JPH04244002A - Method for controlling elution rate of antifouling agent - Google Patents

Abstract

PURPOSE:To suitably control the elution of an antifouling agent to allow the antifouling effect of a fibrous or rope-like material to persist over a long period, by treating the fibrous or rope-like material with an elution-controlling agent containing a specific hydrophilic polymer, a dialkylpolysulfide derivative, etc. CONSTITUTION:A fibrous or rope-like material is treated with a marine antifouling agent containing (A) 4,5-dichloro-2-n-octylisothiazolin-3-one, (B) a hydrophilic homopolymer of an unsaturated monomer of formula I (X is H. methyl; n1 is 1-50; R is 1-18C alkyl or acyl) such as 2-methoxyacrylate or a copolymer thereof with a copolymerizable monomer, and (C) a compound selected from C1: a compound of formula II (R<2>, R<3> are 1-20C alkyl; n2 is 1-5), C2: polybutene having a polymerization degree of 2-100, C3: xylene.formaldehyde polycondensation product having an average mol.wt. of 300-1000, and C4: a 9C aromatic hydrocarbon.formaldehyde polycondensation product having an average mol.wt. of 350-700.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for controlling the elution rate of an antifouling agent eluted from a fibrous or rope-like material treated with a novel underwater antifouling agent and submerged in the sea.

0002

[Prior Art] Fishing nets for aquaculture and fixed use that are immersed in the sea for long periods of time, materials such as ropes that support them, nets to prevent jellyfish and other intrusion at cooling seawater intakes, seawater used for coastal construction, etc. Pollution prevention curtains, etc. will be submerged in the sea for a long period of time. As a result, it is contaminated by marine fouling organisms,
Various fish infections due to blockage of the mesh and decrease in seawater inflow,
Problems arise such as parasitic diseases, damage due to weight gain, and reduced buoyancy. Conventionally, as a method to prevent pollution caused by such marine organisms, TBT (tributyltin compound) has been used.
Marine antifouling agents containing organic tin compounds as active ingredients have been widely used, but there is a growing movement to refrain from using them due to suspicions that the active ingredients may accumulate in the environment. On the other hand, as an antifouling treatment agent that does not contain these organotin compounds, (a) Japanese Patent Publication No. 62-43962 describes a technology using a dialkyl sulfide compound as an active ingredient (
b) JP-A No. 60-38306 discloses technologies related to antifouling agents for fishing nets containing tetraalkylthiuram disulfide, dialkyl polysulfide, 2-(thiocyanomethylthio)benzothiazole, etc. as active ingredients. . Furthermore, apart from these techniques, (c) the present inventors have disclosed in JP-A-1-178562 a fishing net antifouling agent containing a copolymer exhibiting specific hydrophilicity and a thiocyanoalkylthiobenzoheterozole. We are proposing technology.

0003

[Problems to be Solved by the Invention] However, it is not possible to obtain effective antifouling performance only with the dialkyl sulfide compound disclosed as the technique (a) above, and also, the dialkyl sulfide compound disclosed as the technique (b) above cannot obtain effective antifouling performance. Tetraalkylthiuram disulfide, dialkyl polysulfide, and 2-(thiocyanomethylthio)benzothiazole exhibit effective antifouling properties in the short term, but these alone do not allow sufficient amounts of active ingredients to be leached from the fishing net treatment agent over the long term. This was extremely difficult. Furthermore, as technology (c) above, the copolymer exhibiting specific hydrophilicity and thiocyanoalkylthiobenzoheterozole that the present inventors previously proposed are still insufficient to maintain effective antifouling performance over a long period of time. It has been found. An object of the present invention is to provide a method for necessary and sufficient control over a long period of time of the elution rate of an antifouling agent from a fibrous or rope-like material treated with an underwater antifouling agent.

