JP4410286B2 - Antifouling paint composition - Google Patents

Description

  The present invention relates to fishing nets for aquaculture or stationary nets and fishing net equipment used therefor, such as floats and ropes (hereinafter also referred to as fish nets), and underwater such as cooling water conduits for power plants. Antifouling paint composition for preventing long-term adhesion of chickenpox fouling organisms to structures, etc., antifouling coating film formed from the antifouling paint composition agent, and fishing net coated with the antifouling paint composition And an antifouling treatment method for applying the antifouling coating composition to fishing nets or underwater structures.

  Fishing nets, fishing net tools, underwater structures, etc. are installed in the water for a long time (eg in the sea), so when used without treatment with antifouling paint for fishing nets, seaweeds, barnacles, cell plastics, bryozoans, mollusks Various aquatic fouling organisms such as sea urchins may adhere, the flow of seawater will be worse, a large amount of cultured fish will die due to lack of oxygen, infectious diseases will occur and shipping may be damaged, and it may be seriously damaged.

  Conventionally, antifouling paint compositions for fishing nets using organotin compounds have been widely used to prevent the adhesion of these waterpox fouling organisms, but they cannot be used because of environmental considerations.

  Therefore, various researches and proposals have been made as antifouling paint compositions for fishing nets to replace organic tin compounds, and inorganic compounds and organic compounds are used as antifouling agents, and these are blended with natural or synthetic resin spreading resins. Antifouling paint compositions for fishing nets have been used. However, these have problems such as poor physical properties of the coating film and a short antifouling period. In order to solve these problems, antifouling paint compositions for fishing nets in which a specific polyether-modified silicone oil is blended with a spreading resin as a drug elution control agent have been proposed (Patent Documents 1 to 4, 8).

  These proposals improved the coating properties and improved the antifouling performance in many sea areas. However, the activity of adherent organisms such as barnacles and cell plastics is strong, and the activity of coelenterates such as hydroworms. The effect was not enough in the strong waters.

  In addition, an underwater antifouling composition comprising bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate and a specific polyether-modified silicone oil was proposed as an excellent antifouling agent for coelenterates such as hydroworms ( Patent Document 5). In addition, an underwater antifouling composition containing cuprous oxide and a specific polyether-modified silicone oil has been proposed as an excellent antifouling agent for animals such as barnacles and cell plastics and intestinal animals such as hydroworms. (Patent Document 6). Furthermore, as an antifouling agent excellent for coelenterate, barnacles, and seaweed, it contains both a specific amount of ethyleneoxy groups and a specific amount of propyleneoxy groups, and oxyalkylene group-containing organopolysiloxane (polyether-modified silicone). A blended underwater antifouling agent has been proposed (Patent Document 7).

  However, these inventions show that bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate has an excellent antifouling effect on coelenterates such as hydroworms, and cuprous oxide has an excellent antifouling effect on animals such as barnacles and cell plastics. However, in the case of the silicone oil having the molecular structure used in these inventions, the use of polyether-modified silicone oil improves the initial effect, but the drug elutes early and has a long-term antifouling effect. I couldn't maintain it.

Therefore, fishing nets that have excellent coating properties and excellent workability when applying fishing nets, and can exhibit antifouling effects for a long period of time as designed in marine areas where animals such as barnacles and cell plastics and coelenterates such as hydroworms are highly active The development of antifouling agents was eagerly desired.
JP-A-3-20370 JP-A-4-142373 JP-A-5-263022 JP-A-5-320538 Japanese Patent Laid-Open No. 9-176576 Japanese Patent Laid-Open No. 9-176777 Japanese Patent Laid-Open No. 2001-19848 JP 2002-265849 A

  This invention is made | formed in view of such a situation, and provides the antifouling coating composition which can maintain an antifouling effect for a long period of time.

Means for Solving the Problems and Effects of the Invention

  The antifouling coating composition of the present invention is [A] 1 of modified silicone oil (a-1) in which a part of methyl groups in the side chain of dimethyl silicone oil is substituted with one or more organic groups. Elution control agent containing seeds or two or more, [B] spreading resin, [C] cuprous oxide, copper powder, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, bisdimethyl It contains an antifouling agent containing one or more selected from the group consisting of dithiocarbamoyl zinc ethylenebisdithiocarbamate and pyridine triphenylboron, and the modified silicone oil (a-1) contains the spreading resin [B 0.5 to 50 parts by weight per 100 parts by weight, and the antifouling agent [C] is contained in 1 to 200 parts by weight per 100 parts by weight of the spreading resin [B], and the organic group , Aralkyl groups and number of carbon atoms is characterized in that it comprises at least one comprises and polyether groups of 6 or more alkyl groups optionally.

  As a result of intensive studies, the present inventors have found that an antifouling paint composition containing an elution control agent, a spreading resin, and an antifouling agent can be used by using the modified silicone oil having the above structure as an elution control agent. In addition, it has been found that an antifouling coating composition capable of exhibiting an excellent antifouling effect for a long period of time in a sea area where the activity of animals such as barnacles and cell plastics and coelenterate such as hydroworms is strong is obtained. Completed.

  The action of the antifouling coating composition of the present invention to exert a long-term antifouling effect is not necessarily clear, but an aralkyl group or an alkyl group having 6 or more carbon atoms is present in the side chain of the modified silicone oil. Is considered to be related.

