JP2963254B2 - Sustainable underwater antifouling composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to fishing nets, ship bottoms, seawater intake channels, etc., to prevent attached organisms, particularly those attached to the sea, from adhering to fishing nets, ship bottoms, seawater intake channels, etc. for a long time. Water-resistant antifouling composition. More specifically, the present invention relates to a persistent underwater antifouling composition capable of maintaining its dissolution over a long period of time using a highly safe antifouling active ingredient.

[0002]

2. Description of the Related Art Conventionally, various antifouling agents have been proposed to suppress the adherence of attached organisms in order to prevent the attached organisms from adhering to fishing nets, ship bottoms, seawater intake channels, and the like, thereby causing adverse effects. in use. For example,
8730, JP-B-54-37008, JP-A-55-92774, JP-A-58-120678.
JP, JP-A-59-133267 and JP-B-1
JP-A-54388 proposes an antifouling agent containing an antifouling active ingredient of a highly toxic compound such as an organotin compound, an organic or inorganic copper compound or an organic chlorine compound, and a specific acrylic acid polymer. ing. However, these antifouling active ingredients are so toxic as to cause a problem of marine pollution and have a property of accumulating in living bodies. For this reason, especially when dealing with edible cultured organisms in the aquaculture industry, there is a concern that there is a concern about the effects on human bodies and also on workers who directly handle antifouling agents.

In order to enhance safety, antifouling agents using a polyisocyanate compound or a metal compound capable of chelating a carboxyl group in place of the above-mentioned poisons are disclosed in, for example, JP-B-53-21883 and JP-B-53-1983. 21885
No. pp. 139 to 163. However, these highly safe antifouling agents also did not have sufficient antifouling effects over a long period of time.

[0004] Therefore, an antifouling agent which has high safety and maintains the antifouling effect for a long period of time is desired. Some of the present inventors have previously found that a specific higher aliphatic amine having low toxicity and good biodegradability has an excellent antifouling effect, and this amine and a specific polycarboxylic acid copolymer A persistent underwater antifouling agent containing a coalescing (polymer) film-forming agent has already been proposed (JP-A-1-103103).
672).

Further, the inventors of the present invention have made an invention (higher aliphatic amine and alkylene oxide-containing polycarboxylic acid copolymer) in which the dissolving property of a higher aliphatic amine which is an active ingredient of the above-mentioned antifouling agent in water is adjusted. (Japanese Patent Application No. 2-49) (Japanese Patent Application No. 2-49).
918).

[0006]

Generally, the effective antifouling composition is that the antifouling active ingredient exhibits an appropriate antifouling effect and that the antifouling active ingredient is a highly safe compound. It must be uniformly dispersed in the film-forming agent (polymer). It must be able to elute at a constant rate over a long period of time from the surface to which the antifouling active ingredient has been applied. After elution, film forming agent (polymer)
It is necessary to satisfy conditions such as that the antifouling composition has an appropriate viscosity and is easy to handle.

Among the above conventional antifouling agents, those using a highly toxic organic or inorganic metal compound do not satisfy the conditions,
Those using a polyisocyanate compound or a metal compound capable of chelating a carboxyl group do not satisfy the conditions. On the other hand, an antifouling agent using a higher aliphatic amine satisfies the conditions and conditions, but the higher aliphatic amine is an organic or inorganic metal compound, tetraethyl, which is another known effective antifouling active ingredient. Thiuram disulfide (TE
T), zinc pyrithione (ZPT), tetrachloroisophthalonitrile (daconyl), dichlorophenylmaleimide, methylenebisthiocyanate (MBTC), etc. are significantly different in the following points, and are preparations as antifouling compositions It is a compound that is difficult to convert.

(1) The higher aliphatic amine is liquid at normal temperature and has higher solubility in seawater than other antifouling active ingredients. (2) The higher aliphatic amine has poor compatibility with a polymer (an acrylate polymer or the like) as a coating film forming agent (elution controlling agent), and thus separates and emerges on the coating film surface.

Therefore, the above-mentioned Japanese Patent Laid-Open Publication No.
The persistent underwater antifouling agent containing higher aliphatic amines described in Japanese Patent Publication No. 2 and Japanese Patent Application No. 2-49918 is also applied to fishing nets, ship bottoms, seawater intake channels, etc. for a long period of time when immersed in the ocean. The elution amount of higher aliphatic amine, which is an active ingredient of the antifouling agent, can be adjusted to some extent, but it is not sufficient yet, and the elution amount immediately after immersion becomes large, and the elution amount tends to decrease with time. For this reason, while the antifouling effect is maintained for a considerable period in the sea area with few attached organisms, the antifouling effect for a long time (for example, 6 months or more) in the sea area with many attached organisms is not yet sufficiently satisfactory. Was.

[0010] This is considered to be due to the fact that the polycarboxylic acid-based copolymer has a low ability to immobilize the amine compound.
In addition, since the copolymer becomes insoluble with time and remains on the fishing net or the like as a coating film, when the antifouling agent is applied again, the adhesion to the remaining coating film is poor and the antifouling agent is peeled off. It also had the problem of being easy.

Further, since the viscosity of the antifouling agent increases remarkably during the coating operation, there are also problems that the consumption of the antifouling agent increases, the flexibility of fishing nets and the like after coating is impaired, and that the antifouling agent cannot be used repeatedly. . The cause is considered to be mainly that the carboxyl group in the copolymer reacts with the hardness component of seawater.