0004

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have conducted intensive research and found that 4,5-dichloro-
A marine antifouling treatment agent containing 2-n-octylisothiazolin-3-one as an antifouling agent contains a specific hydrophilic polymer, a specific dialkyl polysulfide compound, polybutene, xylene formaldehyde polymer, etc. as an elution control agent. By combining the condensate and the C9 aromatic hydrocarbon formaldehyde polycondensate, the elution rate of 4,5-dichloro-2-n-octylisothiazolin-3-one, which is an antifouling agent, can be controlled in a necessary and sufficient manner over a long period of time. This discovery led to the completion of the present invention.

That is, the present invention provides sea-soaked fibrous or rope-like materials by treating the fibrous or rope-like materials with an underwater antifouling treatment agent containing the following components (A) to (C). This is a method for controlling the elution rate of an antifouling agent from: (A) 4,5-dichloro-2-n-octylisothiazolin-3-one, (B) General formula (1)

[Chemical formula 3]

(In the formula, X is hydrogen or a methyl group, nl is an integer of 1 to 50, and R is an alkyl group or acyl group having 1 to 18 carbon atoms.) Hydrophilic copolymer with polymer or other unsaturated monomer copolymerizable with these, (C) One or more types selected from the following (C1) to (C4): (C1) General Formula (2)

[Formula 4] R2-(S)n2-R3
(2)

[0007] (In the formula, R2, R3
each represents an alkyl group having 1 to 20 carbon atoms, and n2 is 1
Indicates an integer between ~5. ), (C2) polybutene with a degree of polymerization of 2 to 100, (C3)
A xylene/formaldehyde polycondensate having an average molecular weight of 300 to 1000, and (C4) a C9 aromatic hydrocarbon/formaldehyde polycondensate having an average molecular weight of 350 to 700.

Component (A) which is an antifouling agent in the marine antifouling treatment agent used in the present invention, that is, 4,5-dichloro-
2-n-octylisothiazolin-3-one is known as a low toxicity antifouling agent.

The component (B), that is, the hydrophilic copolymer used as the elution control agent in the marine antifouling treatment agent used in the present invention, has the unit (B1), that is, the general formula (1) as its constituent unit. A polymer or unit (B2) of one or more unsaturated monomers represented by (B2), that is, a unit (
One or two other unsaturated monomers copolymerizable with B1)
It is a copolymer of one or more types of units (B1) and one or more types of units (B1).

Examples of the unit (B1) include 2-methoxyethyl acrylate, methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate,
-Ethoxyethyl acrylate, ethoxydiethylene glycol acrylate, ethoxytriethylene glycol acrylate, ethoxytetraethylene glycol acrylate, ethoxypolyethylene glycol acrylate, 2-propioxyethyl acrylate, propioxydiethylene glycol acrylate, propyoxytriethylene glycol acrylate, propioxytetraethylene glycol Acrylate, propioxypolyethylene glycol acrylate, 2-acetoxyethyl acrylate, acetoxydiethylene glycol acrylate, acetoxytriethylene glycol acrylate, acetoxytetraethylene glycol acrylate, acetoxypolyethylene glycol acrylate, 2-methoxyethyl methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate , methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-ethoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, ethoxytriethylene glycol methacrylate, ethoxytetraethylene glycol methacrylate, ethoxypolyethylene glycol methacrylate, 2-propoxyethyl methacrylate, propioxydiethylene glycol methacrylate , propioxytriethylene glycol methacrylate, propioxytetraethylene glycol methacrylate, propioxypolyethylene glycol methacrylate, 2-acetoxyethyl methacrylate, acetoxydiethylene glycol methacrylate, acetoxytriethylene glycol methacrylate, acetoxytetraethylene glycol methacrylate, acetoxypolyethylene glycol methacrylate, etc. It will be done.

Examples of the unit (B2) include acrylic acid alkyl ester, methacrylic acid alkyl ester, crotonic acid ester, itaconic acid ester, acrylamide, acrylonitrile, ethylene, vinyl chloride, vinyl acetate, vinylidene chloride, methyl vinyl ether, butadiene, Examples include cyclohexene, styrene, vinyltoluene, α-methylstyrene, and chlorostyrene.

