JPH04318073A - Antifouling coating compound - Google Patents

Abstract

PURPOSE:To obtain the title new long-term effective composition suitable for fishing nets, facilities in contact with sea water, having low toxicity, comprising a vehicle component composed of an acetoacetyl group-containing copolymer and an antifouling component composed of cuprous oxide, etc. CONSTITUTION:(A) 100 pts.wt. copolymer composed of (i) 99-20mol% acetoacetyl group-containing monomer and (ii) 1-80mol% monomer copolymerizable with the component (i) is blended with (B) (i) usually 100-300 pts.wt. cuprous oxide, (ii) usually 10-50 pts.wt. rosin and (iii) usually 0.5-20 pts.wt. thiabendazole to give the objective composition.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new antifouling coating composition for use in fishing nets or equipment that comes into contact with seawater. More specifically, there are marine organisms such as barnacles, purple mussels, and seaweed that grow on fishing nets such as aquaculture nets and stationary nets, as well as coastal oil refineries, power plants, and other plants and equipment that use seawater. The present invention relates to an antifouling paint composition that prevents it from adhering to a substrate.

0002

[Prior Art] Fishing nets such as aquaculture nets and stationary nets, plants and equipment that utilize seawater are used to support aquatic organisms, such as barnacles, sea squirts, sea squirts, mussels, oysters, and other animals.
Fishing nets are infested with algae such as sea lettuce, blue seaweed, and Shioshiro, as well as various types of bacteria called slime, mold, and diatom.As a result, the performance of fishing nets decreases, and cooling channels of plants and equipment are blocked and corroded. When this progresses to an extreme, it causes a great deal of damage, such as the need to shut down the plant for disassembly and removal, and the need to update equipment, causing a great deal of damage in removing, repairing, and repainting.

[0003] Conventionally, in order to prevent these problems, mercury-based compounds were used in the past, and after mercury-based compounds were banned, organic tin compounds, organic tin polymers, etc. were mainly used.

However, in recent years, the accumulation of organotin compounds and organotin polymers, mainly in fish, has become a problem, and the use of them as antifouling ingredients has tended to be restricted from the standpoint of public health. be. On the other hand, in place of these organotin compounds and organotin polymers, the use of inorganic copper compounds, mainly cuprous oxide, which do not accumulate in fish and have been used for a long time, is attracting renewed attention. It has become.

However, as is well known in the past, polymers such as triphenyltin methacrylate have a so-called "water-soluble paint" function in which a polymer such as triphenyltin methacrylate flows out from the surface in small amounts in water. It is said that it is difficult for paints whose antifouling component is cuprous oxide, a type compound, to have this property.

[0006] Water-soluble paints that use cuprous oxide as an antifouling component include paints that use rosin as a vehicle, but they are subject to severe wear and tear in seawater and do not have a long-term antifouling effect. There are also antifouling paints that use chlorinated rubber vehicles as water-insoluble paints, but it is said that the antifouling effect disappears after the cuprous oxide present on the surface is eluted.

[0007] In order for a coating film containing cuprous oxide to exhibit an antifouling effect, it is said that at least 8 to 11 μg/cm2/day of cuprous oxide must be eluted, and this value is maintained at a constant value over a long period of time. It is essential for an antifouling paint to work stably.

[0008] Numerous studies have been carried out in order to obtain a vehicle for paints that contains the required amount of cuprous oxide and is constantly renewed to provide a sufficient amount of cuprous oxide from the surface of the paint film. ing.

Among them, there are examples in which a monomer forming a water-soluble polymer, such as vinyl pyrrolidone, is used as a component of a copolymer, or a monomer having a tertiary amino group is used.

The desired property is that of the previously mentioned "water-soluble paint", that is, the surface of the polymer is constantly renewed so that it can supply a constant amount of cuprous oxide.

