JP5462235B2 - Antifouling agent composition, antifouling treatment substrate, and antifouling treatment method for substrate - Google Patents

Description

  The present invention relates to an antifouling agent composition, an antifouling treatment substrate, and an antifouling treatment method for a substrate, and more particularly impregnating a substrate that comes into contact with seawater or fresh water, such as a fishing net, fishing gear, ship or underwater structure. -It is related with the antifouling agent composition which can exhibit the antifouling performance if apply | coated, an antifouling processing base material, and the antifouling processing method of a base material.

  Fishing nets, underwater structures, etc. are used for a long time in water, especially in seawater, so a lot of marine organisms such as hydro-insects, sandy beetles, Aosa, Aonori, cell plastic, oysters adhere to the seawater, Breeding may damage the original functions of fishing nets. Among fishing nets, aquaculture nets and stationary nets are kept in seawater for a long time, so marine organisms are prone to corrosion and propagation, and must be replaced frequently, resulting in a large economic loss.

  In order to solve such problems, antifouling agents or antifouling paints are widely applied to the surface of fishing nets for the purpose of preventing the attachment of marine organisms. As a marine organism adhesion prevention method, antifouling agent composition which mixes rosin and vinyl resin or acrylic resin as a color developing agent for properly eluting these antifouling agents to cuprous oxide or organic antifouling agents Products, or cuprous oxide or organic antifouling agents, and a wide range of antifouling compositions containing hydrolyzable resins (acrylic acid polymers such as silicon, copper, zinc and tin alkyl esters or alkoxy esters) as colorants It is used. Further, a color developing agent having antifouling property, such as room temperature curable silicone rubber, is also used as an antifouling agent. However, satisfactory antifouling properties are not obtained with these antifouling agent compositions.

  In addition, (1) JP-A-4-142373 (Patent Document 1, corresponding patent: Japanese Patent No. 2140275) describes a hydrophilic / lipophilic balance (HLB) based on the amount (% by weight) of polyoxyethylene in a polymer. ) Is an antifouling paint containing an oxyalkylene group-containing chain organopolysiloxane which is a silicone oil of 2 to 10, and in this publication, when the HLB is 2 or less, the coating itself exhibits water repellency and is antifouling. It is described as inferior in durability. However, when the antifouling paint described in the publication is used, a coating film having an effect of preventing adhesion of seaweed can be obtained, but it is inferior to the effect of preventing adhesion of luminal animals such as hydroworms.

  In addition, (2) Japanese Patent Publication No. 6-104793 (Patent Document 2) discloses a non-silicone film-forming resin and an oxyalkylene having an HLB of 3 to 12 based on the amount (% by weight) of polyoxyethylene in the polymer. An antifouling paint containing a group-containing chain organopolysiloxane in a specific amount ratio is disclosed, and in this publication, if this HLB is smaller than 3, the antifouling effect is inferior and it is difficult to maintain the antifouling effect over a long period of time. It is described that. Further, it is described that when the composition described in the publication is used, an antifouling coating film particularly useful for fishing nets can be obtained. However, there has been room for further improvement in terms of the antifouling property of aquatic organisms on fishing nets and underwater structures.

  In order to solve such problems, the applicant of the present invention, in (3) Japanese Patent Laid-Open No. 9-176576 (Patent Document 3), disclosed a hydrophilic / lipophilic balance (HLB) based on polyoxyethylene in a polymer. ) Is an underwater antifouling agent composition containing oxyalkylene group-containing chain organopolysiloxane having 2 to 7 and bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate in a specific amount ratio. The coating film can effectively prevent adhesion of coelenterate such as hydroworms to fishing nets, underwater structures and the like.

  In addition, the applicant of the present application described in (4) JP-A-9-176777 (Patent Document 4), an oxyalkylene group-containing chain organopolysiloxane described in JP-A-9-176576, cuprous oxide, Has been proposed, and the coating film made of the composition has an antifouling property to aquatic organisms such as shellfish, hydroworms, and algae against fishing nets and underwater structures. Is excellent.

