JPH0444833A - Prevention of marine organism adhesion to frp product - Google Patents

Abstract

PURPOSE:To raise the density of a copper ion that melts into water, and enable the copper ion to melt out under stable conditions for long period by adding a specific water soluble high polymeric material suitable for gel coating and respective antifouling agents into a gel coating layer containing copper or a copper group alloy. CONSTITUTION:When copper is added as an antifouling agent into a gel coating material, a kind or more water soluble high polymeric materials selected from a group consisting of cellulose, modified starch, gelatin, gum Arabic, and locust bean gum are added to the gel coating layer. When a copper group alloy is added as an antifouling agent into a gel coating layer, a kind or more water soluble high polymeric materials selected from a group consisting of cellulose, methyl cellulose, gelatin, gum Arabic, and locust bean gum are added to the gel coating layer. For matrix resin used for the gel coating layer, in order to improve the seawater solubility of the gel coat layer, flexible orthophthalate unsaturated polyester resin is preferably used that has relatively good seawater solubility in unsaturated polyester resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is an FRP (fiber-reinforced plastic) product that prevents shellfish, algae, etc. from adhering to FRP (fiber-reinforced plastic) products in the sea.
This law concerns the law for preventing marine organisms from adhering to products.

(Prior Art) Conventionally, organic tin-based paints (tributyltin or triphenyltin-based paints) have been widely used as a method to prevent marine organisms from adhering to the surface, but although these are extremely effective when used as ship bottom paints, Due to its strong toxicity, it has recently been regulated to prevent pollution and cannot be used continuously.

Therefore, as an alternative non-polluting antifouling agent, we have utilized the fact that it has been known empirically that marine organisms do not adhere to cupola nickel (copper-nickel alloy). It is known that this can be used as a staining agent to prevent marine organisms from landing on marine structures, etc. by applying a 115-layer barrier using a PRP (fiber-reinforced plastic) gel coat method (for example, Omotesho 5
(Refer to Publication No. 7-501382).

(Problems to be Solved by the Invention) Samples of FRP boards or FRP pipes provided with an antifouling gel coat layer by the method described in Japanese Patent Publication No. 57-501382 described in the prior art were actually tested in Kagawa Prefecture. After immersing it in the sea at Naoshima and Makiminato, Okinawa Prefecture, we observed and observed the state of marine life attached to it.
For an initial period (3-4 months), something that seemed to be effective was observed, but after that, it was no different from a solid FRP board immersed in an underwater IC, and 6 months had passed since the immersion. At the time of 1, on Naoshima there were Fujibbo, Murasaki mussel,
Although many sea creatures such as oysters, oysters, and oysters were attached, and in Makiminato, barnacles were attached, there were problems in that they were not satisfactory in terms of practicality.

The reason why sea creatures stick to copper or copper-based alloys, except for the early Ippaku period, is that sea creatures do not adhere to copper or copper-based alloys because the copper ions dissolved in the water are absorbed by sea creatures. It is said that this is because the presence of copper ions acts as a repellent, but if copper or copper alloy powder is simply hardened with unsaturated polyester (4m1 nB), vinyl ester resin, epoxy resin, etc. by gel coating, these resins Because of its good seawater resistance, copper ions are leached into the water for a short period of time at the beginning, but the concentration is low and the antifouling agent is hardened with a resin that has good seawater resistance, so the copper ions continue to elute into the water. This is because the ions are not eluted.