In addition, according to the present invention, even when the HLB is less than 2, the antifouling agent is appropriately eluted to exert the antifouling effect. In the prior art, when the hydrophilic / lipophilic balance (HLB) of the modified silicone oil is less than 2, the dissolution rate of the antifouling agent becomes very small and the antifouling effect is not exhibited. It is a surprising result that the antifouling effect is exhibited even when is less than 2.
Hereinafter, various embodiments of the present invention will be exemplified.

The organic group is an aralkyl group, an alkyl group having 6 or more carbon atoms, both an aralkyl group and an alkyl group having 6 or more carbon atoms, or an aralkyl group and an alkyl group having 6 or more carbon atoms and a polyether group. It may consist of all of
The hydrophilic / lipophilic balance (HLB) of the modified silicone oil (a-1) may be 0 or more and less than 2.
The elution control agent [A] further includes one or more of polyolefins (a-2), and the polyolefins (a-2) are added to 100 parts by weight of the modified silicone oil (a-1). It may be included in an amount of 1 to 1000 parts by weight.
The polyolefins (a-2) may be one or more selected from the group of polybutenes and ethylene-α-olefins.
The spreading resin [B] may be a (meth) acrylic acid ester copolymer having a glass transition temperature of −40 to 40 ° C.
Moreover, this invention also provides the antifouling processing method which forms an antifouling coating film on the surface of a coating-film formation object using the antifouling coating composition as described above.
The present invention also provides an antifouling coating film formed using the antifouling coating composition described above.
The present invention also provides a fishing net, a fishing net tool, and an underwater structure having the antifouling coating film described above on the surface.
The various embodiments and the like exemplified here can be combined with each other.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The contents shown in the drawings and the following description are examples, and the scope of the present invention is not limited to those shown in the drawings and the following description.

An antifouling coating composition according to an embodiment of the present invention includes: [A] a modified silicone oil in which a part of methyl groups in the side chain of dimethyl silicone oil is substituted with one or more organic groups (a- 1) an elution control agent comprising one or more types, [B] a spreading resin, [C] cuprous oxide, copper powder, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide An antifouling agent containing one or more selected from the group consisting of zinc, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, and pyridine triphenylboron, and the modified silicone oil (a-1) 0.5 to 50 parts by weight with respect to 100 parts by weight of the resin [B], and the antifouling agent [C] is included with 1 to 200 parts by weight with respect to 100 parts by weight of the resin [B]. The organic groups, aralkyl groups and number of carbon atoms is characterized in that it comprises a and polyether groups contains at least one of the 6 or more alkyl groups optionally.
Hereinafter, each component will be described.

1. Elution control agent [A]
The elution control agent [A] of the present invention contains one or more modified silicone oils (a-1). In addition, the elution control agent [A] may contain another component such as one or more polyolefins (a-2).
Hereinafter, the modified silicone oil (a-1) and the polyolefins (a-2) will be described.

1-1. Modified silicone oil (a-1)
In the modified silicone oil (a-1), part of the methyl group in the side chain of the dimethyl silicone oil is substituted with one or more organic groups, and the organic group has an aralkyl group and a carbon atom number. It contains at least one of 6 or more alkyl groups (hereinafter also referred to as “long-chain alkyl groups”) and optionally contains a polyether group, and is represented by the following general formula (I).

［ 式中、ｌは、１以上の整数であり、ｍ，ｎ，ｏは全て０以上の整数であり、且つ（ｍ＋ｎ）は１以上の整数である。また、Ｒ¹はアラルキル基、Ｒ²は長鎖アルキル基、Ｒ³はポリエーテル基である。〕

[Wherein, l is an integer of 1 or more, m, n, o are all integers of 0 or more, and (m + n) is an integer of 1 or more. R ¹ is an aralkyl group, R ² is a long-chain alkyl group, and R ³ is a polyether group. ]

1-1-1. Repeating unit In general formula (I), a repeating unit in which the side chain methyl group is unsubstituted is called an unsubstituted repeating unit, and one of the side chain methyl groups is substituted with an aralkyl group, a long chain alkyl group or a polyether group. These repeating units are referred to as an aralkyl group-substituted repeating unit, a long-chain alkyl group-substituted repeating unit, and a polyether group-substituted repeating unit, respectively. In the general formula (I), the order in which the four types of repeating units are arranged is not particularly limited, and may be random, alternating, or continuous.
Hereinafter, each repeating unit will be described.

(1) Unsubstituted repeating unit In general formula (I), l represents the number of unsubstituted repeating units and is an integer of 1 or more.
It is an integer of ~ 100. Specifically, l is, for example, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100. l may be within a range between any two of the numerical values exemplified here.

(2) Aralkyl group-substituted repeating unit m in the general formula (I) represents the number of aralkyl group-substituted repeating units and is an integer of 0 or more, for example, an integer of 0 to 100. Specifically, m is, for example, 0, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100. m may be within a range between any two of the numerical values exemplified here.

  An aralkyl group is a group in which one hydrogen atom of an alkyl group is substituted with an aryl group. The alkyl group in the aralkyl group is, for example, one having 1 to 4 carbon atoms (linear or branched), and specifically, for example, a methyl group, an ethyl group, or a propyl group. The aryl group in the aralkyl group is, for example, a phenyl group.

