JP2008007655A - Aqueous antifouling paint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous antifouling paint having antifouling properties comparable to an organic solvent-based antifouling paint. <P>SOLUTION: This aqueous antifouling paint comprises an alkenyl succinic anhydride, having an alkenyl group of ≥16C, liquid at a room temperature, and a surfactant emulsifying the anhydride in water. The aqueous antifouling paint exerts such an antifouling effect comparable to the organic solvent-based antifouling paint as to prevent adhesion of aquatic organisms for long periods by virtue of containing the alkenyl succinic anhydride. The aqueous antifouling paint has good workability in handling and enables to control a load to environment because it contains no or little organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous antifouling paint for preventing fouling due to adhesion of aquatic organisms.

  Fishery materials such as fish farming or stationary fishing nets, ropes, floats, etc. are used by immersing in water, but aquatic organisms on the surface, i.e. bivalves, crustaceans, Animals such as hydro-insects, plants such as wakame, aosa, and kombu are attached and flourish. If the attached amount of aquatic organisms increases, the original function of the material is impaired. For example, in a fishing net for stationary use, resistance to waves increases and breaks. In the case of fish farming nets (ginger), water passage deteriorates and oxygen deficiency occurs. These necessitate a repair and replacement of materials, which consumes considerable time and effort.

As antifouling measures for aquatic organisms, various antifouling paints have been proposed and used as fishing net antifouling agents. However, organic solvents such as xylene are used as solvents in conventional antifouling paints, and organic solvents are flammable and addictive as is well known, so care must be taken during handling during coating or painting. Otherwise, there is a risk of fire and poisoning. This also results in the release of organic solvents into the environment during work. In recent years, water-based antifouling paints using water as a solvent, such as those used in household paints, have been proposed (for example, Patent Document 1).
JP 2005-213336 A

However, water-based antifouling paints have not yet been put into practical use with antifouling performance equivalent to that of organic solvent antifouling paints.
In view of the above problems, an object of the present invention is to provide an aqueous antifouling paint having an antifouling performance comparable to an organic solvent antifouling paint.

  As a result of intensive studies to solve the above problems, the present inventors have found that when an aqueous antifouling paint contains alkenyl succinic anhydride, the formed coating film is an adherend such as a fishing net, rope, float, etc. In addition to exhibiting the performance expected of paints that are immersed in water, such as having the flexibility to follow the movement of the adherend and prevent adhesion of aquatic organisms over a long period of time The inventors have found that the dirt performance is exhibited, and have completed the present invention. Since it does not contain an organic solvent, the handling workability is good and the environmental load can be reduced.

  That is, the water-based antifouling paint of the present invention is characterized by containing an alkenyl succinic anhydride that has an alkenyl group having 16 or more carbon atoms and is liquid at room temperature and a surfactant obtained by emulsifying the alkenyl succinic anhydride in water. The alkenyl group may be linear or branched and may have a substituent. For example, if the total atomic weight of the alkenyl hydrocarbon skeleton is in the range of 150 to 4000, it is usually at atmospheric pressure and normal temperature. If it is liquid (has fluidity) and the liquid is selected, it can be used because it can be emulsified with a surfactant in water without using an organic solvent. Here, normal temperature means 25 ° C. However, when the number of carbon atoms is small, organic solvent properties such as flammability are exhibited, so those having 16 or more carbon atoms are used.

  In addition to the binder component and the antifouling active component, alkenyl succinic anhydride is emulsified in water as a solvent. Furthermore, it is preferable to contain an elution regulator. Although the mechanism by which the antifouling performance is exhibited over a long period of time is not clear, it is considered that the alkenyl succinic anhydride is gradually hydrolyzed in water to perform a sustained release function. Alkenyl succinic anhydride consists only of C, H, O, and itself and its degradation products are also non-toxic.

