 65,000.

Example 7

75 g of 3-benzyloxy-2,3-dioxopropyl acrylate in a 50-Om 1 four-necked flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, methoxethyl acrylate Add 25 g, xylene 60 g, methyl ethyl ketone 40 g and azobisisobutyronitrile (AIBN) 2 g, polymerize under nitrogen atmosphere at 80-85 ° C for 2 hours, and add AI BNO. Δ g. Polymerization was further performed for 2 hours. The resulting dark brown copolymer solution (Copolymer Solution G) had a viscosity of 850 cps and a heating residue of 48.5%. The child size was 95,000.

Example 8

3-benzyloxy-2,3-dioxopropyl acrylate 80 g, methyl methacrylate 20 g, xylene 60 g in a 50 Om 1 four-necked flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel Then, 40 g of methyl isobutyl ketone and 2 g of benzoyl peroxide (BPO) were added, and the mixture was polymerized under a nitrogen atmosphere at 95 to 100 for 2 hours, and 0.5 g of BPO was added to perform polymerization for another 2 hours. The resulting dark brown copolymer solution (Copolymer Solution H) had a viscosity of 1200 cps, a heating residue of 48.2%, and a molecular weight of 81,000.

Example 9

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, 41.3 g of 3-hydroxypropyl methacrylate, 30 g of ethyl acrylate, 200 g of methyl ethyl ketone and 200 g of azobisisobutyronitrile (AI 2 g of BN) and polymerized at 80-85 ° C for 4 hours under a nitrogen atmosphere. After cooling to room temperature, ethyl chloroglyoxylate was added dropwise over 1 hour while maintaining at room temperature. While keeping the temperature at room temperature, 30.8 g of triethylamine was diluted with 50 g of xylene and added dropwise over 30 minutes. Thereafter, the reaction mixture was stirred at 60 for 5 hours, and the reaction mixture was filtered to remove triethylamine hydrochloride. The mixture was concentrated under reduced pressure to prepare a 50% solids solution. The obtained yellow copolymer solution (copolymer solution I) containing 3-ethoxyxaryloxypropyl methacrylate as a constitutional unit had a viscosity of 930 cps, a heating residue of 50.5%, and a molecular weight of 42,000. Met.

Example 10 In a 50 Om 1 four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 64 g of the benzyloxalyloxhexyl methacrylate obtained in Production Example 5, 16 g of methyl acrylate, and propylene 120 g of glycol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) are added, and polymerized under a nitrogen atmosphere at 85 to 90 ° C for 4.5 hours to obtain a pale yellow copolymer. A solution (copolymer solution J) was obtained. The obtained copolymer solution J had a viscosity of 226 cps, a heating residue of 39.5%, and a molecular weight of 57,000.

Example 11

In a 50-Om 1 four-necked flask equipped with a thermometer, a flow cooler, a stirrer, and a dropping funnel, 64 g of benzyloxalyloxhexyl methacrylate obtained in Production Example 5, 8 g of methyl methacrylate, and acrylic 8 g of butyl acid, 120 g of propylene glycol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) were polymerized under a nitrogen atmosphere at 85 to 90 for 4.5 hours, and the pale yellow copolymer was obtained. A combined solution (copolymer solution K) was obtained. The resulting copolymer solution K had a viscosity of 135 cps, a heating residue of 39.5%, and a molecular weight of 40,000.

Example 12

In a 50-Om 1 four-necked flask equipped with a thermometer, a flow cooler, a stirrer, and a dropping funnel, 56 g of benzyloxalyloxyxethyl methacrylate obtained in Production Example 5, 16 g of benzyl methacrylate Then, 8 g of butyl acrylate, 120 g of propylene glycol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) were added, and the mixture was polymerized under a nitrogen atmosphere at 85 to 90 ° C for 4.5 hours. Yellow copolymer solution (Copolymer solution L) I got The resulting copolymer solution L had a viscosity of 138 cps, a heating residue of 39.2%, and a molecular weight of 44,000.

Example 13

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 48 g of benzyloxalyloxhexyl methacrylate obtained in Production Example 5, 24 g of t-butyl methacrylate, acrylyl 8 g of butyl acrylate, 120 g of propylene dalicol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) were polymerized under a nitrogen atmosphere at 85 to 90 ° C for 4.5 hours. A polymer solution (copolymer solution M) was obtained. The obtained copolymer solution M had a viscosity of 175 cps, a heating residue of 39.9%, and a molecular weight of 50,000.

Example 14

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, 56 g of the benzyloxalyloxhexyl acrylate obtained in Production Example 6, 24 g of methyl methacrylate, propylene Glycol monomethyl acetate 120 g and azobisisobutyronitrile

2 g of (AIBN) was added thereto, and polymerized at 85 to 90 ° C. for 4.5 hours under a nitrogen atmosphere to obtain a pale yellow copolymer solution (copolymer solution N). The obtained copolymer solution N had a viscosity of 262 cps, a heating residue of 39.9%, and a molecular weight of 6,000.