  Examples of the aralkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 2-methyl-2-phenylethyl group and the like, and 2-methyl-2-phenylethyl group is preferable.

(3) Long-chain alkyl group-substituted repeating unit n in the general formula (I) indicates the number of long-chain alkyl group-substituted repeating units, and is an integer of 0 or more, for example, an integer of 0 to 100. Specifically, n is, for example, 0, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100. n may be within a range between any two of the numerical values exemplified here.

  A long-chain alkyl group is an alkyl group having 6 or more carbon atoms. The number of carbon atoms of the long-chain alkyl group is, for example, 6 to 18, and specifically, for example, 6, 8, 10, 12, 14, 16, 18. The number of carbon atoms may be within a range between any two of the numerical values exemplified here. The long chain alkyl group may be linear or branched.

  Examples of the long chain alkyl group include a hexyl group, an octyl group, a 2-ethylhexyl group, a lauryl group, and a stearyl group, and preferably an alkyl having 8 or more carbon atoms such as an octyl group, a 2-ethylhexyl group, and a lauryl group. It is a group.

  Since the modified silicone oil (a-1) has at least one of an aralkyl group-substituted repeating unit and a long-chain alkyl group-substituted repeating unit, (m + n) is an integer of 1 or more. (M + n) is, for example, 1 to 200, specifically, for example, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160. , 170, 180, 190, 200. (M + n) may be within a range between any two of the numerical values exemplified here.

(4) Polyether group-substituted repeating unit “o” in the general formula (I) represents the number of polyether group-substituted repeating units, and is an integer of 0 or more, for example, an integer of 0 to 100. Specifically, o is, for example, 0, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100. o may be within a range between any two of the numerical values exemplified here.

（式中、ｐは１以上の整数、ｑは０以上の整数である。また、Ｒ⁴は炭素数１〜４のアルキレン基、Ｒ⁵は水素原子又は炭素数１〜３のアルキル基、ｐは１以上の整数、ｑは０以上の整数である）で表される。 The polyether group is, for example, the general formula (II):

(In the formula, p is an integer of 1 or more, q is an integer of 0 or more. R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, p Is an integer of 1 or more, and q is an integer of 0 or more.

R ⁴ is an alkylene group having 1 to 4 carbon atoms, and specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and an ethylene group and a propylene group are preferable.
R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, and a propyl group, and a hydrogen atom or a methyl group is preferable.

p is an integer of 1 or more, for example, an integer of 1 to 50. Specifically, p is, for example, 1, 10, 20, 30, 40, 50. p may be within a range between any two of the numerical values exemplified here.
q is an integer of 0 or more, for example, an integer of 0 to 10. Specifically, q is, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. q may be within a range between any two of the numerical values exemplified here.

1-1-2. Specific Example of Modified Silicone Oil (a-1) Next, a specific example of the modified silicone oil (a-1) will be described. Specifically, the organic group of the modified silicone oil (a-1) is, for example, an aralkyl group, a long-chain alkyl group, both an aralkyl group and a long-chain alkyl group, or an aralkyl group, a long-chain alkyl group, and a polyether group. Of all.

  When the organic group is an aralkyl group (in the general formula (I), m is 1 or more and n and o are 0), the modified silicone oil (a-1) is referred to as an aralkyl-modified silicone oil.

  When the organic group is a long chain alkyl group (in the general formula (I), n is 1 or more and m and o are 0), the modified silicone oil (a-1) is a long chain alkyl modified silicone. Called oil.

  When the organic group is both an aralkyl group and a long-chain alkyl group (in the general formula (I), m and n are 1 or more and o is 0), the modified silicone oil (a-1) is It is called aralkyl-long chain alkyl modified silicone oil.

When the organic group is all of an aralkyl group, a long-chain alkyl group, and a polyether group (in the general formula (I), m, n, and o are 1 or more), the modified silicone oil (a-1) is It is called aralkyl-long chain alkyl-polyether modified silicone oil.
Hereinafter, each case will be described.

(1) Aralkyl-modified silicone oil The aralkyl-modified silicone oil has, for example, a weight average molecular weight of 7000 to 30000, a viscosity of 450 to 1800 (mm ² / s), and a specific gravity of 0.97 to 1 at 25 ° C. 07, those having a refractive index of 1.43 to 1.53 and having an aralkyl group in the side chain. Specifically, for example, KF-410 (HLB = 0, weight average molecular weight) of Shin-Etsu Chemical Co., Ltd. = 15016, viscosity at 25 ° C. = 900 (mm ² / s), specific gravity = 1.02, refractive index = 1.480.

Specifically, the weight average molecular weight is, for example, 7000, 10000, 12000, 14000, 16000, 18000, 20000, 25000, 30000. This molecular weight may be within a range between any two of the numerical values exemplified herein. In the present invention, the weight average molecular weight means a value measured under the following conditions.
(Measurement method, equipment, conditions, etc.)
Measurement method: GPC method calibration curve: using standard polystyrene Creation device: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZ4000 (1), TSKgel SuperHZ2000 (1)
Mobile phase: THF
Detector: RI
Temperature: 40 ° C
Flow rate: 0.35 ml / min
Injection volume: 3 μl

Specifically, the viscosity is, for example, 450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1500, 1800 (mm ² / s). This viscosity may be within a range between any two of the numerical values exemplified herein.
Specifically, the specific gravity is, for example, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1 .07. This specific gravity may be within a range between any two of the numerical values exemplified here.
Specifically, the refractive index is 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, for example. 1.53. This refractive index may be within a range between any two of the numerical values exemplified here.