The alkenyl group of the alkenyl succinic anhydride may be an alkyl-propenyl group having a propenyl moiety attached to the succinic anhydride and having an alkyl attached to one or two carbons thereof. For example, (CH ₃ ) ₃ CR ⁰ _n -or (CH ₃ ) ₃ CR ⁰ _n CH _2- (R ⁰ is a C ₄ hydrocarbon fraction, n is an integer of 2 to 70) A succinic anhydride having an alkyl-propenyl group, which has a group on one carbon and may have a linear alkyl having 1 to 20 carbon atoms on another carbon, can be preferably used. . Here, the C ₄ hydrocarbon fraction means —CH ₂ C (CH ₃ ) ₂ —.

It is also possible to use succinic anhydrides having an alkyl-propenyl group in which A or ACH ₂ — (where A is a succinic anhydride group) is further bonded on the propenyl carbon to which no alkyl is bonded. .

  Succinic anhydrides having such alkyl-propenyl groups are represented by the formula (I)

を用いて、また水素をＨで表し、（ＣＨ_３）_３ＣＲ^０ _ｎをＢで表し、直鎖状アルキルをＡｌｋで表して例示すると、Ｒ^１／Ｒ^２／Ｒ^３が順に、Ｈ／Ｈ／ＢＣＨ_２、あるいはＨ／Ｂ／Ａｌｋ、Ｈ／Ｂ／ＡＣＨ_２、あるいはＨ／Ａ／ＢＣＨ_２、であるアルケニルコハク酸無水物が挙げられる。

In addition, when hydrogen is represented by H, (CH ₃ ) ₃ CR ⁰ _n is represented by B, and linear alkyl is represented by Alk, R ¹ / R ² / R ³ is H / H in order. Alkenyl succinic anhydride which is / BCH ₂ , or H / B / Alk, H / B / ACH ₂ , or H / A / BCH ₂ .

R ¹ and R ² are both hydrogen, R ³ is (CH ₃ ) ₃ CR ⁰ _n CH ₂ — (where R ⁰ is a C ₄ hydrocarbon fraction, and n is an integer from 3 to 40) Or R ¹ is hydrogen, R ² is (CH ₃ ) ₃ CR ⁰ _n — (R ⁰ and n are as defined above), and R ³ has 1 to 4 carbon atoms. An alkenyl succinic anhydride which is an alkyl is more preferable. Such an alkenyl succinic anhydride can be produced by adding maleic anhydride to polybutene obtained from naphtha decomposition described below. Those having a molecular weight of about 1000 can also be obtained as commercial products.

Succinic acid having an alkyl-propenyl group having 1 or 2 linear alkyls, which is obtained by adding maleic anhydride to a linear internal olefin (alkene) having 16 or more carbon atoms and causing ene addition reaction. Anhydrides, ie succinic acids with alkyl-propenyl groups in which R ¹ / R ² / R ³ are in turn H / Alk / H, Alk / H / H, Alk / Alk / H, Alk / H / Alk Anhydrides can also be used. Those in which the succinic anhydride portion is partially hydrolyzed are also effective.

  Resin etc. can be used as a binder component. The use of a resin emulsion, such as an acrylic resin emulsion, is convenient. Those having a glass transition point of -20 to + 30 ° C are preferred. When it is lower than −20 ° C., stickiness occurs, and when it exceeds + 30 ° C., film formation is difficult. The monomer composition is not particularly limited, although it is necessary to consider water resistance, adhesion to and adherence to an adherend, and compatibility with other compounds. The amount is usually 50 to 400 parts, preferably 80 to 300 parts, based on 100 parts of alkenyl succinic anhydride (representing the number of parts by weight). If it is less than 50 parts, the adhesiveness becomes insufficient, and if it exceeds 400 parts, the viscosity is large, so the elongation is poor, resulting in thick coating, stiffness, large amount of use, and the like. 80 parts or more is desirable from the viewpoint of dispersion stability.

  Any surfactant can be used without particular limitation as long as it has both the dispersion stabilizing effect of alkenyl succinic anhydride and the wettability improving effect on the adherend. For example, one of the following surfactants is used alone or in combination of two or more, and blended at a ratio of 0.5 to 5%, preferably 0.5 to 3%, based on the total amount of the water-based antifouling paint. can do. If it is less than 0.5%, long-term storage stability is insufficient, and if it exceeds 5%, the water resistance is lowered and the antifouling performance tends to be adversely affected.