Accordingly, an object of the present invention is to provide a persistent underwater antifouling composition that satisfies all of the above conditions (1) to (4).

[0013]

Means for Solving the Problems The inventors of the present invention provide:
As a result of studying that a higher aliphatic amine is fixed to a polymer as an elution modifier to adjust its elution property and to elute the polymer at a similar rate, a copolymer having a specific monomer composition was obtained. (Polymer) specifically retains and fixes the higher aliphatic amine, and the copolymer itself is eluted in water such as seawater at the same rate, and after a certain period of time, the polymer does not remain in the fish net or the like. After confirmation, the present invention was completed.

Accordingly, the present invention relates to a method for producing a monomer (A) represented by the following general formula (I): 50 to 80% by weight, and a monomer (B) comprising hydroxyethyl acrylate and / or hydroxyethyl methacrylate: 50% by weight, and another monomer containing only one polymerizable double bond copolymerizable with the above (A) and (B) and containing no carboxyl group (hereinafter referred to as “monoethylenically unsaturated monomer”). (C) 0 to 30% by weight (however, the total amount of the monomers (A), (B) and (C) is 100% by weight). A persistent underwater antifouling composition comprising 5 to 80% by weight of a copolymer obtained by polymerizing body components; and 20 to 95% by weight of a higher aliphatic amine represented by the following general formula (II): Offer things.

[0015]

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[0016]

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In the present invention, the group R ² of the monomer (A) represented by the general formula (I) includes, for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Groups, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and other alkyl groups; phenyl, naphthyl, octylphenyl, nonylphenyl and other aralkyl groups; cyclohexyl groups And the like.

If the number of carbon atoms in the group R ² is less than 6, the resulting copolymer will have high hydrophilicity, and if it has more than 20, the obtained copolymer will have high hydrophobicity and will be effective in antifouling. It is not preferable because the dissolution of the higher aliphatic amine compound as a component fluctuates easily. In the present invention, the monoethylenically unsaturated monomer (C) is used as necessary to adjust the performance of a film formed by applying the persistent underwater antifouling composition of the present invention to an object. Is a monomer that is
There is no particular limitation as long as the monomer contains only one polymerizable double bond copolymerizable with the monomers (A) and (B) and does not contain a carboxyl group. Specific examples of the monomer (C) include, for example, methyl (meth) acrylate,
(Meth) acrylic esters having a hydrocarbon group having less than 6 carbon atoms, such as ethyl (meth) acrylate and butyl (meth) acrylate; dodecene, styrene, α-
Unsaturated hydrocarbons such as methylstyrene, butadiene and vinyltoluene; halogenated unsaturated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate and vinyl butyrate; methyl vinyl ether;
Examples include vinyl ethers such as octyl vinyl ether and dodecyl vinyl ether, methoxypolyethylene glycol (meth) acrylate, and acrylonitrile.

As the monomers (A), (B) and (C), one compound may be used alone, or two or more compounds may be used in combination. The proportion of the monomers (A), (B) and (C) used is such that the monomer (A) is 5
The range is from 0 to 80% by weight, and the content of the monomer (B) is from 20 to 50% by weight. In addition, the monomer (C) is 0 to 30% by weight.
It is used as needed within the range.

When the amount of the monomer (A) is less than 50% by weight or the amount of the monomer (B) exceeds 50% by weight, the amount of the antifouling active ingredient which can be stably held and fixed by the obtained copolymer is small. It is not preferable in terms of antifouling performance. Further, when the monomer (A) is 8
If the amount exceeds 0% by weight or the amount of the monomer (B) is less than 20% by weight, the dissolution of the antifouling active ingredient tends to fluctuate, which is not preferable. 30% by weight of monomer (C)
When the ratio exceeds the above range, the proportion of the monomer (A) or the monomer (B) used is out of the above range, and the above-mentioned problems occur, which is not preferable.

The copolymer of the present invention contains, in addition to the monomers (A) and (B) and the monomer (C) used as required,
Unless the effects of the present invention are impaired, unsaturated carboxylic acids such as (meth) acrylic acid, maleic anhydride, and fumaric acid (hereinafter sometimes referred to as “monomer (D)”) are further used. It can also be polymerized. However, it is not preferred that the proportion of the unsaturated carboxylic acid used is 2% by weight or more in the monomer component, because the effect of the present invention is impaired.

The weight average molecular weight of the copolymer of the present invention is
20,000 to 500,000 is appropriate, and 50,000 to 200,000 is preferably used. Further, the Tg (glass transition temperature) of the copolymer is preferably kept at −5 ° C. or less from the viewpoint of handling in winter. In order to produce the copolymer of the present invention,
What is necessary is just to copolymerize the said monomer component using a polymerization initiator. The copolymerization can be carried out by a known method such as polymerization in a solvent, emulsion polymerization, suspension polymerization or bulk polymerization.

In the solution polymerization, alcohols such as ethyl alcohol, isopropyl alcohol, 2-ethoxyethyl alcohol, propylene glycol monomethyl ether, benzene, toluene, xylene, cyclohexane,
aromatic or aliphatic compounds such as n-hexane; ketones such as methyl ethyl ketone; organic solvents such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide in solvents such as esters such as ethyl acetate; The reaction can be carried out in the presence of a polymerization initiator such as an azo compound such as 2,2'-azobisisobutyronitrile and 2,2'-azobisdimethylvaleronitrile. The polymerization temperature is usually in the range of 0 to 150 ° C., and the polymerization apparatus may use a stirring tank or a kneader.