(2) Long-chain alkyl-modified silicone oil The long-chain alkyl-modified silicone oil has, for example, a weight average molecular weight of 7000 to 30000, a viscosity of 10 to 1000 (mm ² / s), and a specific gravity of 0. 88-0.98, a refractive index of 1.38-1.48 and having a long chain alkyl group in the side chain, specifically, for example, KF-414 (HLB) manufactured by Shin-Etsu Chemical Co., Ltd. = 0, weight average molecular weight = 15463, viscosity at 25 ° C = 100 (mm ² / s), specific gravity = 0.93, refractive index = 1.428). Long chain alkyl-modified silicone oils are KF-412, KF-413, KF-415, KF-4003, KF-4701, KF-4917, KF-7235B, X-22-7232 from Shin-Etsu Chemical Co., Ltd. HLB = 0) or the like.

Specifically, the weight average molecular weight is, for example, 7000, 10000, 12000, 14000, 16000, 18000, 20000, 25000, 30000. This molecular weight may be within a range between any two of the numerical values exemplified herein.
Specifically, the viscosity is, for example, 10, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 500, 1000 (mm ² / s). This viscosity may be within a range between any two of the numerical values exemplified herein.
Specifically, the specific gravity is, for example, 0.88, 0.89, 0.90, 0.91, 0.92.0.93, 0.94, 0.95, 0.96, 0.97, 0. .98. This specific gravity may be within a range between any two of the numerical values exemplified here.
Specifically, the refractive index is, for example, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48. This refractive index may be within a range between any two of the numerical values exemplified here.

(3) Aralkyl-long-chain alkyl-modified silicone oil As the aralkyl-long-chain alkyl-modified silicone oil, for example, the weight average molecular weight is 10,000 to 40000, and the viscosity is 400 to 1700 (mm ² / s) at 25 ° C. Specific gravity of 0.87 to 0.97, refractive index of 1.41 to 1.51, and those having an aralkyl group and a long-chain alkyl group in the side chain can be mentioned. Specifically, for example, Shin-Etsu Chemical Co., Ltd. X-22-1877 (HLB = 0, weight average molecular weight = 2221, viscosity at 25 ° C. = 850 (mm ² / s), specific gravity = 0.92, refractive index = 1.466).

Specifically, the weight average molecular weight is, for example, 10,000, 15,000, 16000, 18000, 20000, 22000, 24000, 25000, 26000, 28000, 30000, 40000. This molecular weight may be within a range between any two of the numerical values exemplified herein.
Specifically, the viscosity is, for example, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700 (mm ² / s). This viscosity may be within a range between any two of the numerical values exemplified herein.
Specifically, the specific gravity is, for example, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92.0.93, 0.94, 0.95, 0.96, 0 .97. This specific gravity may be within a range between any two of the numerical values exemplified here.
Specifically, the refractive index is, for example, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51. This refractive index may be within a range between any two of the numerical values exemplified here.

(4) Aralkyl-long-chain alkyl-polyether-modified silicone oil The aralkyl-long-chain alkyl-polyether-modified silicone oil has, for example, a weight average molecular weight of 2500 to 10,000 and a viscosity of 35 to 140 at 25 ° C. mm ² / s), a specific gravity of 0.91 to 1.01, a refractive index of 1.37 to 1.47, and having an aralkyl group, a long chain alkyl group and a polyether group in the side chain, Specifically, for example, X-22-2516 (HLB = 1, weight average molecular weight = 5424, viscosity at 25 ° C. = 70 (mm ² / s), specific gravity = 0.96, refractive index = Shin-Etsu Chemical Co., Ltd. 1.424). As this type of modified silicone oil, SF8419 (HLB = 1) manufactured by Toray Dow Corning Co., Ltd. can also be used.

Specifically, the weight average molecular weight is, for example, 2500, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000. This molecular weight may be within a range between any two of the numerical values exemplified herein.
Specifically, the viscosity is, for example, 35, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 (mm ² / s). This viscosity may be within a range between any two of the numerical values exemplified herein.
Specifically, the specific gravity is, for example, 0.91, 0.92.0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1 .01. This specific gravity may be within a range between any two of the numerical values exemplified here.
Specifically, the refractive index is, for example, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46. 1.47. This refractive index may be within a range between any two of the numerical values exemplified here.
As the modified silicone oil (a-1), it has been experimentally revealed that aralkyl-long chain alkyl-polyether modified silicone oil is most preferable from the viewpoint of durability of the antifouling effect.

1-1-3. Hydrophilic / lipophilic balance of modified silicone oil (a-1) (HLB)
The HLB of the modified silicone oil (a-1) is not particularly limited, but is preferably in the range of 0 or more and less than 2 from the viewpoint of maintaining the antifouling effect for a long period of time. Specifically, the HLB of the modified silicone oil (a-1) is, for example, 0, 0.5, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7 and 1.8.1.9. This HLB may be within a range between any two of the numerical values exemplified here.