In order to examine this from a different endothelium, a test piece cut out from a gel-coated PAL plate was immersed in a certain amount of purified water, and copper ions in the water were measured using an atomic absorption spectrometer. However, the results are as shown in Figure 2.
As can be seen from Figure 2, simple gel-coat products containing copper-nickel antifouling agents have a low level of copper ion concentration dissolved in water, and a high concentration of copper ions.
After 2 to 3 months, the concentration tends to be low. This is because the unsaturated bo9ester resin used has good seawater resistance, and the resin wraps around the copper-nickel antifouling agent. This is thought to be due to the inability to effectively dissolve copper ions over a long period of time. The unsaturated polyester resin used in this experiment was a soft orthophthalic acid polyester resin (manufactured by Hitachi Chemical Co., Ltd., PS-15), which is relatively easy to elute additives among unsaturated polyester resins. Although the resin is suitable for

In parallel with this, we also experimented with a gel coat product using an epoxy resin (Epicoat 828, manufactured by Yuka Sil Eboxy Co., Ltd.), but the results showed that it was unsaturated. IJ and v were worse than products using Nistil resin.

In addition, "the remarkable level of the 1'effect" in Figure 2 means:
Antifouling paint using the same antifouling agent (Dai [manufactured by Hontoyo Co., Ltd.,
M p -200) was temporarily applied to FRP (coating thickness approx. 2 (
)0μIT1) The results were measured under the same conditions as -) on a test piece that had been immersed in water.Although a remarkable effect was obtained as a result of the underwater immersion test, the coating melted away after about 2 years and the base layer It is exposed and the lifespan is 2 years), and it is 6 points.

The invention was made in view of the above-mentioned problem 1 of the conventional technology. The object of the present invention is to provide a method for preventing the adhesion of marine organisms to r'Rp products, which can be put to practical use by dissolving copper ions in a stable state over a long period of time.

(Means for Solving the Problem) In order to achieve the above object, the present inventors
of! As a result of soaking, a gel containing 100% copper thread alloy]
- By gel coating and adding a specific water-soluble high-grade material suitable for each antifouling agent,
It was discovered that the solubility of the gel coat layer in seawater is promoted, the concentration of copper ions dissolved in water increases, and copper ions can be dissolved for a long period of time in a more stable state, and the present invention has been achieved. is.

In other words, in the case of FP products containing steel as an antifouling agent in the gel coat layer, the method for preventing the adhesion of marine organisms of the present invention is to prevent cellulose, modified starch, gelatin, gum arabic, and locust bean gum from being added to the gel coat layer. In the case of a PBPi product that contains one or more water-soluble polymeric materials selected from the group consisting of: and also contains a copper-based alloy as an antifouling agent in the gel coat layer, cellulose, metrose, and gelatin are added in the gel coat layer. , gum arabic, and locust bean gum.

As the matrix resin used for forming the gel coat layer, in order to improve the seawater solubility of the gel coat layer, a soft orthophthalic acid-based unsaturated polyester resin, which has relatively good seawater solubility among unsaturated polyester resins, is preferable. .

In the present invention, cellulose is a derivative of cellulose that has been converted into hydroxyethyl cellulose and water-soluble, modified starch is a soluble starch obtained by oxidizing corn starch, and gum arabic is a sap secreted from the trunk of the genus Acacia in the Fabaceae family. Locust bean gum is made by removing the outer skin of beans from the legume family that grows in the Mediterranean region and pulverizing them. Metrose is a type of methylcellulose and is made by reacting cellulose with methyl chloride.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Examples 1 to 6, Comparative Examples 1 to 7 The unsaturated polyester resin was 72x resin, copper powder as an antifouling agent, and a water-soluble polymer material as an additive.
A gel coat layer (thickness approx. 8
FAP products of Examples 1 to 6 and Comparative Examples 1 to 7 were prepared, and each of the obtained FRP products was tested for gel coatability (workability, whether a good smooth surface could be obtained or not). Evaluation of whether peeling occurs) and adhesion prevention effect (
Steel ion concentration) was evaluated.

The evaluation results are shown in Table-1.

Examples 7 to 14, Comparative Examples 8 to 13 Unsaturated polyester resin was used as a matrix resin, and copper-nickel alloy powder as an antifouling agent and a water-soluble polymer material as an additive were added in the proportions shown in Table 2. Examples 7 to 14 in which gel coat layers (thickness approximately 800 μm) were formed by blending
FRP products of Comparative Examples 8 to 13 were prepared, and the resulting PAP products were evaluated for lζ gel coatability and adhesion prevention effect in the same manner as described above.