The emulsion polymerization can be carried out in a temperature range of 0 to 100 ° C. while using an emulsifier having a high HLB value and feeding a polymerization initiator such as ammonium persulfate and potassium persulfate and a monomer component into water. Thus, an aqueous dispersion containing the copolymer of the present invention can be obtained. Suspension polymerization uses, for example, an emulsifier having a high HLB value, a protective colloid agent such as polyvinyl alcohol, hydroxyethyl cellulose, and gelatin, suspends the monomer components in water, and conducts the polymerization in the above-mentioned solvent. The polymerization may be performed in the presence of the same oil-soluble polymerization initiator as in the case. The polymerization temperature is preferably in the range of 50 to 150 ° C.

In the present invention, the higher aliphatic amine which is an antifouling active ingredient of the long-lasting underwater antifouling composition has a general formula (I)
It is a compound represented by I). The group R ³ in the general formula (II)
Is a higher aliphatic hydrocarbon group, which may be saturated or unsaturated. The group R ⁴ is hydrogen or a lower aliphatic hydrocarbon group, and the hydrocarbon group may be either saturated or unsaturated. The group R ⁵ is hydrogen, an aliphatic hydrocarbon group, or a lower aliphatic hydrocarbon group substituted with an amino group (however, hydrogen of the amino group may be substituted with a lower aliphatic hydrocarbon group). And when the group R ⁵ is an aliphatic hydrocarbon group, it may be lower or higher. The lower or higher aliphatic hydrocarbon groups mentioned here may be either saturated or unsaturated.

When the groups R ³ , R ⁴ and R ⁵ are other than the above-mentioned groups, a good antifouling effect cannot be obtained. Examples of the lower aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a saturated hydrocarbon group such as a pentyl group and a hexyl group; an ethenyl group, a propenyl group, a butenyl group, an ethynyl group and a propynyl group. And unsaturated hydrocarbon groups.

The higher aliphatic hydrocarbon group includes an aliphatic hydrocarbon group having 12 to 20 carbon atoms. In addition,
When both groups R ³ and R ⁵ are higher aliphatic hydrocarbon groups, they may be the same or different. Also,
When both groups R ⁴ and R ⁵ are lower aliphatic hydrocarbon groups, they may be the same or different.

Specific examples of the higher aliphatic amine represented by the general formula (II) include, for example, dodecylamine, octadecylamine, tetradecylamine, hexadecylamine, oleylamine, myristreylamine, palmitoleylamine, tallowfat Primary amines such as alkylamines and cocoalkylamines; di (dodecyl) amine, di (octadecyl) amine, di (oleyl) amine, di (tallowalkyl) amine, di (cocoalkyl) amine;
Dodecyltetradecylamine, dodecylhexadecylamine, dodecyloctadecylamine, tetradecylhexadecylamine, tetradecyloctadecylamine, hexadecyloctadecylamine, dodecyloleylamine, dodecylmethylamine, oleylethylamine, hexadecylmethylamine, octadecylmethylamine,
Secondary amines such as tallow alkylmethylamine, cocoalkylmethylamine, hexadecylbutylamine, and cocoalkylpropylamine; dodecyldimethylamine;
Hexadecyldimethylamine, octadecyldimethylamine, tetradecyldimethylamine, tallowalkyldimethylamine, cocoalkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, ditallowalkylmethylamine, di (cocoalkyl) methylamine, dodecyltetradecyl Methylamine, dodecylhexadecylmethylamine, dodecyloctadecylmethylamine, tetradecylhexadecylmethylamine, tetradecyloctadecylmethylamine, hexadecyloctadecylmethylamine, dodecylmethylpropylamine,
Tertiary amines such as hexadecylmethylethylamine, tallowalkylethylpropylamine, tallowalkyldiethylamine, tallowalkyldipropylamine, tallowalkyldibutylamine, tallowalkylmethylhexylamine, cocoalkyldipentylamine, and cocoalkyldihexylamine; Methylene diamine, hexadecyl trimethylene diamine, octadecyl trimethylene diamine, tallow alkyl trimethylene diamine, coco alkyl trimethylene diamine, tallow alkyl methylene diamine, coco alkyl ethylene diamine, N-tallow alkyl-N'-dimethyl trimethylene diamine, N-
Diamines such as cocoalkyl-N'-dibutyltrimethylenediamine and the like can be mentioned. Among these amines, "cocoalkyl (...) amine" and "tallow alkyl (...) amine" refer to the above-mentioned amines produced by known means from coconut oil, coconut fat, tallow, and the like. A mixture of amines (mixed alkylamines) in which the group R ³ and / or R ⁵ in the general formula (II) is a saturated or unsaturated aliphatic hydrocarbon group having a carbon number of 12 to 20 and whose main component is a mixture thereof It means there is. As the higher aliphatic amine, any one of the compounds represented by the general formula (II) may be used alone, or
Two or more may be used together.