In the present invention, HLB is calculated by the following equation, and the larger the numerical value of HLB, the greater the hydrophilicity. HLB is represented in the range of 0-20.
HLB = weight% of polyether group in modified silicone oil ÷ 5

1-1-4. Use amount of modified silicone oil (a-1) In the antifouling coating composition of the present invention, the use amount of the modified silicone oil (a-1) is 100 parts by weight of the spreading resin [B] in the antifouling agent. 0.5 to 50 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight. When the amount is less than 0.5 parts by weight, the amount of the antifouling agent eluted is small and the antifouling effect is weakened and the fouling organisms are likely to adhere. This is because it may not be possible to maintain for a long time. The amount of the modified silicone oil (a-1) used is specifically 0.5, 1, 5, 10, 15, 20, for 100 parts by weight of the spreading resin [B] in the antifouling agent. 30, 40, and 50 parts by weight. This usage amount may be within a range between any two of the numerical values exemplified here.

（式中、Ｒ⁶はアルキル基、ｒ、ｓ及びｚは全て１以上の整数）で表わされるエチレン・α−オレフィン共重合体等が挙げられる。 1-2. Polyolefins (a-2)
Polyolefins (a-2) include polybutenes, general formula (III):

(Wherein, R ⁶ is an alkyl group, and r, s, and z are all integers of 1 or more) and an ethylene / α-olefin copolymer.

  Examples of polybutenes include polybutene LV-7, polybutene LV-10, polybutene LV-25, polybutene LV-50, polybutene LV-100, polybutene HV-35, polybutene HV-100, manufactured by Nippon Petrochemical Co., Ltd. Polybutene HV-300, Polybutene HV-1900, Polybutene 0N, Polybutene 0H, Polybutene 5H, Polybutene 10H, Polybutene 300H, Polybutene 2000H, Polybutene 0R, Polybutene 15R, Polybutene 35R, Polybutene 100R, Polybutene 350R, manufactured by Idemitsu Petrochemical Co., Ltd. Polybis OSH manufactured by Nippon Oil & Fats Co., Ltd., and the like, preferably polybutene 0N, polybutene 0H, and polybis OSH. These polybutenes are used alone or in combination of two or more.

  The ethylene / α-olefin copolymer represented by the general formula (III) may be any of a random copolymer, a block copolymer, and a graft copolymer.

R ⁶ is an alkyl group, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc., preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

r is an integer greater than or equal to 1, Preferably it is an integer of 1-100.
s is an integer greater than or equal to 1, Preferably it is an integer of 1-100.
z is an integer greater than or equal to 1, Preferably it is an integer of 1-1000.

  Specific examples of the ethylene / α-olefin copolymer represented by the general formula (III) include, for example, Lucant HC-10, Lucant HC-20, Lucant HC-40, and Lucant HC-100 manufactured by Mitsui Chemicals, Inc. Lucant HC-150, Lucant HC-600, Lucant HC-2000, and the like.

  These ethylene / α-olefin copolymers are used alone or in combination of two or more. These ethylene / α-olefin copolymers may be used alone or in combination with polybutenes.

  In the antifouling coating composition of the present invention, the amount of polyolefin used is 1-1000 parts by weight with respect to 100 parts by weight of the modified silicone oil (a-1) in the antifouling coating composition, The amount is 1 to 500 parts by weight, and more preferably 50 to 300 parts by weight. If the amount of polyolefin used exceeds 1000 parts by weight, the coating film becomes so soft that it may not be practically used. The amount of polyolefin used is specifically 1,10,50,100,200,300,400,500,1000 parts by weight with respect to 100 parts by weight of the modified silicone oil (a-1). This usage amount may be within a range between any two of the numerical values exemplified here.

2. Spreading resin [B]
As the spreading resin [B] used in the present invention, a synthetic resin and / or a natural resin is used. Synthetic resin spreading resins include vinyl chloride / vinyl acetate copolymer, vinyl chloride / alkyl vinyl ether copolymer, vinyl resin such as vinyl chloride resin, alkyd resin, (meth) acrylic resin, urethane resin Polyester resin, synthetic rubber, and chlorinated polyethylene. Examples of natural resins include wood rosin, gum rosin, modified rosin, rosin metal salt and rosin ester. As the resin used for the spreading resin, a (meth) acrylic resin is particularly preferable.

  The spreading resin [B] is preferably a resin having a glass transition temperature of −60 ° C. to + 60 ° C., more preferably −40 ° C. to + 40 ° C. This is because if the glass transition temperature is less than −60 ° C., the coating film is soft and cannot be used, and if it exceeds + 60 ° C., the coating film becomes brittle and easily peels off.

  Further, the spreading resin [B] preferably has a number average molecular weight of 1,000 to 100,000, more preferably 10,000 to 50,000. When the number average molecular weight is less than 1,000, the viscosity of the antifouling coating composition does not increase, so the adhesion rate to the fishing net decreases, and as a result, the antifouling effect cannot be sustained for a long period of time, exceeding 100,000 This is because the viscosity of the antifouling coating composition becomes too high and handling becomes difficult.