  Anionic surfactants that can be used are polyoxyethylene or POE alkyl ether carboxylates, N-acyl amino acid salts, acylated peptides, alkyl sulfonates, sulfosuccinates, α-olefin sulfonates, N-acyl sulfonates. Sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyethylene or POE alkyl allyl ether sulfate, alkyl phosphate, polyoxyethylene or POE alkyl ether phosphate, polyoxyethylene or POE alkyl allyl ether phosphate Such as salt.

  Nonionic surfactants include polyoxyethylene alkyl and alkyl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ether, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether. , Polyoxyethylene ether of sorbitol ester, polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester, sucrose ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, amino oxide And silicone surfactants.

  As the elution regulator, one or more selected from dialkyl polysulfides, silicone oils, and polybutenes can be used. Examples of dialkyl polysulfides that can be used include diethyl polysulfide, dipropyl polysulfide, dioctyl polysulfide, ditertiary butyl polysulfide, ditertiary nonyl polysulfide, ditertiary decyl polysulfide, and the like. One kind can be blended alone, or two or more kinds can be blended.

  Silicone oils include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, carboxyl modified silicone oil, alkyl and alkyl aralkyl modified silicone oil, alkyl aralkyl polyether modified silicone oil, polyether modified silicone. Although oil etc. are mentioned and it is not limited to these, It is preferable to select considering the defoaming in the whole coating material. These can be blended alone or in combination of two or more.

The polybutene preferably has a low molecular weight having an average molecular weight of 200 to 1,000, and polymers having different average molecular weights can be blended singly or in combination of two or more. Such polybutenes _{e.g., (CH 3) 3 C (} CH 2 C (CH 3) 2) n CH 2 C (CH 3) = represented by CH _2, butane produced by naphtha cracking - isobutylene of butene fraction Various grades are commercially available as a copolymer which is mainly composed of n-butene and partially reacted with n-butene.

  The total amount of elution modifier is usually 50 to 500 parts per 100 parts alkenyl succinic anhydride. If it is less than 50 parts, alkenyl succinic anhydride and the like are not easily eluted and the antifouling performance is lowered, and if it exceeds 500 parts, the viscosity is too low to function as a paint. What is necessary is just to adjust suitably the mixing ratio of each elution control agent according to the characteristic of the adhering organism of the water area where a coating adherend is used, water temperature, salt concentration, etc.

  Antifouling active ingredients used in the aqueous antifouling paint of the present invention include conventionally used copper powder, cuprous oxide, rhodan copper, zinc and copper salts of 2-pyridinethiol-1-oxide, dimethyldithiocarbamate Zinc and copper salts, bis (dimethyldithiocarbamoylzinc) ethylenebisdithiocarbamate, 3- (3,4 dichlorophenyl) -1,1-dimethylurea, N-dichlorofluoromethylthio-N ′, N′-dimethyl-N— Examples thereof include phenylsulfamide, N- (fluorodichloromethylthio) phthalimide, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. The amount of the antifouling active ingredient is usually 30 to 500 parts, preferably 100 to 400 parts, based on 100 parts of alkenyl succinic anhydride. When the blending amount is less than 30 parts, the antifouling effect due to the antifouling active ingredient cannot be sufficiently obtained, and when it exceeds 500 parts, the coating film after drying tends to be brittle.

  Commonly blended pigments, dyes, colorants, anti-settling agents, thickeners, color separation inhibitors, preservatives, antifoaming agents, and the like can be appropriately blended. A water-soluble organic solvent such as alcohols may be blended as a film-forming aid for promoting drying at low temperatures. However, as described above, since the main object is to eliminate the harmful effects of organic solvents, the blending amount is limited to 0.1 to 5 parts with respect to 100 parts of the water-based antifouling paint. If it is less than 0.1 part, the effect as an auxiliary agent is low, and if it exceeds 5 parts, a flammability problem occurs.

  The water-based antifouling paint of the present invention is obtained by mixing all the desired components in the above-mentioned paint components with stirring and mixing, or by mixing a liquid component and then dispersing it in water together with other components. Can be What is necessary is just to apply | coat or paint the water-based antifouling paint which became uniform to adherends, such as a fishing net, a rope, and a float, by methods, such as a dipping, a brush coating, and a spray, and to dry.