However, even in the antifouling paints described in these publications proposed by the applicant of the present application, there is room for further improvement in terms of antifouling properties of aquatic organisms such as shellfish, hydroworms, and algae against fishing nets and underwater structures. It was. Therefore, the present inventors conducted further diligent research. As a result, the hydrophilic parent based on propyleneoxy group (C ₃ H ₆ O) has an HLB value based on the amount of ethyleneoxy group as shown in the above publications in a specific range. Use of oxyalkylene group-containing organopolysiloxanes with an oil balance (HLB _PO ) in a specific range is excellent for various marine organisms such as coelenterates (eg, cell plastics, hydroworms, etc.), barnacles, seaweeds, etc. The inventors have found that an antifouling agent composition capable of forming an antifouling coating film exhibiting antifouling properties has been obtained, and the present invention has been completed.

  The publications described in the above (1) to (4) do not describe or suggest any HLB based on the amount of propyleneoxy group.

JP-A-4-142373 Japanese Patent Publication No. 6-104793 Japanese Patent Laid-Open No. 9-176576 Japanese Patent Laid-Open No. 9-176777

  The present invention is intended to solve the problems associated with the prior art as described above, and is capable of exhibiting excellent antifouling properties against aquatic animals such as hydroworms and aquatic organisms such as seaweeds. It aims at providing the antifouling agent composition which can form a dirty coating film.

  In addition, the present invention provides an anti-fouling technique for fishing nets, ships, underwater structures, etc. having an anti-fouling coating film that can exhibit excellent anti-fouling properties against aquatic animals such as hydro-insects and aquatic organisms such as seaweed as described above. An object of the present invention is to provide a soil-treating substrate and a soil-resisting treatment method for the substrate.

  The first antifouling agent composition according to the present invention has the following formula [I]:

[In the formula [I], R ⁵ represents an alkyl group or a phenyl group, and R ¹ , R ² and R ³ each independently represents an alkyl group, a phenyl group or X: “(CH ₂ ) _p O (C ₂ H ₄ O) _q (C ₃ H ₆ O) _r R ⁴ (R ⁴ represents a hydrogen atom or an alkyl group, aryl group, aralkyl group or acyl group each having 1 to 15 carbon atoms, and p is 0 to 5) Q and r each independently represents a number from 1 to 50.)], m represents a number from 1 to 1000, and n represents a number from 0 to 50. However, when n is 0, R ₁ and / or R ₂ is the above X. The oxyalkylene group-containing organopolysiloxane represented by formula (1) is a hydrophilic property represented by the following formula (A) based on the ethyleneoxy group (C ₂ H ₄ O) of the organopolysiloxane. The lipophilic balance HLB _EO is 1 to 2.5, and the hydrophilic lipophilic balance HLB _PO represented by the following formula (B) based on the propyleneoxy group (C ₃ H ₆ O) is 1 to 10. It is characterized by.
(A): HLB _EO = [(total amount of ethyleneoxy groups (C ₂ H ₄ O) in organopolysiloxane (% by weight) / 5)]
(B): HLB _PO = [(total amount of propyleneoxy groups (C ₃ H ₆ O) in organopolysiloxane (wt%) / 5)].

In the said invention, it is preferable that the hydrophilic-lipophilic balance HLBEO _{+ PO of} organopolysiloxane represented by the following formula (C) based on ethyleneoxy group and propyleneoxy group is 2-12.
(C): HLB _{EO + PO} = [(total amount of ethyleneoxy group and propyleneoxy group in organopolysiloxane (% by weight)) / 5].

The second antifouling agent composition according to the present invention contains an oxyalkylene group-containing organopolysiloxane represented by the above formula [I], and the organopolysiloxane is an ethyleneoxy group (C ₂ H ₄ O). The hydrophilic / lipophilic balance HLB _EO represented by the above formula (A) based on the formula is 1 to 2.5, and the ethyleneoxy group (C ₂ H ₄ O) and the propyleneoxy group (C ₃ H ₆ O) It is characterized in that the hydrophilic / lipophilic balance HLB _{EO + PO of} the organopolysiloxane represented by the above formula (C) is 2-12.

  In the first and second present inventions (hereinafter, both are collectively referred to as “the present invention”), the oxyalkylene group-containing organopolysiloxane [I] is contained in the composition in an amount of 1 to 50% by weight. It is preferable to contain in the quantity. Moreover, in this invention, it is preferable that (b) copper and / or an inorganic copper compound are further contained, and especially that this copper and / or inorganic copper compound (b) is cuprous oxide or rhodan copper. desirable. In the present invention, such a copper and / or inorganic copper compound (b) is preferably contained in the composition in an amount of 1 to 50% by weight.