These spreading resins may be used alone or in combination of two or more.
The spreading resin used in the present invention is used in an amount of 1 to 50% by weight in the antifouling coating composition, and preferably 5 to 30% by weight. If it is less than 1% by weight, the adhesion to the fishing net is weak and the antifouling effect cannot be maintained for a long time. On the other hand, if it exceeds 50% by weight, the adhesion to the fishing net will be strong, but since there are too many spreading resins, the amount of antifouling agent eluted will be small and the antifouling effect will be poor. The content of the spreading resin in the antifouling paint composition is, for example, 1, 5, 10, 20, 30, 40, 50% by weight. This content may be in a range between any two of the numerical values exemplified here.

3. Antifouling agent [C]
Antifouling agents used in the present invention include cuprous oxide, copper powder, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, pyridine tri Phenylboron is mentioned.

 Examples of the antifouling agent include copper thiocyanate, cupronickel, zinc ethylene bisdithiocarbamate, bis (dimethyldithiocarbamate) zinc, 3,4-dichlorophenyl-N-N-dimethylurea, 2-methylthio-4-t- One or more antifouling agents that are substantially insoluble in a solvent such as butylamino-6-cyclopropylamino-s-triazine may be used in combination.

  These antifouling agents preferably have an average particle size of 10 μm or less, and most preferably 3 μm or less, from the viewpoint of dispersibility. These average particle diameters can be measured by a particle size distribution meter manufactured by Nikkiso Co., Ltd., model Microtrac MT3300EXII (measurement principle laser diffraction / scattering method).

  In the antifouling coating composition of the present invention, the total amount of antifouling agent used is 1 to 200 parts by weight, preferably 1 to 100 parts by weight, more preferably 100 parts by weight of the spreading resin. Is 10 to 50 parts by weight. When the amount of the antifouling agent used is less than the above range, the antifouling property is not sufficient, while when it exceeds the above range, the coating performance and the physical properties of the coating film tend to deteriorate. Specifically, the total amount of antifouling agent used is, for example, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 100 parts by weight of the spreading resin. 200 parts by weight. This usage amount may be within a range between any two of the numerical values exemplified here.

4). Other components The antifouling coating composition of the present invention is an anti-settling agent, an anti-sagging agent, a plasticizer, a surfactant, a dye, a pigment, an organic solvent, water, etc., as long as the object of the present invention is not impaired. It can be contained at a blending ratio.

  Examples of the organic solvent optionally used in the present invention include xylene, toluene, isobutanol, methyl isobutyl ketone, butyl acetate, butyl cellosolve, propylene glycol monomethyl ether acetate and the like.

  Examples of the anti-settling agent / sagging agent optionally used in the present invention include polyethylene wax, hydrogenated castor oil wax type, polyamide wax type, amide wax type, and oxidized polyethylene type wax. These are added castor oil wax, polyamide wax, amide wax, and oxidized polyethylene wax. These anti-settling agents and sagging inhibitors may be used alone or in combination of two or more.

  Examples of the plasticizer optionally used in the present invention include phthalic acid esters, adipic acid esters, phosphoric acid esters, paraffins, petrolatums, dialkyl sulfide compounds and the like.

  As phthalates, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, as adipates, dibutyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, phosphates as phosphate Examples include tricresyl and trioctyl phosphate.

  Examples of paraffins include n-paraffin (manufactured by Nippon Petrochemical Co., Ltd.), solid paraffin (manufactured by Nippon Seiwa Co., Ltd.), liquid paraffin (Sumoyl P-100, manufactured by Matsumura Oil Co., Ltd.), and smoil. P-150), chlorinated paraffin (A-40, A-50, A-70, A-145, A-150, A-265, A-270, etc., manufactured by Tosoh Corporation) and the like.

  Examples of petrolatum include white petrolatum and yellow petrolatum (manufactured by Ando Parachemy Co., Ltd.).

  Dialkyl sulfide compounds include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide, dipentyl decasulfide, dioctyl tetrasulfide, dioctyl pentasulfide, dinonyl tetrasulfide, dinonyl pentasulfide, di-tert-nonyl tetra Examples thereof include sulfide, di-tert-nonyl pentasulfide, didecyl tetrasulfide, didodecyl tetrasulfide, dioctadecyl tetrasulfide, dinonadecyl tetrasulfide and the like.

  Preferred plasticizers are tricresyl phosphate, yellow petrolatum and di-tert-nonyl pentasulfide.

  These plasticizers may be used alone or in combination of two or more.

  The antifouling coating composition of the present invention can be produced by dissolving or mixing and dispersing an elution control agent, a spreading resin, an antifouling agent and other additives in an organic solvent or water. The mixing method of each component and the adding method of various additives are not particularly limited, and can be performed by various methods. The mixing order and the adding order can also be performed by various methods.

5). Antifouling treatment method,
The present invention also provides an antifouling treatment method for fishing net tools and the like that prevents the adhesion of water fouling organisms and exhibits excellent antifouling properties by applying the antifouling paint composition of the present invention to fishing net tools and the like. can do. As a method for applying the antifouling coating composition to a fishing net tool or the like, for example, various coating methods such as immersion coating and spray coating can be applied, and immersion coating is preferable. In the case of a fishing net, the adhesion amount is preferably in the range of 1 to 20% by weight of the fishing net weight.

  Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.

Examples 1-15 and Comparative Examples 1-6
The blending components described in Table 1 and Table 2 were mixed to obtain antifouling compositions of Examples 1 to 15 and Comparative Examples 1 to 6. The amount of each component in Tables 1 and 2 is shown in parts by weight. The following test was done about the obtained antifouling composition.