  Since the water-based antifouling paint of the present invention contains alkenyl succinic anhydride, it exhibits an antifouling effect for preventing the attachment of aquatic organisms over a long period of time. Comparable to dirty paint. Since it contains no or almost no organic solvent, there is no danger of ignition, organic solvent poisoning, etc. in handling operations, and it is safe, and the burden on the environment can also be suppressed.

Hereinafter, embodiments of the present invention will be described with reference to specific examples. These examples do not limit the scope of the invention.
(Examples 1 and 2 and Comparative Examples 1 and 2)
The compositions shown in Table 1 below were uniformly stirred and mixed to prepare an aqueous antifouling paint. The maleated polybutene shown in the table is an alkenyl succinic anhydride in which R ³ is methyl in the structure described in claim 5 and has a number average molecular weight of 1100.

（防汚効果試験）
各実施例および比較例の水性防汚塗料を、ポリエチレン製無結節網（７節４００デニール／５０本撚り）にディッピング法で塗布し、５日間天日乾燥させることにより、試験網を作成した。各試験網を無処理網とともに平成１７年３月中旬から４ヶ月間、大阪府泉南郡岬町淡輪の海面下約１ｍに浸漬し、生物の付着状況を調べた。結果を表２に示す。

(Anti-fouling effect test)
The water-based antifouling paints of each Example and Comparative Example were applied to a polyethylene knotless net (7 knots 400 denier / 50 twists) by a dipping method, and sun dried for 5 days to prepare a test net. Each test net was immersed in an untreated net for about 4 m from the middle of March 2005 under about 1 m below the sea level in Misawa-cho, Sennan-gun, Osaka, and the state of organisms was examined. The results are shown in Table 2.

表２から、本発明の水性防汚塗料を用いた実施例１及び２は、比較例１及び２に比べて生物付着を防止する効果が大きく且つ長期間持続していることが明らかである。

From Table 2, it is clear that Examples 1 and 2 using the water-based antifouling paint of the present invention have a greater effect of preventing biofouling than Comparative Examples 1 and 2, and are sustained for a long time.

  The water-based antifouling paint of the present invention has good workability, has a low environmental impact, and has an excellent antifouling effect for preventing the attachment of aquatic organisms. It can also be used for hulls.

Claims (8)

  A water-based antifouling paint comprising an alkenyl succinic anhydride having an alkenyl group having 16 or more carbon atoms and a liquid alkenyl succinic anhydride emulsified in water.   The water-based antifouling paint according to claim 1, wherein the binder component, the antifouling active ingredient and the alkenyl succinic anhydride are emulsified in water as a solvent.   The water-based antifouling paint according to claim 1 or 2 containing an elution regulator. Alkenyl ^{_{groups, (CH 3) 3 CR 0}} n - represented by ^{(R 0} is a _{C 4} hydrocarbon fraction, n is an integer of 2-70) - or ^{_{(CH 3) 3 CR 0 n}} CH 2 The water-based antifouling paint according to claim 1, which is an alkyl-propenyl group which has an alkyl group on one carbon and may have a linear alkyl having 1 to 20 carbon atoms on another carbon. Alkyl unbound further on propenyl carbon, A or ACH 2 - _(wherein, A is succinic anhydride groups) according to claim 1 or claim 4, wherein the water-based anti-fouling paints are attached. Alkenyl succinic anhydride is represented by the formula (I)

[Wherein R ¹ and R ² are both hydrogen, R ³ is (CH ₃ ) ₃ CR ⁰ _n CH ₂ — (where R ⁰ is a C ₄ hydrocarbon fraction, n is 3 to 40 Or R ¹ is hydrogen, R ² is (CH ₃ ) ₃ CR ⁰ _n — (R ⁰ and n have the same meaning as described above), and R ³ is carbon The water-based antifouling paint according to claim 4, which is an alkyl having a number of 1 to 4.   The water-based antifouling paint according to claim 2, wherein the binder component is a resin emulsion.   The water-based antifouling paint according to claim 3, wherein the elution regulator is one or more selected from dialkyl polysulfides, silicone oils, and polybutenes.