  In any of the above aspects, the present invention preferably further contains (c) an organic antifouling agent. In the present invention, the organic antifouling agent (c) is a metal pyrithione salt compound, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, an amine complex of triphenylborane, tetraethylthiuram disulfide, 4,5-dichloro-2- n-octyl-4-isothiazolin-3-one, alkylphenyldichloromaleimide, chloromethyl-n-octyldisulfide, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio- Desirably, one or more selected from the group consisting of 4-tert-butylamino-6-cyclopropyl S-triazine and 2,4,5,6-tetrachloroisophthalonitrile.

  The metal pyrithione salt compound is preferably copper pyrithione and / or zinc pyrithione. The amine complex of triphenylborane is preferably a triphenylborane pyridine complex and / or a triphenylborane alkylamine complex. In the present invention, the organic antifouling agent (c) is preferably contained in the composition in an amount of 1 to 20% by weight.

  The antifouling coating film according to the present invention is characterized by being formed from the antifouling agent composition described above. The antifouling treatment substrate according to the present invention has a surface of a substrate represented by a fishing net, fishing gear, ship or underwater structure in contact with seawater or fresh water, comprising the antifouling agent composition described above. It is characterized by being coated with a coating film, that is, a coating film formed by applying or impregnating the antifouling agent composition and curing.

  The antifouling method for a substrate according to the present invention comprises applying or impregnating the antifouling agent composition described above on the surface of a substrate that contacts seawater or fresh water, and applying the antifouling coating to the surface of the substrate. It is characterized by forming a film.

  According to the present invention, when impregnated and applied to a base material that comes into contact with seawater or fresh water, such as fishing nets, fishing gear, ships or underwater structures, it is excellent against various marine organisms such as hydro-insects and seaweeds. An antifouling agent composition capable of forming an antifouling coating film exhibiting antifouling properties is provided. The antifouling treatment substrate according to the present invention is coated with the antifouling coating film as described above, and can exhibit the antifouling performance. ADVANTAGE OF THE INVENTION According to this invention, the antifouling processing method of a base material which is excellent in the safety to an environment and can obtain the said base material with an antifouling coating film efficiently is provided.

  Hereinafter, the antifouling agent composition, the antifouling treatment substrate, and the antifouling treatment method for the substrate according to the present invention will be specifically described.

<Anti-fouling agent composition>
The antifouling agent composition according to the present invention contains an oxyalkylene group-containing organopolysiloxane represented by the following formula [I]. Moreover, in the preferable aspect, this antifouling agent composition also contains an antifouling agent as described later, that is, copper and / or an inorganic copper compound (b), an organic antifouling agent (c) and the like. .

  Hereinafter, the oxyalkylene group-containing organopolysiloxane [I], the antifouling agent, and the like will be sequentially described.

<Oxyalkylene group-containing organopolysiloxane [I]>
Formula [I]:

In the formula [I], R ⁵ represents an alkyl group, preferably each alkyl group in the following examples having 1 to 5 carbon atoms or further 1 to 3 carbon atoms, or phenyl group, and R ¹ , R ² and R ³ are Each independently an alkyl group, preferably each alkyl group, phenyl group or X: “(CH ₂ ) _p O (C ₂ H ₄ O) _q ( C ₃ H ₆ O) _r R ⁴ [R ⁴ is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, an aryl group, preferably an aryl group having 6 to 15 carbon atoms, an aralkyl group, preferably carbon. An aralkyl group (arylalkyl group) having 7 to 15 or an acyl group, preferably an acyl group having 1 to 15 carbon atoms, p is a number of 0 to 5, q and r are each independently 1 to 50 ]] ”.

  In addition, when several X exists in Formula [I], these X may mutually be same or different. The alkyl group having 1 to 15 carbon atoms may be linear or branched. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, t-butyl group, s-butyl group, n-pentyl group, isopentyl group, t-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, Examples include isooctyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, pentadecyl group and the like. Among these alkyl groups, those having 1 to 5 carbon atoms are preferable, and specifically, a methyl group is desirable.

As an aryl group having 6 to 15 carbon atoms, in addition to an unsubstituted aromatic group, an aromatic group in which part of the hydrogen atom may be substituted with an alkyl group having about 1 to 3 carbon atoms. Specifically, for example, phenyl group, tolyl group (CH ₃ C ₆ H ₄ —), xylyl group (CH ₃ ) ₂ C ₆ H ₃ —), biphenylyl group (C ₆ H ₅ C ₆ H) ₄ -), a naphthyl group (C ₁₀ H ₇ -), anthryl (C ₁₄ H ₉ -), a phenanthryl group (C ₁₄ H ₉ -), and the like. Among these aryl groups, those having 6 to 10 carbon atoms are preferable, and specifically, phenyl is desirable.