The evaluation results are shown in Table-2.

In addition, when the copper ion concentration was measured for the test pieces of each FRP product of Examples in Tables 1 and 2 above, the first
As shown in the figure, those that use copper as an antifouling agent are those that have a cellulose rust conductor (hydroxyethyl cellulose) added as a water-soluble polymer material, and those that use copper-nickel alloy as an antifouling agent. When locust bean gum and acacia cum were added as water-soluble polymer materials, the results were close to the desired level of copper ions of 1 degree. In addition, FRs subjected to gel coat treatment according to the examples in Tables 1 and 2
The P plates and PaP pipes were immersed in the sea at Mie Toba and Hitachi Port, Ibaraki Prefecture, respectively, and observed. Six months after immersion, there was no shellfish attached to Examples 1o and 11, and no other shellfish were observed. In the example, there was only slight adhesion.

In addition, among the water-soluble polymers in Tables 1 and 2, the details of gum arabic powder are unknown, but gum arabic is processed to be used as an emulsifier, thickener, and stabilizer for foods (person #4). Powdered candy is a processed starch product made from cornstarch (using processed Japanese food products), and branched dextrin is obtained by heating starch in powder form, also known as roasted starch ( (Uses Sanmatsu industrial products).

Table-1 (Blending unit: alI) Table-2 (Blending unit: 2 parts) □ (Gel coat button O: Good △: Slightly female ×: Tough/(adhesion prevention effect) O: Effective Δ: Slightly weak (However,
More effective than conventional products
, II product name) Viscosity 6th-110cps Cell C-s 5p-600 (Daicel Chemical Industry @tl!, 111i
Product name) Viscosity 48011h4000cpa Metrose 5M-16 (Shin-Etsu Chemical ei & RJi name)
Muko1113+8ep*Methods 908H-3
0000 (made by Shin-Etsu Chemical * Ijim, #1 product name) Viscosity 2
6,000-a, 5,000 eps (Effect of the Invention) As is clear from Fig. 1, the present invention improves the ability of copper to dissolve in water, compared to conventional products that simply contain copper or steel alloy antifouling agents in the gel coat layer. The increase in ion concentration improves the anti-fouling effect, and although the longevity of the antifouling effect is currently unclear, the gel coat layer itself may be at least thicker (about 2-2) than conventional coated products. Since this is possible, a significant improvement in service life can be expected.

By using a soft orthophthalic acid-based unsaturated polyester resin as the matrix resin for forming the gel coat layer, the seawater solubility of the gel coat layer is improved.
The concentration of copper ions dissolved in the water increases, further improving the effectiveness of preventing marine life from adhering.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the trends in copper ion concentration over time in Examples of the present invention, conventional products with gel foot layers containing an antifouling agent, and painted products. FIG. 2 is a diagram showing the level of dissolved copper ions and changes over time in a conventional gel coat layer using an unsaturated polyester resin as a matrix resin and a copper-nickel alloy as an antifouling agent.

Claims (1)

[Scope of Claims] 1. A method for preventing the adhesion of marine life to FRP products by forming a gel coat layer containing copper, wherein the gel coat layer contains a group consisting of cellulose, modified starch, gelatin, gum arabic, and locust bean gum. FR characterized by adding one or more water-soluble polymer materials selected from
Law for preventing marine organisms from adhering to P products. 2. In a method for preventing marine organisms from adhering to FRP products in which a gel coat layer containing a copper-based alloy is formed, a type selected from the group consisting of cellulose, metrose, gelatin, gum arabic, and locust bean gum is added to the gel coat layer. A method for preventing marine organisms from adhering to FRP products, which is characterized by adding the above water-soluble polymeric material. 3. The method for preventing marine organisms from adhering to FRP products according to claim 1 or 2, wherein the matrix resin for forming the gel coat layer is a soft orthophthalic acid-based unsaturated polyester resin.