The higher aliphatic amine is represented by the above general formula
In the compound represented by (II), a group R ^ThreeHas 12 or more carbon atoms
20 saturated or unsaturated aliphatic hydrocarbon groups, radicals R^FourBut
Hydrogen or an alkyl group having 1 to 6 carbon atoms, a group R^FiveIs hydrogen,
C1-C6 alkyl group, C12-C20 saturation also
Or an unsaturated aliphatic hydrocarbon group or amino group
A substituted alkyl group having 1 to 6 carbon atoms (however, amino
The hydrogen of the group is substituted by an alkyl group having 1 to 6 carbon atoms,
Is also good. ) Is preferably used. like this
Compounds are relatively inexpensive industrially available.
You.

The persistent underwater antifouling composition of the present invention can be obtained by mixing the above copolymer in a solid content of 5 to 80% by weight and the above-mentioned higher aliphatic amine in an amount of 20 to 95% by weight. This mixing is performed, for example, by adding the above higher aliphatic amine to a solution in which the copolymer is dissolved using a suitable solvent for improving coating workability, and mixing and stirring.

The mixing ratio of the higher aliphatic amine is 20% by weight.
If it is less than this, it is necessary to apply a large amount of the antifouling composition in order to secure the antifouling performance, which is not preferable because the economic efficiency and workability deteriorate. This ratio is 95
If the content is more than 10% by weight, it is difficult to adjust the dissolution of the higher aliphatic amine, and the properties of the coating film deteriorate.
Mixing the copolymer in a mixing ratio of 5 to 80% by weight as a solid content and 20 to 90% by weight of the higher aliphatic amine,
It is preferable from the viewpoints of dissolution control of the antifouling active ingredient, coating film properties, economy, and coating workability.

Examples of the solvent for improving the coating workability of the continuous underwater antifouling composition of the present invention include water, methyl alcohol, ethyl alcohol, xylene, toluene, kerosene, methyl isobutyl ketone, butyl acetate and dimethyl acetate. Formamide, naphtha, methyl cellosolve and the like are used, but various solvents used in the field of paints can also be used.

The sustained-release underwater antifouling composition of the present invention is usually used in the form of a solution or dispersion dissolved or dispersed in an appropriate solvent. As the solvent, for example, a solvent used for mixing the above copolymer and a higher aliphatic amine is used. It is preferable that the solid content concentration is about 20 to 50% by weight in terms of film formability, film strength, and the like. The solution or dispersion prepared in this way is easy to handle at the time of application work, and avoids extra adhesion,
The cost can be reduced.

As described above, the antifouling composition of the present invention can be used as it is by dissolving or dispersing it in an appropriate solvent. However, it can be used together with a vehicle, a pigment, a plasticizer, a surfactant, a solvent or a diluent. It can be prepared as an antifouling paint. In this case, the total amount of the copolymer and the higher aliphatic amine is 10 to the total paint.
Suitably, it is used so as to be 60% by weight. The vehicle, pigment, plasticizer, surfactant, solvent, diluent, and the like are not particularly limited as long as they can be used in a paint, and can be used as appropriate.

Further, the persistent underwater antifouling composition of the present invention may contain, if necessary, known compounds such as TET, ZPT, tetrachloroisophthalonitrile (daconyl), MBTC, and thiocyanomethylthiobenzothiazole (TCMTB). An antifouling active ingredient may be used in combination with the higher aliphatic amine. The persistent underwater antifouling composition of the present invention is applied by using an appropriate coating method such as dipping, brush coating, spraying, or the like according to an object, dried at room temperature or by heating, and baked if necessary. A film is formed on the surface of the object. The formed film shows good adhesion to the object, adheres to the natural sea without falling off for more than 12 months, and gradually elutes in seawater. In the meantime, attachment of attached organisms is prevented. Since the coating film does not remain, the adhesion of a new coating film formed on the object is good when re-application is performed after elution.

Examples of the objects include fishing nets such as fixed nets and aquaculture nets, ship bottoms, seawater intake channel walls, various structures in a cooling water system using seawater, and various underwater structures such as bridges.

[0037]

The copolymer (polymer) having a specific monomer composition according to the constitution of the present invention has an action of holding and fixing a higher aliphatic amine specifically and uniformly and releasing it gradually. This higher aliphatic amine is a highly safe antifouling active ingredient.
Furthermore, since this copolymer elutes in water such as seawater at a constant rate, higher aliphatic amines can be eluted at a substantially constant rate without being influenced by external factors such as water quality and water temperature, and can be used for a long time. The antifouling effect is maintained for a long time, and the antifouling composition does not remain in the fishing net or the like. Therefore, when a new antifouling composition is applied, the adhesion of the new coating film is good.

Further, the copolymer used in the present invention is:
Since it does not substantially contain a carboxyl group, it does not react with the hardness component in seawater, and the antifouling composition of the present invention does not thicken during the coating operation, and can maintain an appropriate viscosity.

[0039]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.
Production Examples 1 to 6 of the copolymer used in the present invention and Production Examples 7 to 14 of the copolymer as a comparative example are shown below.