Specific examples of the aralkyl group (arylalkyl group) having 7 to 15 carbon atoms include a benzyl group (C ₆ H ₅ CH ₂ —), a phenethyl group (C ₆ H ₅ CH ₂ CH ₂ —) and the like. Is mentioned. Or the acyl group having 1 to 15 carbon atoms, and specific examples thereof include a formyl group (HCO-), acetyl group (CH ₃ CO-), propionyl group (C ₂ H ₅ CO-), butyryl group ( C ₃ H ₇ CO-), aliphatic acyl groups such as valeryl (C ₄ H ₉ CO-); benzoyl group (C ₆ H ₅ CO-), toluoyl group (CH ₃ -C ₆ H ₄ -CO -), salicyloyl group _{(HO-C 6 H 4 -CO-} ), cinnamoyl group _{(C 6 H 5 -CH = CHCO-} ), naphthoyl group (C ₁₀ H ₇ CO-), phthaloyl group (CO-C ₆ H _And aromatic acyl groups such as _4- CO-). Among these acyl groups, the acyl group having about 7 to 13 carbon atoms is preferable.

Of these R ⁴ , a methyl group is preferred. Moreover, in said formula [I], m is 1-1000, Preferably, the number of 10-200 is shown, n shows 0-50, Preferably, the number of 2-20 is shown. However, when n is 0, R ¹ and / or R ² is the above X. In the present invention, each component unit-[Si (R ⁵ ) ₂ O]-(dimethylsilyleneoxy group) present in the formula [I] and-[SiR ³ (R ⁵ ) O]- The bonding order is arbitrary. For example, n-[SiR ³ (R ⁵ ) O] -units are present at an arbitrary position between arranged m-[Si (R ⁵ ) ₂ O] -units. They may be present in an arbitrary number in the range of 0 to 50 so that the total number is n.

In the present invention, the organopolysiloxane [I] has a hydrophilic / lipophilic balance HLB _EO represented by the following formula (A) based on an ethyleneoxy group (C ₂ H ₄ O) of 1 to 2.5, preferably Is 1.5 to 2.5 and the hydrophilic / lipophilic balance HLB _PO represented by the following formula (B) based on a propyleneoxy group (C ₃ H ₆ O) is 1 to 10, preferably 2 to 5.
(A): HLB _EO = [(total amount of ethyleneoxy groups (C ₂ H ₄ O) in organopolysiloxane (% by weight) / 5)]
(B): HLB _PO = [(total amount of propyleneoxy groups (C ₃ H ₆ O) in organopolysiloxane (% by weight) / 5)]

Such an antifouling agent composition containing an organopolysiloxane [I] having HLB _EO and HLB _PO is excellent in antifouling properties against various marine organisms such as hydroworms, chrysanthemum bugs, Aosa, Aonori, Serpura and oysters. A coating film can be formed. Even if the HLB _EO is in the above range (1 to 2.5), the antifouling property tends to decrease if the HLB _PO is out of the above range (1 to 10).

Moreover, the antifouling agent composition according to the present invention has an organopolysiloxane hydrophilic / lipophilic balance HLB _{EO + PO} of 2 to 12 represented by the following formula (C) based on an ethyleneoxy group and a propyleneoxy group. More preferably, it is desirably 3.5 to 7.5.
(C): HLB _{EO + PO} = [(total amount of ethyleneoxy group and propyleneoxy group in organopolysiloxane (% by weight)) / 5]

When the organopolysiloxanes HLB _EO and HLB _PO are in the above range, and more preferably, HLB _{EO + PO} is also in the above range, it is more excellent against various marine organisms such as hydroenteric and seaweeds. An antifouling agent composition capable of forming an antifouling coating film exhibiting antifouling properties is obtained.

In the antifouling agent composition according to the present invention, the organopolysiloxane [I] is a hydrophilic / lipophilic balance HLB _EO represented by the formula (A) based on an ethyleneoxy group (C ₂ H ₄ O). 1 to 2.5, preferably 1.5 to 2.5, and the hydrophilic / lipophilic balance HLB _EO of the organopolysiloxane represented by the above formula (C) based on ethyleneoxy group and propyleneoxy group _{+ PO} may be 2 to 12, preferably 3.5 to 7.5.