1. Test Example 1 (Confirmation test for antifouling effect on animal debris)
1-1. Hydroworm active sea immersion test (Obama, Fukui Prefecture)
Each antifouling composition obtained in Examples 1 to 8 and Comparative Examples 1 to 3 shown in Table 1 was dip-coated on a polyethylene fishing net (400 denier, 40 bars, 8 sections) and dried at room temperature for 2 days. did. The fishing net thus coated with the antifouling composition and dried is fixed to a frame of 40 × 60 cmSUS, and the depth of the water is about 1 m from the sea at the foot of Obama, Fukui Prefecture, which is a sea area where the activity of coelenterate such as hydroworms is strong. The antifouling performance was regularly observed over 8 months. The results are shown in Table 3. The numbers in the table represent the adhesion area (%) of the water fouling fouling organism fouling organism.

1-2. Barnacles and cell plastics active water immersion test (Hiroshima Prefecture)
The antifouling compositions for fishing nets obtained in Examples 9 to 15 and Comparative Examples 4 to 6 described in Table 2 were dip coated on polyethylene fishing nets (400 denier, 40 bars, section 8) and room temperature was maintained for 2 days. And dried. The fishing net thus applied with the antifouling composition for fishing nets and dried is fixed to a 40 × 60 cm SUS frame, and it is underwater at the foot of Hiroshima Prefecture Land Gozen, which is a highly active area of animals such as barnacles and cell plastics. And then immersed in a water depth of about 1 m, and its antifouling performance was regularly observed over 8 months. The results are shown in Table 4. The numbers in the table represent the adhesion area (%) of the water fouling fouling organism fouling organism.

As is apparent from Tables 3 and 4, the antifouling compositions of Examples 1-15 using the modified silicone oil of the present invention and the antifouling compositions of Comparative Examples 1-6 using other silicone oils were used. In comparison of antifouling performance against animal fouling organisms, there is a difference in effect duration, and it can be seen that the antifouling composition using the modified silicone oil of the present invention exhibits an excellent antifouling effect over a long period of time. .
Moreover, when Table 3 and Table 4 are referred, in Examples 1-2, 6-10, 14-15, it turns out that the animal fouling organism did not adhere even after 8 months passed. Examples 1-2, 6-10, and 14-15 all use aralkyl-long-chain alkyl-polyether-modified silicone oil as the modified silicone oil. The results in Tables 3 and 4 are as follows: As the modified silicone oil, aralkyl-long chain alkyl-polyether modified silicone oil is most preferred.

2. Test example 2 (antifouling agent residual amount confirmation test)
After each of the antifouling compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 6 was dip-coated on a polyethylene fishing net (400 denier, 40, section 8) cut into 2 × 2, room temperature For 24 hours or more. Four sets were made. The fishing nets thus coated with the antifouling composition are soaked (aged) in artificial seawater for a certain period, and the residual rate (%) of the antifouling agent is quantified by instrumental analysis for each fishing net after 2 months and 4 months. ,confirmed. The results are shown in Tables 5 and 6.

2-1. Aging method Artificial seawater, "Aquamarine" manufactured by Yasu Pharmaceutical Co., Ltd. is adjusted with ion-exchanged water in a 60L container made of resin (polyethylene or polypropylene), pH 8.1 ± 2.0, salinity 30-35 ‰ The temperature was controlled to be 25 ± 2 ° C. The antifouling agent eluted in the artificial seawater was removed by adsorption with an activated carbon cartridge filter so that it was not saturated in the artificial seawater. The removal circulation is performed at a flow rate at which the artificial seawater in the container is changed 6 to 8 times per hour. The replacement of the artificial seawater and the activated carbon cartridge filter was performed at least once a month, and each fishing net was immersed (aging).

2-2. Antifouling agent residual ratio measurement method (1) Measurement of residual amount of 2-mercaptopyridine N-oxide zinc Each antifouling composition obtained in Examples 1 to 5 and 7 and Comparative Examples 1 to 3 in Table 1 was applied. Each fishing net is lifted from artificial seawater and washed with water. Each dried fishing net is put into a 100 ml mayonnaise bottle, dichloromethane is added, the remaining coating film is dissolved with an ultrasonic cleaner, and then diluted to a predetermined concentration with acetonitrile. The residual amount of 2-mercaptopyridine N-oxide zinc was measured by HPLC, and the residual rate (%) was calculated.

(2) Measurement of residual amount of bisdimethyldithiocarbamoylethylenebisdithiocarbamate Pull up each fishing net coated with each antifouling composition obtained in Examples 1 to 7 and Comparative Examples 1 to 3 in Table 1 from artificial seawater and wash with water Then, each dried fishing net is put into a 100 ml mayonnaise bottle, acetone is added to dissolve the remaining coating film with an ultrasonic cleaner, 35% hydrochloric acid is further added to wet decomposition, and the lower layer portion is predetermined with 1 N hydrochloric acid. After dilution to a concentration, atomic absorption flame analysis was performed to determine the total amount of residual zinc. The residual zinc amount of 2-mercaptopyridine N-oxide zinc obtained above was subtracted from the total residual zinc amount, and the residual rate (%) of bisdimethyldithiocarbamoylethylenebisdithiocarbamate was calculated from the calculation of the zinc amount.