Production Example 1 A 500 ml flask equipped with a thermometer, a stirrer, two dropping funnels, a gas inlet tube and a reflux condenser was charged with 60 parts by weight of 2-ethoxyethyl alcohol (ethyl cellosolve) and stirred. The atmosphere in the flask was replaced with nitrogen, and the flask was heated to 50 ° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, a monomer mixture comprising 60 parts by weight of nonylphenyl acrylate as the monomer (A) and 40 parts by weight of 2-hydroxyethyl acrylate as the monomer (B) was added. The polymerization initiator solution consisting of 1.5 parts by weight of 2,2'-azobisisobutyronitrile and 38.5 parts by weight of 2-ethoxyethyl alcohol was added dropwise from the other dropping funnel over 180 minutes. Dropped over minutes.
After completion of the dropwise addition, the reaction solution was heated to 95 ° C., and further maintained at the same temperature for 60 minutes to complete the polymerization.
A viscous solution containing 0% by weight was obtained. As a result of gas chromatography analysis, the polymerization rate of each monomer at this time was 98.0% by weight of nonylphenyl acrylate and 98.5% by weight of 2-hydroxyethyl acrylate. As a result of gel permeation chromatography (GPC) analysis using polystyrene as a standard, the weight average molecular weight was 100,000 (also in the following production examples, the polymerization rate of the monomer was The weight average molecular weight of the copolymer was determined by chromatography analysis,
C analysis).

Production Example 2 A reactor similar to that of Production Example 1 was charged with 60 parts by weight of propylene glycol monomethyl ether, the atmosphere in the flask was replaced with nitrogen under stirring, and the flask was heated to 50 ° C. under a nitrogen stream. Then, while maintaining the same temperature under a nitrogen stream, the monomer (A)
50 parts by weight of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate 3 as monomer (B)
0 parts by weight and a monomer mixture comprising 20 parts by weight of styrene as the other monomer (C) were added dropwise over 120 minutes, and at the same time, 2,2 ′ was added from the other dropping funnel.
A polymerization initiator solution consisting of 1.2 parts by weight of azobisisobutyronitrile and 38.8 parts by weight of propylene glycol monomethyl ether was added dropwise over 180 minutes. After completion of the dropwise addition, the reaction solution was heated to 95 ° C.
The polymerization was completed by maintaining the mixture for 1 minute to obtain a viscous solution containing 50% by weight of the copolymer (2). At this time, the polymerization rate of each monomer was 98.6% by weight for 2-ethylhexyl acrylate, 98.8% by weight for 2-hydroxyethyl acrylate, 97.2% by weight for styrene, and the copolymer (2 )
Had a weight average molecular weight of 950,000.

Production Example 3 Into the same reactor as in Production Example 1, 100 parts by weight of propylene glycol monomethyl ether was charged, the atmosphere in the flask was replaced with nitrogen with stirring, and the flask was heated to 50 ° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, 50 parts by weight of dodecyl acrylate as the monomer (A) and 2-hydroxyethyl acrylate 40 as the monomer (B).
Parts by weight and 2-hydroxyethyl methacrylate 10
Parts by weight of the monomer mixture was added dropwise over 120 minutes, and simultaneously, 0.75 parts by weight of 2,2'-azobisdimethylvaleronitrile and 49.25 of propylene glycol monomethyl ether were added from the other dropping funnel. A polymerization initiator solution consisting of parts by weight was added dropwise over 180 minutes.
After completion of the dropwise addition, the reaction solution was heated to 80 ° C., and further maintained at the same temperature for 60 minutes to complete the polymerization.
A viscous solution containing 0% by weight was obtained. At this time, the polymerization rate of each monomer was 98.0% by weight of dodecyl acrylate,
98.5% by weight of hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate was 97.2% by weight, and the weight average molecular weight of the copolymer (3) was 75,000.

Production Example 4 A reactor similar to that of Production Example 1 was charged with 60 parts by weight of 2-ethoxyethyl alcohol, the atmosphere in the flask was replaced with nitrogen under stirring, and the flask was heated to 40 ° C. under a nitrogen stream. Then, while maintaining the same temperature under a nitrogen stream, 2- (monomer) (A)
A monomer mixture comprising 70 parts by weight of ethylhexyl acrylate and 30 parts by weight of 2-hydroxyethyl acrylate as the monomer (B) was added dropwise over 120 minutes, and simultaneously, 2,2 from the other dropping funnel. A polymerization initiator solution consisting of 0.75 parts by weight of '-azobisdimethylvaleronitrile, 64.25 parts by weight of 2-ethoxyethyl alcohol and 25 parts by weight of xylene was added dropwise over 180 minutes. After the completion of the dropwise addition, the reaction solution was heated to 80 ° C. and further maintained at the same temperature for 60 minutes to complete the polymerization, thereby obtaining a viscous solution containing 40% by weight of the copolymer (4). At this time, the polymerization rate of each monomer was 98.2% by weight for 2-ethylhexyl acrylate and 98.7% by weight for 2-hydroxyethyl acrylate, and the weight average molecular weight of the copolymer (4) was 140,000. Met.

Production Example 5 In Production Example 4, 50 parts by weight of 2-ethylhexyl acrylate and 25 parts by weight of 2-ethylhexyl methacrylate were used as the monomer (A), and 2- (2-ethylhexyl methacrylate) was used as the monomer (B).
Polymerization was carried out in the same manner as in Production Example 4 except that 25 parts by weight of hydroxyethyl acrylate was used, to obtain a viscous solution containing 40% by weight of the copolymer (5). At this time, the polymerization rate of each monomer was 98.2 for 2-ethylhexyl acrylate.
% By weight, 97.0% of 2-ethylhexyl methacrylate
% By weight, 98.1 of 2-hydroxyethyl acrylate
% By weight, and the weight average molecular weight of the copolymer (5) was 16
It was 10,000.