  In the present invention, the number average molecular weight (Mn) of the oxyalkylene group-containing organopolysiloxane [I] is usually 800 to 50000, preferably 1000 to 10,000. When the oxyalkylene group-containing organopolysiloxane [I] having such a number average molecular weight is used, a coating film obtained by coating and curing the resulting antifouling agent composition (underwater antifouling agent composition) is applied to the coating film surface. The polysiloxane [I] is gradually transferred, and with the transition of the polysiloxane [I], the antifouling agent in the coating also gradually moves to the coating surface. Excellent antifouling property over the whole area.

<Anti-fouling agent>
Examples of the antifouling agent include (b) copper and / or an inorganic copper compound, and (c) an organic antifouling agent. Among the above “copper and / or inorganic copper compound” (b), the inorganic copper compound (also simply referred to as copper compound) may be any of inorganic copper compounds, such as cuprous oxide, thiocyanate, and the like. Examples thereof include copper chloride (cuprous thiocyanate, rhodan copper), basic copper sulfate, basic copper acetate, basic copper carbonate, cupric hydroxide and the like. Preferably, cuprous oxide and rhodan copper are used. Such a copper compound is particularly preferably used for a colored paint other than a white paint.

  Such inorganic copper compounds can be used alone or in combination of two or more in place of copper or together with copper. Such copper and / or inorganic copper compound (b) is based on 100 parts by weight of oxyalkylene group-containing organopolysiloxane [I] (coating-forming solid content) in the antifouling agent composition of the present invention. Usually, it is desirable to be contained in an amount of 50 to 5000 parts by weight, preferably 200 to 2000 parts by weight. Further, in 100% by weight of the antifouling agent composition (coating composition), the copper and / or the inorganic copper compound (b) is generally in an amount of 1 to 50% by weight, preferably 5 to 40% by weight. It is desirable that it be included.

  When the content of the copper and / or inorganic copper compound (b) is in the above range, the resulting antifouling coating film tends to be excellent in antifouling properties. Examples of the organic antifouling agent (c) include metal pyrithione salt compounds, carbamate compounds, amine complexes of triphenylborane, tetramethylthiuram sulfide, tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl- 4-isothiazolin-3-one, alkylphenyldichloromaleimide, chloromethyl-n-octyldisulfide, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert- Examples thereof include butylamino-6-cyclopropyl S triazine, 2,4,5,6-tetrachloroisophthalonitrile and the like.

Among these, as the metal pyrithione salt-based compound, more specifically, metal-pyrithiones represented by the following formula [II] [wherein R ^{1 to} R ⁴ are each independently hydrogen, an alkyl group, an alkoxy group, Represents a halogenated alkyl group, M represents a metal such as Cu, Zn, Na, Mg, Ca, Ba, Pb, Fe, Al, and n represents a valence]:

Is mentioned. Of these, copper pyrithione and zinc pyrithione are preferred. Examples of the carbamate compounds include bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate, and bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate is preferably used. .

  Specific examples of the amine complex of triphenylborane include a triphenylborane pyridine complex and a triphenylborane alkylamine complex (the carbon number of the alkyl group: usually 3 to 30). A phenylborane pyridine complex and the above triphenylborane alkylamine complex are preferred. Among these organic antifouling agents (c), metal pyrithione salt compounds, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, amine complexes of triphenylborane, tetraethylthiuram disulfide, 4,5-dichloro-2-n- Octyl-4-isothiazolin-3-one, alkylphenyldichloromaleimide (carbon number of alkyl group: usually 1 to 5), chloromethyl-n-octyldisulfide, N, N-dimethyldichlorophenylurea, 2,4, 6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropyl S-triazine, and 2,4,5,6-tetrachloroisophthalonitrile are preferred.