Example 15

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 64 g of the benzyloxalyloxhexyl acrylate obtained in Production Example 6, 16 g of benzyl methacrylate, Propylene glycol mono 120 g of methyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) were added, and the mixture was polymerized at 85 to 90 ° C for 4.5 hours under a nitrogen atmosphere to obtain a pale yellow copolymer solution (copolymer). A polymer solution 0) was obtained. The obtained copolymer solution 0 had a viscosity of 142 cps, a heating residue of 39.1%, and a molecular weight of 43,000.

Example 16

In a 500 ml four-neck flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 64 g of t-butoxalyloxhexyl methacrylate obtained in Production Example 7, 16 g of methyl acrylate, propylene glycol 120 g of monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) were added, and the mixture was polymerized under a nitrogen atmosphere at 85 to 90 for 4.5 hours to obtain a pale yellow copolymer solution (copolymer). A polymer solution P) was obtained. The resulting copolymer solution P had a viscosity of 460 cps, a heating residue of 39.1%, and a molecular weight of 860000.

Example 1

48 g of the t-butoxalyloxyxethyl acrylate obtained in Production Example 8, 32 g of benzyl methacrylate in a 500 ml four-neck flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 120 g of propylene glycol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) were added, and the mixture was polymerized under a nitrogen atmosphere at 85 to 90 for 4.5 hours. A polymer solution (copolymer solution Q) was obtained. The resulting copolymer solution Q had a viscosity of 135 cps, a heating residue of 39.5%, and a molecular weight of 4000.

Comparative Example 1 The same procedure as in Example 1 was repeated, except that 90 g of funasyl acrylate was used in place of 90 g of 2-ethoxyoxalyloxyshetyl acrylate in Example 1. Polymerized for hours. The obtained funasyl ester-containing copolymer solution (comparative copolymer solution 1) had a viscosity of 850 cps, a heating residue of 49.2%, and a molecular weight of 43,000.

Comparative Example 2

In a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, 85 g of p-chlorobenzyl methacrylate, 15 g of methoxethyl acrylate, 100 g of xylene and 100 g of azobisisobutyronitrile (AI 1 g of BN) was added, and the mixture was polymerized for 2 hours at 80 to 85 ° C in a nitrogen atmosphere, and 0.5 g of AI BN was added for further polymerization for 2 hours. The obtained benzyl ester-containing copolymer solution (comparative copolymer solution 2) had a viscosity of 980 cps, a heating residue of 49.1%, and a molecular weight of 38,000.

3. Preparation of Marine Antifouling Paint

(1) Preparation of antifouling marine antifouling paint

Examples 18-34, Comparative Examples 3-4

Using the copolymer solutions A-Q obtained in Examples 1 to 17 and the comparative copolymer solutions 1 to 2, the respective components were added according to the formulations shown in Table 1 below, and the marine defense system for ship bottoms of the present invention was added. A dirty paint was obtained.

The numbers in the table represent weight (g). Table 1

* Anti-settling agent (Kusumoto Kasei) Table 1 (continued)

* 1 Anti-settling agent (Kusumoto Kasei Co., Ltd.)

* 2 Propylene glycol monomethyl ether acetate (2) Preparation of marine antifouling paint for fish net

Example 3 5 to 51, Comparative Examples 5 to 6

Using the copolymer solutions A-Q obtained in Examples 1 to 17 and the comparative copolymer solutions 1 to 2, the respective components were added in accordance with the formulations shown in Table 2 below, and the ocean for fish nets of the present invention was used. An antifouling paint was obtained.

The numbers in the table represent weight (g).

Table 2

Table 2 (continued) Example of implementation

44 45 46 47 48 49 50 51 Copolymer solution J 62.5

Copolymer solution K 62.5 Copolymer solution L 62.5 Copolymer solution M 62.5

Co-copolymer solution N 62.5 Co-polymer solution 0 62.5 Co-polymer solution P 62.5 Co-polymer solution Q 62.5

12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 Fluid balaffin 5 5 5 5 5 5 0 5 Cyanine blue with lid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

ΡΜΑ * 2 42 42 42 42 42 42 42 42 42

4. Solubility test of coating film

A rotating drum with a diameter of 31.8 mm and a height of 450 mm was attached to the center of the water tank, and this could be rotated by a motor. Next, a heating device and a cooling device were installed to keep the seawater temperature constant, and a pH automatic controller was installed to keep the seawater pH constant.

Each of the copolymer solutions and marine antifouling paints obtained in Examples 1-34 and Comparative Examples 1-2 was coated on a 1 mm thick hard vinyl chloride plate so as to have a dry film thickness of about 100 microns. After drying, it was dried at 50 ° C. for 24 hours. The test plate coated with the marine antifouling paint is brought into contact with seawater on the rotating drum of the above rotating device.

Fixed at I 0 and rotated in seawater for three months at a speed of 37 km hr. During that period, the seawater temperature was kept at 25 and the pH was kept at 8.0 to 8.2, and the seawater was replaced every week.

The initial film thickness of each coated test plate and the remaining film thickness after three months were measured with a microscope, and the thickness of the dissolved coating film was calculated from the difference. Table 3 shows the results.