Production Example 6 A reactor similar to Production Example 1 was charged with 60 parts by weight of 2-ethoxyethyl alcohol, the atmosphere in the flask was replaced with nitrogen under stirring, and the flask was heated to 30 ° C. under a nitrogen stream. Then, while maintaining the same temperature under a nitrogen stream, 2- (monomer) (A)
A monomer mixture comprising 75 parts by weight of ethylhexyl acrylate and 25 parts by weight of 2-hydroxyethyl acrylate as the monomer (B) was added dropwise over 120 minutes, and simultaneously, 2,2 from the other dropping funnel. 0.90 parts by weight of '-azobisdimethylvaleronitrile and 2
A polymerization initiator solution consisting of 89.1 parts by weight of ethoxyethyl alcohol was added dropwise over 180 minutes. After dropping,
The reaction solution was heated to 80 ° C. and further maintained at the same temperature for 60 minutes to complete the polymerization, thereby obtaining a viscous solution containing 40% by weight of the copolymer (6). At this time, the polymerization rate of each monomer was 2-
98.3% by weight of ethylhexyl acrylate, 98.5% by weight of 2-hydroxyethyl acrylate,
The weight average molecular weight of the copolymer (6) was 160,000.

Production Example 7 In Production Example 2, 20 parts by weight of 2-ethylhexyl acrylate was used as the monomer (A), and 2 parts as the monomer (B).
-Polymerization was carried out in the same manner as in Production Example 2 except that 40 parts by weight of hydroxyethyl acrylate and 40 parts by weight of butyl acrylate as the monomer (C) were used, and a copolymer (7) was obtained.
A viscous solution containing 50% by weight was obtained. At this time, the polymerization rate of each monomer was 98.2-ethylhexyl acrylate.
4% by weight, 2-hydroxyethyl acrylate
3 wt%, butyl acrylate was 98.2 wt%, and the weight average molecular weight of the copolymer (7) was 105,000.

-Preparation Example 8-In Preparation Example 3, 95 parts by weight of dodecyl acrylate as the monomer (A), 4 parts by weight of 2-hydroxyethyl acrylate and 1 part by weight of 2-hydroxyethyl methacrylate as the monomer (B) Production Example 3 except that
Polymerization was carried out in the same manner as described above, and 40% by weight of the copolymer (8) was used.
A viscous solution containing At this time, the polymerization rate of each monomer is
Dodecyl acrylate is 98.3% by weight, 2-hydroxyethyl acrylate is 98.2% by weight, 2-hydroxyethyl methacrylate is 98.2% by weight, and the weight average molecular weight of the copolymer (8) is 950,000. Met.

Production Example 9 Production Example 9 was repeated except that 90 parts by weight of 2-ethylhexyl acrylate was used as the monomer (A) and 10 parts by weight of 2-hydroxyethyl acrylate was used as the monomer (B). Polymerization was carried out in the same manner as in Example 4 to obtain a viscous solution containing 40% by weight of the copolymer (9). At this time, the polymerization rate of each monomer was 98.8% by weight for 2-ethylhexyl acrylate and 98.7% by weight for 2-hydroxyethyl acrylate, and the weight average molecular weight of the copolymer (9) was 13. It was 10,000.

-Production Example 10-In Production Example 1, 20 parts by weight of nonylphenyl acrylate as the monomer (A) and 2-parts as the monomer (B)
Polymerization was carried out in the same manner as in Production Example 1 except that 80 parts by weight of hydroxyethyl acrylate was used to obtain a copolymer (10).
A viscous solution containing 50% by weight was obtained. At this time, the polymerization rate of each monomer was 98.6% by weight for nonylphenyl acrylate and 98.7% by weight for 2-hydroxyethyl acrylate, and the weight average molecular weight of the copolymer (10) was 7.
It was 20,000.

-Production Example 11-The same reactor as in Production Example 1 was charged with 60 parts by weight of 2-ethoxyethyl alcohol, the atmosphere in the flask was replaced with nitrogen under stirring, and the flask was heated to 40 ° C under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, 2- (monomer (B))
Hydroxyethyl acrylate 100 parts by weight was dropped over 120 minutes, and at the same time, from the other dropping funnel,
A polymerization initiator solution consisting of 0.75 parts by weight of 2,2'-azobisdimethylvaleronitrile and 89.25 parts by weight of 2-ethoxyethyl alcohol was added dropwise over 180 minutes. After completion of the dropwise addition, the reaction solution was heated to 80 ° C., and further maintained at the same temperature for 60 minutes to complete the polymerization.
A viscous solution containing 40% by weight of 1) was obtained. 2-
The polymerization rate of hydroxyethyl acrylate was 98.7% by weight, and the weight average molecular weight of homopolymer (11) was 90,000.

Production Example 12 A similar reactor as in Production Example 1 was charged with 60 parts by weight of 2-ethoxyethyl alcohol, the atmosphere in the flask was replaced with nitrogen under stirring, and the flask was heated to 40 ° C. under a nitrogen stream. Thereafter, while maintaining the same temperature under a nitrogen stream, 2- (monomer (B))
A monomer mixture comprising 8 parts by weight of hydroxyethyl acrylate, 50 parts by weight of butyl acrylate as a monomer (C) and 42 parts by weight of methyl methacrylate was added dropwise over 120 minutes, and at the same time, from the other dropping funnel. 0.75 parts by weight of 2,2'-azobisdimethylvaleronitrile and 2-ethoxyethyl alcohol 6
A polymerization initiator solution consisting of 4.25 parts by weight and xylene 25 parts by weight was added dropwise over 180 minutes. After completion of the dropwise addition, the reaction solution was heated to 80 ° C., and further maintained at the same temperature for 60 minutes to complete the polymerization, thereby obtaining a viscous solution containing 40% by weight of the copolymer (12). At this time, the polymerization rate of each monomer was 2-
Hydroxyethyl acrylate was 98.7% by weight, butyl acrylate was 98.6% by weight, methyl methacrylate was 97.2% by weight, and the weight average molecular weight of copolymer (12) was 135,000.