  These organic antifouling agents (c) are used alone or in combination of two or more. In the antifouling agent composition containing such an organic antifouling agent (c), the above organic antifouling agent is used together with the copper and / or inorganic copper compound (b) or in place of the copper and / or inorganic copper compound (b). It is desirable that the soiling agent (c) is usually contained in an amount of 1 to 20% by weight, preferably 2 to 15% by weight. The organic antifouling agent (c) is usually 10 to 10 parts by weight based on 100 parts by weight of the oxyalkylene group-containing organopolysiloxane [I] (coating-forming solid content) in the antifouling agent composition of the present invention. It is desirable that it is contained in an amount of 2000 parts by weight, preferably 100 to 1000 parts by weight. In such an amount, when the organic antifouling agent (c) is contained in the antifouling agent composition together with the copper and / or inorganic copper compound (b), the resulting antifouling coating film is used in a wide range of ships. There is a tendency that even better antifouling performance against attached organisms can be demonstrated over a long period of time.

<Other ingredients>
In the antifouling composition according to the present invention, in addition to the oxyalkylene group-containing organopolysiloxane [I] and the above antifouling agent, a color developing agent may be blended within a range that does not impair the object of the present invention. it can. Examples of the color developing agent include an acrylic resin, a vinyl resin, a modified vinyl resin, a styrene / butadiene copolymer resin, and a polyester resin, and an acrylic resin is preferably used. These resins for color extender have the effect of giving strength to the coating film of the antifouling agent composition (underwater antifouling agent composition) and suppressing the dissolution of the antifouling agent. Therefore, these resins are effective when the antifouling agent coating film is allowed to exhibit antifouling properties over a long period of time.

  In addition, in the antifouling agent composition according to the present invention, at least one component selected from polyolefins, paraffins and rosins which are liquid or solid and all have water repellency is impaired in the object of the present invention. It can mix | blend in the range which is not. Specific examples of the liquid or solid water-repellent polyolefin include polyethylene, polypropylene, and polybutene. Among these, polybutene having a number average molecular weight of 200 to 1000 is preferable. Such polybutenes are commercially available from Nippon Oil Co., Ltd. under trade names such as LV-5, LV-10, LV-25, LV-50, and LV-100. Such polyolefins can be used alone or in combination of two or more.

  Specific examples of the water-repellent paraffins include liquid paraffin, paraffin wax, and chlorinated paraffin. These paraffins can be used alone or in combination of two or more. When at least one component of polyolefins, paraffins and rosin as described above is blended in the antifouling agent composition according to the present invention, it comprises only the antifouling agent and the oxyalkylene group-containing organopolysiloxane [I]. The excellent antifouling performance exhibited by the coating film comprising the antifouling agent composition can be maintained, and the cost of the antifouling agent composition can be reduced.

  Moreover, you may mix | blend the extender pigment, coloring pigment, sagging stop agent, solvent, etc. which are mix | blended with a general antifouling paint as needed in the antifouling agent composition concerning this invention.

Preparation of antifouling agent composition The antifouling agent composition according to the present invention can be prepared according to a conventional method. For example, the antifouling agent composition according to the present invention includes an oxyalkylene group-containing organopolysiloxane [I], if necessary, an antifouling agent, an organic solvent, an acrylic resin, a vinyl resin, a modified vinyl resin, and a styrene / butadiene copolymer. Resin, polyester resin, polyolefin having liquid or solid water repellency (eg, polybutene, polyisobutylene), paraffins which may be chlorinated, wax, rosin, extender pigment, color pigment, anti-sagging agent, etc. It can be obtained by mixing and dispersing using a ball mill or the like.

Fishing gear, antifouling antifouling composition according to the fishing nets present invention, as described above, the Tsuruashi such as barnacles, was superior to Hydrozoa and the like is a kind of shellfish and coelenterates mussel etc. Therefore, it is suitable for antifouling treatment for fishing gear such as fishing lines and fishing nets.

  The antifouling treatment of fishing gear and fishing net is performed, for example, by immersing the fishing gear or fishing net in the antifouling agent composition according to the present invention, or by applying the antifouling agent composition to the fishing gear or fishing net. When such an antifouling treatment is performed, the antifouling agent composition can be impregnated into the fishing gear and the fishing net and attached to the surface of the fishing gear and the fishing net.

Hull and underwater structure Antifouling agent composition according to the present invention is a coating film exhibiting excellent antifouling properties against barnacles such as barnacles, shellfish such as mussels, and coelenterates such as hydroworms Therefore, it can be expected to be used for antifouling treatment for hulls and underwater structures.
The antifouling treatment of the hull and the underwater structure is performed by applying the antifouling composition according to the present invention to the surface of the hull or the underwater structure.