[0011] As a result of a long period of research into a vehicle capable of releasing a sufficient amount of copper ions, the inventors of the present invention used a polymer having acetoacetyl groups as part of its components as a vehicle. I found that I could achieve my purpose by doing so, and filed the application first.

0012

However, when cuprous oxide alone is used as the antifouling component, there is a problem in that the antifouling effect is lower than that of organic tin-based products. The object of the present invention is to develop an antifouling paint composition that has cuprous oxide as its main component as an antifouling component, does not use organic tin, and has an effect equivalent to or superior to that of organic tin.

[0013]

[Means for Solving the Problems] The present invention provides that [A] the form of the final copolymer is (1) a monomer having an acetoacetyl group, and (2) at least one monomer copolymerizable therewith. An antifouling agent characterized in that the vehicle component is a polymer having an acetoacetyl group obtained by copolymerizing the above, and [B] cuprous oxide, rosin, and thiabendazole are contained as antifouling components. The above objectives were achieved by developing a coating composition.

The form of the final copolymer used as a vehicle component in the present invention is obtained by copolymerizing a monomer having an acetoacetyl group with a monomer copolymerizable therewith, or It can be synthesized by reacting diketene with a polymer having a hydroxyl group.

The diketene polymer can be synthesized either as a homopolymer or as a copolymer with a copolymerizable monomer.

As is well known, the acetoacetyl group exhibits typical keto-enol tautomerism, so in the homopolymerization of a monomer having an acetoacetyl group, the above-mentioned keto-enol tautomerism is involved. However, as the polymerization rate increases, the polymer rapidly becomes gel-like, making it difficult to obtain a stable polymer unless a large amount of polymerization regulator is used.

However, it has become clear that this drawback can be alleviated by copolymerizing monomers that form a water-insoluble polymer that can be copolymerized with a monomer having an acetoacetyl group, and this problem has been solved.

Furthermore, it has been found that the elution rate of a multicomponent copolymer copolymerized using these copolymerizable monomers can be controlled when an antifouling component such as cuprous oxide is used in combination.

Examples of monomers having acetoacetyl groups for obtaining the polymers having acetoacetyl groups used in the present invention include the following reaction products of unsaturated alcohols and diketenes.

2-Hydroxyethyl acrylate, 2-
These include hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, and allyl alcohol. Primary alcohols react more easily with diketene and are sufficient for the present invention.

[0021] Furthermore, the monomer used to copolymerize with the monomer having an acetoacetyl group and synthesize the vehicle component for obtaining the desired antifouling paint is one in which the polymer formed from this monomer is insoluble in water. For example, the following types are mentioned.

Styrene, vinyltoluene, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, These include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, methacrylonitrile, vinyl acetate, and the like.

The proportion of the monomer having an acetoacetyl group and the monomer copolymerized therewith is 99 mol % to 20 mol % of the monomer having an acetoacetyl group. If the proportion of the monomer having an acetyl group is more than 99 mol%, it is difficult to obtain a stable polymer, and if it is less than 20 mol%, the outflow rate of copper ions will be slow if the monomer used in combination is water-insoluble. Therefore, it is difficult to obtain the desired antifouling effect. A more suitable proportion is 95 mol%
Below, it is 50 mol% or more.

[0024] For polymerization, various conventional methods are applied, but the proportion of monomers having an acetoacetyl group used is 50 mol%.
In such cases, it is appropriate to use a chain transfer agent, typically a mercaptan, in an amount of 1% by weight or more in order to avoid an increase in viscosity at the final stage of polymerization as described above.

[0025] Another method for producing a polymer having an acetoacetyl group is to acetoacetylate a polymer having a hydroxyl group; Examples include saponified products of polyvinyl acetate or copolymers thereof, or acetals, formals, and butyralized polymers thereof. The reaction between a polymer having hydroxyl groups and diketene is carried out in a closed container at 60°C.
It is carried out at a temperature of around 100° C. in the presence of a catalyst such as an organic tin compound or a tertiary amine. In the present invention, the antifouling effect is dramatically improved by further adding thiabendazole to the antifouling component of cuprous oxide-rosin.