Production Example 13 A flask equipped with a thermometer, a stirrer, two dropping funnels, a gas inlet tube and a reflux condenser was charged with 11.4 parts by weight of xylene and 26.6 parts by weight of 2-methoxyethanol. The atmosphere in the flask was replaced with nitrogen under stirring, and the flask was flushed with nitrogen for 8 hours.
Heated to 0 ° C. Then, while maintaining the same temperature under a nitrogen stream, 10.5 parts by weight of xylene, 24.5 parts by weight of 2-methoxyethanol, and acryl were added to the liquid in the flask from one of the two dropping funnels. Acid 25.0
Part by weight, 5.0 parts by weight of 2-hydroxyethyl acrylate, 40.0 parts by weight of methyl methacrylate, and 30.0 parts by weight of 2-ethylhexyl acrylate were dropped over 60 minutes, and at the same time, the other was mixed. A polymerization initiator solution comprising 7.5 parts by weight of xylene, 17.5 parts by weight of 2-methoxyethanol and 2.0 parts by weight of 2,2'-azobisdimethylvaleronitrile was added dropwise from the dropping funnel over 120 minutes. After completion of the dropwise addition, the polymerization was completed by further maintaining the same temperature for 60 minutes, and the copolymer (1
A viscous solution containing 50% by weight of 3) was obtained. At this time, the polymerization rate of each monomer was 97.5% by weight of acrylic acid, 98.4% by weight of 2-hydroxyethyl acrylate, 97.0% by weight of methyl methacrylate, and 98.1% by weight of 2-ethylhexyl acrylate. The weight average molecular weight of the copolymer (13) was 500000.

-Production Example 14-The same reactor as in Production Example 1 was charged with 60 parts by weight of 2-ethoxyethyl alcohol, the atmosphere in the flask was replaced with nitrogen with stirring, and the flask was heated to 40 ° C under a nitrogen stream. Then, while maintaining the same temperature under a nitrogen stream, 2- (monomer) (A)
Ethylhexyl acrylate 100 parts by weight was added dropwise over 120 minutes, and at the same time, from the other dropping funnel,
A polymerization initiator solution consisting of 0.75 parts by weight of 2,2'-azobisdimethylvaleronitrile, 64.25 parts by weight of 2-ethoxyethyl alcohol and 25 parts by weight of xylene was added to 1 part of a polymerization initiator solution.
It was added dropwise over 80 minutes. After completion of the dropwise addition, the reaction solution was heated to 80 ° C. and maintained at the same temperature for 60 minutes to complete the polymerization, thereby obtaining a viscous solution containing 40% by weight of the homopolymer (14). At this time, the polymerization rate of 2-ethylhexyl acrylate was 98.6% by weight, and the weight average molecular weight of homopolymer (14) was 15,000.

Examples 1 to 12 The ratios of the copolymers obtained in Production Examples 1 to 6 and various amine compounds are shown in Table 1 (formulation composition ratio: solid content conversion).
To obtain a persistent underwater antifouling composition of the present invention. -Comparative Examples 1 to 8-The copolymers or homopolymers obtained in the above Production Examples 7 to 14 and various amine compounds were mixed in the proportions shown in Table 1 (formulation composition ratio: solid content conversion), An underwater antifouling composition for comparison was obtained.

In Table 1, the abbreviations in the column of the monomer species used for producing the polymer are as follows. NFA: nonylphenyl acrylate 2EHA: 2-ethylhexyl acrylate 2EHMA: 2-ethylhexyl methacrylate DA: dodecyl acrylate HEA: hydroxyethyl acrylate HEMA: hydroxyethyl methacrylate ST: styrene BA: butyl acrylate MMA: methyl methacrylate AA: acrylic acid Abbreviations in the column of the type of the higher aliphatic amine are as follows. A1: dodecylamine A2: octadecylamine A3: di (dodecyl) amine A4: di (octadecyl) amine A5: N, N-dimethyldodecylamine A6: N, N-dimethyloctadecylamine A7: N-dodecyltrimethylenediamine A8: N-octadecyl trimethylenediamine A9: tallow alkylamine (tallow alkyl; carbon number 12)
-20 saturated or unsaturated aliphatic hydrocarbon group) A10: N-methylethyldodecylamine The antifouling performance of the underwater antifouling compositions of the above Examples and Comparative Examples was examined as follows. The results are summarized in Table 2. Anti-fouling performance evaluation test method As a test net, a polyethylene culture net (10
0, 5 sections, 40 cm × 60 cm, 60 g) were used.

A test net was immersed in the underwater antifouling composition obtained in each of Examples and Comparative Examples shown in Table 1, and then air-dried for 3 days. In this case, the adhesion amount of the underwater antifouling composition was calculated from the weight difference before and after immersion, and was controlled as follows. That is, the amount of the higher aliphatic amine contained in the underwater antifouling composition attached to the test net was 8.0 to 9% based on the weight of the net.
0% by weight.