[0012] Component C in the marine antifouling treatment agent used in the present invention is the above-mentioned components (C1) to (C4), namely dialkyl polysulfide (C1), polybutene (C2), xylene formaldehyde polycondensate (C3). ) and C9
One or more selected from aromatic hydrocarbon formaldehyde polycondensates (C4) are blended. These components (C1) to (C4) are generally used as extreme pressure additives for cutting oils, resin softeners, glues, etc., respectively, but they themselves do not exhibit any inhibitory effect on living organisms. .

Examples of component (C1) include di-t-nonylpentasulfide (specific gravity 1.03) and di-t-dodecylpentasulfide (specific gravity 1.55). Component (C2) polybutene includes, for example, Nissan Polybutene (Polybis) (manufactured by NOF Corporation), and component (C3) xylene formaldehyde polycondensates include, for example, Oligotec (Mitsubishi Oil Corporation). ),
Examples of the C9 aromatic hydrocarbon formaldehyde polycondensate of component (C4) include Generalite types (manufactured by General Petrochemical Co., Ltd.). However, components (C1) to (C4) are not limited to these.

[0014] Marine antifouling treatment agent 100 used in the present invention
The mixing ratio of components (A) to (C) in parts by weight is component (A)
is 0.3 to 20 parts by weight, preferably 0.5 to 20 parts by weight, component (B) is 1 to 30 parts by weight, preferably 2 to 20 parts by weight, and component (C) is 1 to 30 parts by weight, Preferably it is 2 to 25 parts by weight. The remainder is other components such as organic solvents. If the amount of component (A) is less than the above, the antifouling properties will be insufficient, and if it is too much, it will be difficult to form a coating film. When the amount of component (B) is too low, it becomes difficult to form a coating film, and when it is too high, the antifouling properties are insufficient and the elution control function is deteriorated. If the amount of component (C) is too small, the elution control function will be degraded, and if it is too large, the elution control function will also be degraded and it will be difficult to form a coating film. In the marine antifouling treatment agent used in the present invention, the above-mentioned components (A) to (
In addition to C), other additives such as resins, organic solvents, antifouling agents, colorants, additives, thixotropic agents, antifoaming agents, thickeners, and plasticizers may be added as necessary. Other resins include rosin, modified rosin, fatty acids, conventionally used oil-based varnishes, chlorinated rubber, polyvinyl chloride, and styrene.
Various resins such as butadiene copolymer and acrylic resin can be mixed and used within a range that does not impair the effects of the present invention. As the organic solvent, for example, toluene, xylene, solvent naphtha, pseudocumene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, alkyl cellosolve, and the like can be used alone or in combination of two or more.

Furthermore, N-t-butyl-N'-cyclopropyl-6-(
methylthio)-1,3,5-triazine-2,4-diamine, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, N,N-dimethyl-N'-phenyl-N
'-(fluorodichloromethylthio)sulfamide, N
, N-dimethyl-N'-tolyl-N'-(fluorodichloromethylthio)sulfamide, N-(fluorodichloromethylthio)phthalimide, bis(diethylcarbamoyl)disulfide, 2-(thiocyanomethylthio)benzothiazole, 2,4, 5,6-tetrachloro-1,
3-dicyanobenzene, N-(2,6-diethylphenyl)dichloromaleimide, N-(2-ethyl-6-methylphenyl)dichloromaleimide, cuprous oxide, organotin compound, zinc dimethyldithiocarbamate, copper diethyldithiocarbamate , tetraethylthiuram disulfide, N-(ethylmethylphenyl)-dichloromaleimide, N-(diethylphenyl)-dichloromaleimide, and others may be added within a range that does not impair the effects of the present invention. The underwater antifouling treatment agent used in the present invention is usually prepared by dissolving each component in an organic solvent using a dissolver or the like. The prepared underwater antifouling treatment agent is impregnated with a method suitable for each object, such as dipping treatment.