[0026] A suitable blend of the antifouling component varies depending on the environment such as the use and the place of use, but generally the amount of cuprous oxide is 100 to 300 parts by weight per 100 parts by weight of the multi-component copolymer as the vehicle component. parts, rosin, preferably WW grade rosin, 10 to 50 parts by weight, thiabendazole, 0.5 parts by weight.
~20 parts by weight, and this is dissolved and adjusted to an appropriate viscosity with a solvent that dissolves a multi-component copolymer, such as toluene or xylene, to form an antifouling paint. If the blending amount is outside this range, the antifouling ability will be reduced or the coating will become expensive, otherwise problems such as peeling of the paint film and difficulty in painting may occur, and even if the antifouling ability is present, it is not desirable as a paint.

[0027] The production method for producing a paint from these components is not limited, but the following method can be used. Multi-component copolymer polymer (concentration 40-55% by weight, viscosity 70
00-8500 cp, using toluene/xylene as solvent) 150-25 parts of cuprous oxide per 100 parts by weight as solid content
Add a mixture of 0 parts by weight, 20 to 35 parts by weight of rosin, and 10 to 20 parts by weight of thiabendazole, put this in a closed mixer, stir at high speed for 15 minutes, and then add a solvent to reduce the viscosity to 12 to 15 in a Ford cup No. 4. Adjust to 100% and use as antifouling paint for fishing nets, etc. Furthermore, when used as an antifouling paint for plants, etc., the viscosity may be higher than this. It goes without saying that the antifouling coating composition of the present invention may contain fillers, colorants, polymers, oligomers, and antifouling agents other than copper compounds, if necessary.

[0028]

[Effect] As a result of experiments, the effects of the specific combination of paint specified in the present invention in the antifouling paint composition of the present invention have only been discovered; however, the effects of the multi-component copolymer and each antifouling component are still detailed. has not been elucidated. Although it is presumed, the formation of a chelate bond between the acetoacetyl group and the copper compound, the regeneration of the hydroxyl group by promoting the hydrolysis of the acetoacetyl group in an alkaline aqueous solution, and the associated increase in the water solubility of the polymer. I believe that the facts have some kind of relationship.

[0029]

EXAMPLES Next, examples will be shown below to help understand the present invention.

(Example 1) Copolymer polymer [A] (
2-acetoacetylethyl methacrylate/styrene)
Synthesis of 340 g of 2-acetoacetylethyl methacrylate, 40 g of styrene, 60 g of toluene, 320 g of methyl ethyl ketone, and 2.4 g of azobisisobutyronitrile in a 1 liter separable flask equipped with a stirrer, reflux condenser, thermometer, and gas inlet tube. , dodecanethiol 3.8
g was charged and polymerized in a nitrogen gas stream at 65 to 70°C for 8 hours. During this time, 0.7 g of azobisisobutyronitrile was added every 2 hours. 2-acetoacetylethyl methacrylate (80 mol%) and styrene (20 mol%)
A copolymer [A] was obtained. The color was slightly yellow, the polymer concentration was 49.7%, and the viscosity was 9000 cp.

(Example 2) Synthesis of copolymer [B] 315 g of 2-acetoacetylethyl acrylate and 55 g of butyl acrylate were placed in a 1-liter separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer.
g, acrylonitrile 10g, t-butyl lauryl mercaptan 2g, toluene 60g, methyl ethyl ketone 3
20g of azobisisobutyronitrile and 2.4g of azobisisobutyronitrile were charged, and polymerization was carried out at 70 to 75°C for 8 hours in a nitrogen stream. During the process, 0.7 g of azobisisobutyronitrile was added every 2 hours. The polymerization rate was about 93% and the number average molecular weight was 64,000. Pale yellow, polymer concentration 50.1%, viscosity 4000
A copolymer of cp [B] was obtained.