[Effect of the invention]
The antifouling composition according to the present invention contains an oxyalkylene group-containing organopolysiloxane in which ethyleneoxy groups and propyleneoxy groups are present in a specific ratio. Unlike the invention described in Japanese Patent Publication No. 6-104793, the present invention has a hydrophilic / lipophilic balance (HLB _EO ) based on ethyleneoxy groups of less than 3 and a low value of 1 to 2.5. If the antifouling agent composition according to the present invention is used, a coating film exhibiting excellent antifouling properties against aquatic organisms such as algae, barnacles, shellfish (eg mussels) and coelenterate (eg hydroworms) The substrate can be formed on the surface of a fishing gear, fishing net, hull, underwater structure or the like. The antifouling agent composition according to the present invention having the effects as described above is suitable for antifouling treatment of fishing gear and fishing nets, and can be expected to be used for antifouling treatment of hulls and underwater structures.

  According to the antifouling treatment method for a substrate according to the present invention, the surface of the substrate in contact with seawater or fresh water, for example, the surface of a fishing gear, a fishing net, an underwater structure, or the like is impregnated and applied. Can be formed efficiently and economically without causing environmental pollution, and aquatic organisms such as algae, barnacles, shellfish represented by mussels, and coelenterate represented by hydrozoa Can be effectively prevented.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by this Example. The oxyalkylene group-containing organopolysiloxanes S1 to S4 used in the following Examples and Comparative Examples have R ⁵ , R ¹ , R ² , R ³ , m, n values and number average molecular weights in the formula [I], respectively. It is as shown in Table 1 below. The HLB _EO and HLB _PO are as follows. HLB _EO , HLB _{PO, and the} like were determined by proton NMR and quantifying Si, oxyethylene (EO), and oxypropylene (PO).
S1: HLB _EO = 2.3, HLB _PO = 2.4
S2: HLB _EO = 1.8, HLB _PO = 4.0
S3: HLB _EO = 4.5, HLB _PO = 0
S4: HLB _EO = 2.4, HLB _PO = 0

[Examples 1-4, Comparative Examples 1-4]
According to a conventional method, antifouling agent compositions shown in Table 2 were prepared.

The antifouling compositions shown in Table 2 above were each dip-coated on a polyethylene knotless net (7/400 denier / 50) and air-dried (the dry coating amount was 12 parts per 100 parts by weight of the net weight). (14 parts by weight), and immersed in 1 m below the sea surface in Sukumo Bay, Kochi Prefecture for 6 months from June 1 to December 1, 1998, and investigated the state of attachment of marine organisms to the net.

The results are also shown in Table 2.
In addition, the adhesion state of marine organisms was investigated also about the net | network which is not impregnated and apply | coated the antifouling agent composition (reference example 1). The note numbers in Table 2 are as follows.
* 1, 2: Made by Enomoto Kasei Co., Ltd., precipitation inhibitor.
* 3: Acrylic resin (methyl methacrylate / butyl acrylate copolymer, Tg: −10 degrees, solid content 50%).
A: No organism attached.
B: There is a slight amount of organisms attached.
C: There is considerable adhesion of organisms.
D: Significant adhesion of organisms.

  As can be seen from Table 2, the antifouling composition of the present invention exhibited very excellent antifouling properties against organisms in the sea.

Claims (15)