I 5

0 Table 3

5. Antifouling test

(1) Ship bottom antifouling test The marine defense paint for ship bottoms of Example 18 34 and Comparative Example 34 was applied to both sides of a hard vinyl chloride plate so as to have a dry film thickness of 200 microns. The test plate was immersed 1.5 m below the sea surface in Oga Bay, Mie Prefecture, and the test plate was stained for 18 months with attached organisms. Table 4 shows the results.

Note that the numbers in the table represent the percentage of the area where the fouling organisms adhere. Table 4

(2) Fish net antifouling test

After immersing a polyethylene net (20 cm x 20 cm) in the marine antifouling paint for fish nets of Examples 35 to 51 and Comparative Examples 5 to 5 for 5 minutes, it was dried at room temperature for 1 minute. The test plate was immersed 1.5 m below sea level and stained by the attached organisms for 5 months.

The results were evaluated based on the following evaluation criteria and summarized in Table 5. ◎: No organisms adhered or only slime adhered.

〇: Slightly attached organisms, but no problem as a culture net.

Δ: Tolerable to use as a culture net due to the adhesion of living things.

: A large amount of organisms are attached.

number 5

Antifouling effect (month) Pollution content

1 2 3 4 5 i Example 35 ◎ ◎ ® ◎ ◎

1 36 ◎ ◎ ◎ ◎ ◎

37 ◎ ◎ ◎ ◎ ◎

38 ◎ ◎ ◎ ◎ ◎

39 ◎ ◎ ◎ ◎ ◎

! 40 ◎ ◎ ◎ ◎ ◎

41 ◎ ◎ ◎ ◎ ◎

42 ◎ ◎ ◎ ◎ ◎

43 ◎ ◎ ◎ ◎ ◎

44 ◎ ◎ ◎ ◎ ◎

45 ◎ ◎ ◎ ◎

46 ◎ ◎ ◎ ◎ ◎

47 ◎ ◎ ◎ I ί

I

48 ◎ ◎ ◎ ® ◎

!

! 49 ◎ ◎ ◎ ◎ i

50 © ◎ ◎ ◎ ◎!

!

51 ® ◎ ◎ ◎ ◎ i Comparative Example 5 ◎ 〇 Δ χ X Nori Fujibo

6 ◎ 〇 Δ XX Nori Fujibo; Effects of the present invention

The polymer having a non-ketoester group of the present invention has excellent adhesion to base materials such as ship bottoms and fish nets, and the coating film is tough. As is clear from Table 3, it is moderately hydrolyzed in natural seawater.

Therefore, the marine antifouling coating composition of the present invention obtained by adding an antifouling component to the polymer can maintain the antifouling effect for a long period of time, and does not have to worry about marine pollution as seen in conventional antifouling coating compositions.

Claims

The scope of the claims

1.a) Antifouling components

b) As a binder, a compound of the formula (I)

Wherein A represents hydrogen or a methyl group,

B is a group i ((= 0) 01 ^ 0, one 01 ^ 0, -C (= 0) 0CH ₂ -, one _{C (= 0) NHCH 2 0} -, -C (= 0) R 1 0 -. One 0C (= 0)

I o R ^J O—, one 0— or one R! O—, wherein R ¹ represents an alkylene group or a phenylene group,

R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may be optionally substituted in the aryl group.]

5 c) Solvent and if necessary

d) additives

A marine antifouling paint comprising:

2. B represents the group ¹ (= 0) 01 ^ 0—, 1 01 ^ 0—, 1 C (= 0) 0CH ₂ , R ¹ represents a linear or branched alkylene, and R represents a linear 2. The marine antifouling paint according to claim 1, which represents 0 or branched alkyl, phenyl or benzyl.

3. B represents a group —C (= 0) 0R ¹ 0-, —01 ^ 0-, -C (= 0) 0CH ₂ —, and R ¹ represents a linear or branched C! -C ₅ alkylene , R represents Table straight-chain or branched C! -C ₅ alkyl, Fuweniru or benzyl The marine antifouling paint according to claim 2.

4. The marine antifouling paint according to claim 1, wherein the polymer is a copolymer having a repeating unit of the formula (I) in an amount of 40 to 95% by weight.

5. A method for protecting a ship surface or a fish net, comprising applying the marine antifouling paint according to claim 1 to a ship surface or a fish net.

6. Equation (I)

Wherein A represents hydrogen or a methyl group,

B is a group one C (= 0) ORiO-, one ORiO-, - C (= O) OCH 2 -, one _{C (= 0) NHCH 2 0} -., -C (= 0) R 1 0- one OC (= 0) 1 ^ 0—, 1 0— or 1 R′O—, wherein R ¹ represents an alkylene group or a phenylene group,

R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may be optionally substituted in the aryl group.], And has an appropriate hydrolyzability in sea water.

7. B represents the group ¹ (0) 01 ^ 0—, 1 01 ^ 0—, -C (= 0) OCH ₂ , R ¹ represents a linear or branched C! Cs alkylene, and R represents straight or branched C! -C ₅ alkyl, Fuweniru or benzyl polymer of Table I to claim 5, wherein.

8. The polymer according to claim 5, which is a copolymer having 40 to 95% by weight of the repeating unit of the formula (I).