(3) Measurement of residual amount of pyridine / triphenylboron The fishing net coated with the antifouling composition obtained in Example 8 of Table 1 was pulled up from artificial seawater, washed with water, and the dried fishing net was put into a 100 ml mayonnaise bottle. A certain amount of xylene was added thereto, and the remaining coating film was dissolved by an ultrasonic cleaner. The solution was diluted to a predetermined concentration with an HPLC mobile phase containing methanol / water = 70/30 (wt / wt) and 0.1 wt% ethanolamine, analyzed by the HPLC absolute calibration curve method, and pyridine per fishing net. -The residual ratio (%) of triphenylboron was calculated.

(4) Measurement of residual amount of 2-mercaptopyridine N-oxide copper Each fishing net to which each antifouling composition obtained in Examples 9 to 13 and 15 and Comparative Examples 4 to 6 in Table 2 was applied was taken from artificial seawater. Each fishing net that has been pulled up, washed with water and dried is put into a 100 ml mayonnaise bottle, dichloromethane is added, the remaining coating film is dissolved with an ultrasonic cleaner, diluted to a predetermined concentration with acetonitrile, and 2-mercaptopyridine N by HPLC. -The residual amount of oxide copper was measured and the residual rate (%) was calculated.

(5) Measurement of remaining amount of cuprous oxide (copper powder) Each fishing net coated with each antifouling composition obtained in Examples 9 to 15 and Comparative Examples 4 to 6 in Table 2 was pulled up from artificial seawater and washed with water. Each dried fishing net is put into a 100 ml mayonnaise bottle, xylene is added, the remaining coating film is dissolved with an ultrasonic cleaner, and 35% nitric acid is added to wet decompose the lower layer with 0.1 mol / L nitric acid. Dilute to concentration and perform atomic absorption flame analysis to determine the total remaining copper per fishing net. The copper content of the 2-mercaptopyridine N-oxide copper obtained above was subtracted from the total residual copper content, and the residual cuprous oxide (%) was calculated from the copper content.
In Examples 14 and 15, the copper amount obtained by subtracting the copper amount of 2-mercaptopyridine N-oxide copper obtained above from the total residual copper amount is treated as the total residual amount of cuprous oxide and copper powder. The residual (%) was calculated.

As is apparent from Tables 5 and 6, the antifouling compositions of Examples 1-15 using the modified silicone oil of the present invention, and the antifouling compositions of Comparative Examples 1-6 using other silicone oils, In the antifouling composition using the modified silicone oil of the present invention, it can be seen that there is a significant difference in the residual rate (%) of the antifouling agent. It can be seen that the antifouling effect can be demonstrated for a long time as designed.
Moreover, when Example 1 and Example 6, Example 2 and Example 7, Example 9 and Example 14, Example 10 and Example 15 are compared, respectively, the former containing polyolefins does not contain polyolefins. It can be seen that the antifouling agent remains higher than the latter. This result shows that the duration of the antifouling effect can be extended by including polyolefins.

Claims (8)

[A] Elution control agent comprising one or more modified silicone oils (a-1) in which part of the methyl groups in the side chain of dimethyl silicone oil is substituted with one or more organic groups When,
[B] spreading resin;
[C] 1 selected from the group consisting of cuprous oxide, copper powder, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, and pyridine triphenylboron Including an antifouling agent comprising two or more species,
The modified silicone oil (a-1) is included in an amount of 0.5 to 50 parts by weight with respect to 100 parts by weight of the spreading resin [B], and the antifouling agent [C] is the spreading resin [B]. 1 to 200 parts by weight per 100 parts by weight,
The modified silicone oil (a-1) has the general formula

[Wherein, l, m, n, o are all integers of 1 or more. R ¹ is an aralkyl group, R ² is an alkyl group having 6 or more carbon atoms, and R ³ is a polyether group. ],
In the general formula (I), the methyl group in the side chain is an unsubstituted repeating unit, the repeating unit in which one of the methyl groups in the side chain is substituted with R ¹ , and ^one of the methyl groups in the side chain is substituted with R ² The order in which the repeating units and the repeating units in which one of the side chain methyl groups is substituted with R ³ is not particularly limited, and may be random, alternating, or continuous. Composition. The antifouling paint composition according to claim 1 , wherein the modified silicone oil (a-1) has a hydrophilic / lipophilic balance (HLB) of 0 or more and less than 2. The elution control agent [A] further includes one or more of polyolefins (a-2), and the polyolefins (a-2) are added to 100 parts by weight of the modified silicone oil (a-1). The antifouling paint composition according to claim 1 or 2 contained in an amount of 1 to 1000 parts by weight. The antifouling paint composition according to claim 3 , wherein the polyolefin (a-2) is one or more selected from the group of polybutenes and ethylene-α-olefins. The antifouling paint composition according to any one of claims 1 to 4 , wherein the spreading resin [B] is a (meth) acrylic acid ester copolymer having a glass transition temperature of -40 to 40 ° C. The antifouling processing method which forms an antifouling coating film on the surface of a to-be-coated-film formation using the antifouling coating composition as described in any one of Claims 1-5 . The antifouling coating film formed using the antifouling paint composition as described in any one of Claims 1-5 . A fishing net, a fishing net tool and an underwater structure having the antifouling coating film according to claim 7 on the surface thereof.