[0016]

Effects of the Invention According to the method for controlling the elution rate of an antifouling agent of the present invention, the elution of the antifouling agent of component (A) is appropriately controlled, resulting in improved antifouling effect on fibrous or rope-like materials soaked in water. However, it can be sustained for a long period of time, which was not possible before.

[0017]

[Examples] Next, the present invention will be specifically explained with reference to production examples, working examples, and comparative examples. Parts and percentages in the examples are by weight.

Production Examples 1 to 3 Solvent 1, Unit (B1), Unit (B2) and Catalyst 1 were placed in a flask equipped with a stirrer according to the formulation shown in Table 1.
was charged, the temperature was raised to 100°C in 30 minutes while stirring, and stirring was continued at the same temperature for 2 hours. continue,
After an additional mixture of Solvent 2 and Catalyst 2 was added dropwise over 1 hour, stirring was continued at 105°C for 2 hours and further at 120°C for 1 hour. Finally, add the diluting solvent and make it uniform, 3
Different kinds of transparent hydrophilic copolymer solutions were obtained. The solid content, viscosity, and molecular weight of this polymer solution were as shown in Table 1.

[Table 1]
Table 1────────────────
──────────────────────

Production example 1 Production example 2
Production example 3────────────────────
──────────────────Solvent 1
xylene
60 60
60 units (B1) Ethoxy pentate ethylene glycol methacrylate 1
0 Methoxytricosaethylene glycol methacrylate 5
2
2-methoxyethyl acrylate

3
Polyoxytetracyl ethylene glycol methacrylate 21
．． 5 2-acetoxyethyl acrylate
21.4 units (B2) Methyl methacrylate
35 30 50
n-phytyl methacrylate 50
22.1 2-ethylhexyl acrylate

45 Styrene

5 Catalyst 1 t-Phenylhex-oxy-2-ethylhexanoate
1.5 Benzoyl peroxide
1.5 1.5 catalyst 2 t
-Phthylhex-oxy-2-ethylhexanoate
0.5
benzoyl peroxide
1.5 1.5 Solvent 2
xylene
20 20
20 dilution solvent xylene
20
20 20─────
──────────────────────────
────── Characteristic value Viscosity (poise/20℃) 1.3 1
．． 0 1.2
Solid content (wt%)
62.0 49.2 48.8
Weight average molecular weight 73,000 23,000
28,000 ────────────────
──────────────────────

001
9] Examples 1 to 30 and Comparative Examples 1 to 20

[0020]
<Preparation of underwater antifouling treatment agents> Each of the treatment agents of Examples and Comparative Examples was prepared by putting the entire composition into a beaker and stirring with a dissolver to dissolve it according to the formulations in Table 2.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

Note) (*1) DCOITO 4,5-dichloro-2-n-
Octylisothiazolin-3-one 30% xylene solution (manufactured by Rohm & Haas Co., Ltd.) (*2) Acrylic resin Hythaloid 1641A (manufactured by Hitachi Chemical Co., Ltd.) (solid content 100%) (*3) TNPS Jitter Sharinonyl pentasulfide (reagent; manufactured by Tokyo Chemical Industry Co., Ltd.) (*4)
PB Polybutene 06N (manufactured by NOF Corporation) (*5) XF Xylene formaldehyde polycondensate Oligotec (manufactured by Mitsubishi Oil Corporation) (
*6) HCF C9 hydrocarbon formaldehyde resin Generalite (manufactured by General Petrochemical Industries Co., Ltd.)

[0022] For each treatment agent of Examples and Comparative Examples prepared above, an antifouling property test by immersion in the sea and measurement of the amount of elution of the antifouling agent were conducted by the method described below. The results are shown in Table 3.

<Antifouling property test> Polyethylene knotless aquaculture raw fishing net (32
A cut piece of 20 cm wide and 40 cm long of a book (Section 6) was immersed, impregnated, and air-dried for 48 hours. A fishing net impregnated with a treatment agent was suspended 1.5 meters below the sea surface in Aioi Port, Hyogo Prefecture, and
The state of pollution caused by marine organisms was investigated for six months. The results of the stain resistance test were evaluated on the following five scales. 5: No biofouling observed at all. 4: Biofouling is less than 5% of the net area. 3: Biofouling is less than 15% and 5% or more of the net area. 2: Biofouling is less than 50% and 15% or more of the net area. 1: Biofouling covers 50% or more of the net area.