(a) Formula [I] below:
[In the formula [I], R ⁵ represents an alkyl group or a phenyl group, and R ¹ , R ² and R ³ each independently represents an alkyl group, a phenyl group or X: “(CH ₂ ) _p O (C ₂ H ₄ O) _q (C ₃ H ₆ O) _r R ⁴ (R ⁴ represents a hydrogen atom or an alkyl group, aryl group, aralkyl group or acyl group each having 1 to 15 carbon atoms, and p is 0 to 5) Q and r each independently represents a number of 1 to 50.)], and at least one of R ¹ , R ² and R ³ is X. m shows the number of 1-1000, n shows the number of 0-50. However, when n is 0, R ₁ and / or R ₂ is the above X. An oxyalkylene group-containing organopolysiloxane represented by the formula:
(B) containing copper and / or an inorganic copper compound,
The organopolysiloxane has a hydrophilic / lipophilic balance HLB _EO represented by the following formula (A) based on the ethyleneoxy group (C ₂ H ₄ O) of the organopolysiloxane of 1 to 2.5, and propylene An antifouling agent composition having a hydrophilic / lipophilic balance HLB _PO represented by the following formula (B) based on an oxy group (C ₃ H ₆ O) of 1 to 10;
(A): HLB _EO = [(total amount of ethyleneoxy groups (C ₂ H ₄ O) in organopolysiloxane (% by weight) / 5)]
(B): HLB _PO = [(total amount of propyleneoxy groups (C ₃ H ₆ O) in organopolysiloxane (wt%) / 5)]. The antifouling agent composition according to claim 1, wherein the hydrophilic / lipophilic balance HLB _{EO + PO of} the organopolysiloxane represented by the following formula (C) based on an ethyleneoxy group and a propyleneoxy group is 2 to 12;
(C): HLB _{EO + PO} = [(total amount of ethyleneoxy group and propyleneoxy group in organopolysiloxane (% by weight)) / 5]. (a) Formula [I] below:
[In the formula [I], R ⁵ represents an alkyl group or a phenyl group, and R ¹ , R ² and R ³ each independently represents an alkyl group, a phenyl group or X: “(CH ₂ ) _p O (C ₂ H ₄ O) _q (C ₃ H ₆ O) _r R ⁴ (R ⁴ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, an aryl group, an aralkyl group or an acyl group, and R ¹ , R ² and And at least one of R ³ is X. p represents a number of 0 to 5, q and r each independently represents a number of 1 to 50), and m represents a number of 1 to 1000. N represents a number from 0 to 50. However, when n is 0, R ₁ and / or R ₂ is the above X. An oxyalkylene group-containing organopolysiloxane represented by the formula:
(B) containing copper and / or an inorganic copper compound,
The organopolysiloxane has a hydrophilic / lipophilic balance HLB _EO represented by the following formula (A) based on an ethyleneoxy group (C ₂ H ₄ O) of 1 to 2.5, and an ethyleneoxy group (C ₂ An antifouling agent composition represented by the following formula (C) based on H ₄ O) and a propyleneoxy group (C ₃ H ₆ O), wherein the hydrophilic / lipophilic balance HLB _{EO + PO of} the organopolysiloxane is 2-12. object:
(A): HLB _EO = [(total amount of ethyleneoxy groups (C ₂ H ₄ O) in organopolysiloxane (% by weight) / 5)]
(C): HLB _{EO + PO} = [(total amount of ethyleneoxy group and propyleneoxy group in organopolysiloxane (% by weight)) / 5].   The antifouling agent composition according to any one of claims 1 to 3, wherein the oxyalkylene group-containing organopolysiloxane [I] is contained in the composition in an amount of 1 to 50% by weight.   The antifouling agent composition according to any one of claims 1 to 4, wherein the copper and / or inorganic copper compound (b) is cuprous oxide or rhodan copper.   The antifouling agent composition according to any one of claims 1 to 5, wherein the copper and / or inorganic copper compound (b) is contained in the composition in an amount of 1 to 50% by weight.   The antifouling composition according to any one of claims 1 to 6, further comprising (c) an organic antifouling agent.   The organic antifouling agent (c) is a metal pyrithione salt compound, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, an amine complex of triphenylborane, tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl-4 -Isothiazoline-3-one, alkylphenyldichloromaleimide, chloromethyl-n-octyldisulfide, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butyl The antifouling agent composition according to claim 7, wherein the antifouling agent composition is one or more selected from the group consisting of amino-6-cyclopropyl S-triazine and 2,4,5,6-tetrachloroisophthalonitrile.   The antifouling agent composition according to claim 8, wherein the metal pyrithione salt compound is copper pyrithione and / or zinc pyrithione.   The antifouling composition according to claim 8, wherein the amine complex of triphenylborane is a triphenylborane pyridine complex and / or a triphenylborane alkylamine complex.   The antifouling agent composition according to any one of claims 7 to 10, wherein the organic antifouling agent (c) is contained in the composition in an amount of 1 to 20% by weight.   An antifouling coating film formed from the antifouling agent composition according to any one of claims 1 to 11.   An antifouling treatment substrate, wherein the surface of the substrate in contact with seawater or fresh water is coated with a film comprising the antifouling agent composition according to any one of claims 1 to 11.   The antifouling treatment substrate according to claim 13, wherein the substrate is a fishing net, fishing gear, a ship, or an underwater structure.   An antifouling coating composition is formed by applying or impregnating the antifouling agent composition according to any one of claims 1 to 11 onto the surface of a substrate that contacts seawater or fresh water. Antifouling method.