A test net to which the underwater antifouling composition was adhered was suspended on a raft off Tokushima Prefecture at a depth of 1.0 to 1.5 m below the sea surface, and the antifouling effect was periodically evaluated. . The antifouling effect was evaluated by the ratio (percentage) of the area occupied by attached organisms to the area of the test net (40 cm × 60 cm). The immersion time differs greatly between the low water temperature period and the high water temperature period because the species and the amount of attached organisms differ greatly, so that immersion was started on the same sample on May 5 and July 5, respectively. I also checked.

[0058]

[Table 1]

[0059]

[Table 2]

As can be seen from Tables 1 and 2, the antifouling compositions of the examples maintain the antifouling effect over a long period of time.
Although there is little variation due to the season, those of the comparative examples have poor durability of the antifouling effect. According to the comparison between Example 1 and Comparative Example 4 and the comparison between Example 12 and Comparative Example 3, if the monomer composition of the copolymer is out of the range specified in the present invention, the expected effect is obtained. It turns out that it cannot be reached. The same can be seen from a comparison between Example 6 and Comparative Example 2 and a comparison between Example 7 and Comparative Example 1.

Next, the dissolution property of each underwater antifouling composition obtained in Example 8 and Comparative Example 7 was confirmed as follows. The results are shown in FIG. Dissolution test method As a test net, a polyethylene net for cultured fish (10
Using 0 pieces, 5 sections, 25 cm × 15 cm, 7.5 g), the test net was immersed in each of the underwater antifouling compositions obtained in Example 8 and Comparative Example 7 for 3 minutes, and then air-dried for 3 days. This test network (12 pieces in each case) was placed on a raft off Tokushima Prefecture 1.0 below sea level.
Simultaneously immersed to a depth of ~ 1.5 m. The immersion was performed on May 5.

Every 15 days, the test nets were pulled up two by two to extract higher aliphatic amines remaining in the nets and quantified by gas chromatography. The elution amount (mg) of the higher aliphatic amine was calculated from the amount of the higher aliphatic amine attached to the test net before immersion. As shown in FIG. 1, in the antifouling composition of Example 8, the cumulative elution amount of higher aliphatic amine increased in proportion to the passage of time. On the other hand, in the case of Comparative Example 7, the elution amount started to decrease after about 45 days, and almost no elution started about 75 days.

[0063]

According to the present invention, a specific higher aliphatic amine which is an antifouling active ingredient having low toxicity and good biodegradability has a specific monomer composition as a film-forming agent. By being held and fixed in the coalescence, the dissolution property is controlled, and the copolymer is also eluted at the same speed, so that the antifouling effect is maintained for a long time and the underwater protection in which the coating film does not remain on the fishing net etc. A soil composition can be obtained.

Further, even when the antifouling composition of the present invention is applied to a fishing net or the like, the increase in viscosity of the antifouling composition is suppressed, so that the workability is improved. By applying the underwater antifouling composition of the present invention to a fishing net, a ship bottom, a seawater intake channel, and the like, it is possible to suppress, for a long time, the attachment of attached organisms, particularly, the attached organisms in the sea to the fishing net, the bottom of the sea, the seawater intake channel, and the like. be able to.

[Brief description of the drawings]

FIG. 1 is a graph showing the variation with time of the cumulative elution amount of higher aliphatic amines from a coating film of an antifouling composition in water obtained in Example 8 and Comparative Example 7.

[Explanation of symbols]

 1 Curve representing variation in Example 8 2 Curve representing variation in Comparative Example 7

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 55/00 C08L 55/00 C09D 5/16 C09D 5/16 133/08 133/08 133/10 133/10 155/00 155 / 00 (72) Inventor Kenji Rakuya 10-12 Ukishima-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Nippon Shokubai Kawasaki Plant Ukishima Plant (72) Inventor Takayoshi Goto Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 Nippon Shokubai Co., Ltd. Kawasaki Laboratory (56) References JP-A-3-252463 (JP, A) JP-A-1-103672 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB A01N 25/10 A01N 33/04 C08K 5/17 C08L 33/08 C08L 33/10 C08L 55/00 C09D 5/16 C09D 133/08 C09D 133/10 C09D 155/00

Claims (2)

(57) [Claims] 1. 50 to 80% by weight of a monomer (A) represented by the following general formula (I), 20 to 50% by weight of a monomer (B) which is hydroxyethyl acrylate and / or hydroxyethyl methacrylate, And other monomers (C) 0 to 3 containing only one polymerizable double bond copolymerizable with the above (A) and (B) and not containing a carboxyl group.
5 to 80% by weight of a copolymer obtained by polymerizing a monomer component consisting of 0% by weight (the total amount of monomers (A), (B) and (C) is 100% by weight). %; Higher aliphatic amine represented by the following general formula (II): 20 to 95% by weight
And a persistent underwater antifouling composition comprising: Embedded image Embedded image 2. In the general formula (II), R ³ has 12 to 2 carbon atoms.
0 is a saturated or unsaturated aliphatic hydrocarbon group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁵ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a saturated group having 12 to 20 carbon atoms. Alternatively, an alkyl group having 1 to 6 carbon atoms substituted with an unsaturated aliphatic hydrocarbon group or an amino group (however, a hydrogen atom in the amino group may be substituted with an alkyl group having 1 to 6 carbon atoms. The persistent underwater antifouling composition according to claim 1, wherein