<Amount of elution of antifouling agent> A fishing net similar to that used in the antifouling property test was impregnated with a treatment agent in the same manner.
A similar immersion was conducted. The treated fishing nets were pulled out after 6 months and immersed in a beaker containing 1 liter of seawater for 1 hour to dissolve the antifouling agent. The amount of the antifouling agent eluted was measured by analyzing the seawater in which the antifouling agent was eluted using liquid chromatography. The elution amount was expressed as the concentration of the antifouling agent eluted in 1 liter of seawater (ppm).

[Table 6]
1 of Table 3
Antifouling test results Antifouling component volume 1
Months 3 months 6 months ppm
Example 1 5
5 5 0.
23 2 5
5 5 0.19
3 5
5 5 0.18
4 5 5
5 0.20
5 5 5
5 0.14
6 5 5
5 0.13
7 5 5
5 0.13
8 5 5 5
0.15
9 5 5 5
0.12 10
5 5 5
0.12 11
5 5 5
0.10 12 5
5 5 0.
11 13 5
5 5 0.12
14 5 5
5 0.10
15 5 5
5 0.09
16 5 5
5 0.09
17 5 5 5
0.08 1
8 5 5 5
0.06 19
5 5 5
0.07 20 5
5 5 0
．． 06 21 5
5 5 0.06
22 5
5 5 0.07
23 5 5
5 0.06
24 5 5
5 0.08
25 5 5 5
0.25

[Table 7]
2 of Table 3
Antifouling test results
Antifouling component capacity
1 month 3 months 6 months ppm
Example 26
5 5 5
0.16 27 5
5 5 0.
18 28 5
5 5 0.18
29 5 5
5 0.14
30 5 5
5 0.15 Comparative example 1 1 1 1
0 2
1 1 1
0 3 1
1 1 0
4 1
1 1 0
5 1 1
1 0
6 1 1 1
0 7
1 1 1
0 8 1
1 1 0
9 1
1 1 0
10 1 1
1 0
11 1 1 1
0 12
1 1 1
0 13 4
2 1 0
14 4 2
1 0
15 4 2 1
0 16
4 2 1
0 17 5
2 1 0
18 5 1
1 0
19 5 1 1
0 20
3 1 1
0

As is clear from Table 3, the method for controlling the elution rate of the antifouling agent of the present invention has excellent antifouling performance even after 6 months as in Examples 1 to 3, and the elution amount of the antifouling agent is It can be seen that this is an extremely excellent method as it maintains a high value in both cases.

Claims (1)

[Claims] Claim 1: Treatment of fibrous or rope-like materials submerged in the sea by treating the fibrous or rope-like materials with an underwater antifouling treatment agent containing the following components (A) to (C). Method for controlling elution rate of antifouling agent: (A) 4,5-dichloro-2-n-octylisothiazolin-3-one, (B) General formula (1) [Chemical formula 1] (wherein, X is hydrogen or methyl group, nl is an integer of 1 to 50, R is an alkyl group or acyl group having 1 to 18 carbon atoms,
) or a hydrophilic copolymer with other unsaturated monomers copolymerizable with these, (C) from the following (C1) to (C4): One or more selected types: (C1) General formula (2) [Chemical formula 2] R2 -(S)n2-R3
(2) One or more dialkyl polysulfide derivatives represented by (wherein R2 and R3 each represent an alkyl group having 1 to 20 carbon atoms, and n2 represents an integer of 1 to 5); C2) Polybutene with a degree of polymerization of 2 to 100, (C3)
A xylene/formaldehyde polycondensate having an average molecular weight of 300 to 1000, and (C4) a C9 aromatic hydrocarbon/formaldehyde polycondensate having an average molecular weight of 350 to 700.