(Example 3) Synthesis of copolymer [C] Using the composition shown in Table 1, the reaction was carried out in the same manner as in Example 2, and copolymer [C] having a polymer concentration of 50.4% and a viscosity of 4700 cp was prepared. Obtained.

[0033]

(Comparative Example 1) The polymerizable monomers shown in Table 2 below were placed in the same 1 liter four-necked flask as in Example 1, and polymerization was then carried out under the same conditions and procedures as in Example 1, resulting in multi-component copolymerization. Polymer 1 was obtained. In Comparative Example 1, the same amounts of toluene, methyl ethyl ketone and azobylisobutyronitrile as in Example 1 were used.

Table 2

<Formulation of antifouling paint> Based on the composition shown in Table 3, an antifouling paint was prepared using the multi-component copolymer polymers of Examples 1 to 3 and the multi-component copolymer polymer of Comparative Example 1, and the results are shown below. A comparative study of performance was conducted according to the following procedures. The test method was to twist 60 test nets of polyethylene knotless nets onto the paint adjusted to 12 to 15 seconds using Ford Cup No. 4.
Impregnate (20 seconds) a knot (400 mm x 400 mm),
After taking it out, it was dried in the sun. Coating rate = [(dry weight of net after coating - weight of net before coating)/(weight of net before coating)] x 100.

Test net: 60 polyethylene knotless nets twisted with 6 knots (400
mm x 400mm)

Table 4 shows the results of marine experiments on antifouling paints for fishing nets.

*Control area is untreated Test date: April 28, 1990 to July 27, 1990 (3 months) Test location: Fukura, Nandan-cho, Mihara-gun, Hyogo Prefecture (suspended water depth: 1.
5m) Enter the adhesion rate of sessile organisms in the evaluation standard control area as a percentage (total 100%)
) ◎: No adhesion ○: Adhesion is within 1/3 of the control area △: 〃 Within 2/3 ×:
〃 2/3 or more

[0040] Algae: Ulva Amphipod: Warekara Ascidians: Ascidians Bryozoa: Bryozoa Barnacle: Barnacle

[0041]

[Effects of the Invention] Although the effects of the antifouling paint composition of the present invention cannot be elucidated, the vehicle component is easy to manufacture, and the antifouling component is simply a combination of cuprous oxide, rosin, and thiabendazole. The active ingredients of paint can be produced cheaply and easily. In particular, despite being inexpensive and easy to obtain, the antifouling effect can be maintained for a long period of time, the toxicity to fish is at the same level as conventional products, and the object to be coated, especially bending, is required. It is an excellent antifouling paint, as it has sufficient adhesion to fishing nets, etc., and its workability is no different from conventional products.

Claims (3)

[Claims] [Claim 1] [A] The form of the final copolymer is (1) a monomer having an acetoacetyl group, and (2) a monomer having an acetoacetyl group;
) A polymer having an acetoacetyl group obtained by copolymerizing this with at least one type of copolymerizable monomer is used as a vehicle component, and [B] cuprous oxide, rosin, and thiabendazole are added. An antifouling paint composition characterized by containing it as an antifouling component. Claim 2: The form of the final copolymer is an acetoacetyl group-containing polymer in which the monomer having an acetoacetyl group accounts for 99 to 20 mol%, and the monomer copolymerizable with this copolymerizable monomer accounts for 1 to 80 mol%. Item 1. The antifouling paint composition according to item 1. [Claim 3] Polymer 1 having an acetoacetyl group
00 parts by weight, 100 to 300 parts by weight of cuprous oxide, 10 to 50 parts by weight of rosin, and 0.5 to 20 parts by weight of thiabendazole.
The antifouling paint composition according to claim 1, wherein the antifouling paint composition is blended in parts by weight.