JPH0374614B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to the structure of an antifouling sheet applied to seawater contact surfaces of ships, marine structures, etc. for the purpose of preventing marine organisms from adhering to the seawater contact surfaces. <Conventional technology> Conventionally, in ships, marine structures, equipment that uses seawater, and industries that use seawater that come into contact with seawater, barnacles, liverworts,
Due to the attachment and growth of celluloids and ascidians, their functions are impaired and often cause serious damage. For this reason, much research has been conducted on preventing the attached growth of seawater organisms. Among these, a method using a paint containing a toxic antifouling agent dispersed therein is generally used. <Problems to be Solved by the Invention> However, this method involves the complexity of painting work and the danger of organic solvent scattering, and cannot be said to be a complete prevention method. Also, methods using oligomer room temperature curing silicone rubber alone or silicone rubber and a low critical surface tension substance are known as non-toxic antifouling agents.
This is also a paint and has the same problems as the above-mentioned toxic antifouling agents, such as the complexity of the painting process and the use of organic solvents. Furthermore, since this non-toxic antifouling agent cures at room temperature, it also has the disadvantage that it takes a long time to form a film. As a method to solve these drawbacks, antifouling agents are also being considered in the form of sheets, which improve workability during antifouling construction and are more economical during production. However, the substance contained in the sheet-shaped antifouling agent that develops and maintains the antifouling effect migrates to the side of the antifouling agent sheet that adheres to the adhesive, significantly reducing the adhesion with the adhesive. It has this drawback. <Means for Solving the Problems> As a result of intensive studies by the present inventors to solve the problems and drawbacks of conventional antifouling agents as described above,
The present invention was achieved by successfully preventing the deterioration of the adhesive property of the antifouling sheet to the adhesive. That is, in this invention, when adhering an antifouling sheet to a surface to be antifouled using an adhesive, the antifouling agent in the antifouling layer is placed between the adhesive of the antifouling sheet and the antifouling layer. It is provided with a shielding layer that prevents the components from migrating to the adhesive side, thereby effectively preventing the deterioration of the adhesion of the antifouling sheet to the surface of the object to be antifouled. be. <Function> As the antifouling agent in the present invention, conventional antifouling agent compositions containing tin compounds and copper compounds are also used, but more preferably moldable materials and compositions that are essentially incompatible therewith are used. Mixtures with substances that lower the critical surface tension, i.e. oligomeric cold-curing silicone rubbers, polyethylene, polypropylene, polyvinyl chloride, chlorosulfonated polyethylene, saturated polyesters, natural rubber, butyl rubber, SIS,
Using a mixture of molding materials such as SBS and ethylene-propylene terpolymer (EPT) and low critical surface tension substances such as silicone oil, liquid paraffin, petrolactam, petrolatum, and low molecular weight terfluoroethylene, these are formed into sheets or films. Obtained by molding. As the adhesive, a material with an adhesive function such as a known adhesive liquid such as epoxy resin, or a thermosetting or chemical reaction-curing type adhesive film may be used, but if the surface to be antifouled is an underwater structure. In this case, an adhesive made of an underwater curable epoxy resin composition is suitable because it is necessary to be able to perform adhesive work in water and have an adhesive function. In addition, as a shielding layer formed between the adhesive layer and the antifouling layer to prevent the antifouling component in the antifouling layer from migrating to the adhesive side, Any material may be used as long as it is resistant to penetration, such as metal foil such as aluminum, film or resin with a high glass transition point such as polyester or polyimide. In addition to the above-mentioned antifouling layer, shielding layer, and adhesive layer, porous woven fabrics or nonwoven fabrics are used as constituent components in order to facilitate the production of the antifouling sheet and to fully exhibit its properties. Alternatively, a water-soluble protective film may be provided on the surface of the antifouling layer to prevent damage to the antifouling sheet after it is manufactured and before it is applied. In particular, when using a mixture of a moldable material and a substance that is essentially incompatible with the material and lowers the critical surface tension for the antifouling layer, the antifouling agent component in the antifouling layer may migrate. It is also preferable to provide a porous layer between the shielding layer to be prevented and the antifouling layer. <Examples> The present invention will be explained below using examples. Example 1 A composition consisting of 100 parts of addition-reactive silicone rubber and 20 parts of liquid paraffin was applied to a shielding layer obtained by laminating polyester woven fabric on both sides of a saturated polyester crosslinked with an isocyanate component, and heated at 100°C.
It was cured for 15 minutes to obtain an antifouling sheet. Next, the underwater curing epoxy adhesive composition was applied to a steel plate in seawater, and the antifouling sheet obtained above was attached thereon. Example 2 An Al film treated with Al oxide was used as a shielding layer, and after a base treatment was applied to this shielding layer, a tributyltin-based antifouling film was formed thereon to obtain an antifouling sheet. Next, this antifouling sheet was attached to a steel plate via a two-component epoxy adhesive composition in the atmosphere. Example 3 A shielding layer was created by laminating glass cloth on both sides of a heat-activated polyamide resin. Separately, on one side of water-soluble polyvinyl alcohol, a mixture of 100 parts of oligomeric room-temperature curing silicone rubber and 10 parts of perfluoroethylene activator was prepared, and this was formed into a film. was laminated to obtain an antifouling sheet. Next, an underwater curable epoxy adhesive composition was applied to the steel plate in seawater, and the antifouling sheet prepared above was attached thereto. Example 4 A shielding layer was prepared by laminating a polyester woven fabric on one side of a saturated polyester resin sheet crosslinked with isocyanate and containing a polymerization accelerator. Separately, a film made of a mixture of 100 parts of acrylic rubber copolymerized with butyl acrylate and acrylonitrile and 15 parts of polydimethylsiloxane was prepared as an antifouling layer on the polyester woven fabric of the shielding layer obtained above. Next, an antifouling sheet was attached to the anticorrosion-treated steel plate through redox reaction polymerization in the atmosphere using an acrylic adhesive containing a polymerization initiator. Comparative Example 1 A film of a mixture of 100 parts of oligomeric room-temperature curing silicone rubber and 10 parts of perfluoroethylene activator was formed on one side of a film made of water-soluble polyvinyl alcohol, and this was used as an antifouling sheet.
This was attached to a steel plate in seawater via an underwater curable epoxy adhesive composition. Comparative Example 2 A composition consisting of 100 parts of addition-reactive silicone rubber and 20 parts of liquid paraffin was coated on one side of a water-soluble polyvinyl alcohol film and cured at 100° C. for 15 minutes to prepare an antifouling sheet. This antifouling sheet was then attached to a steel plate in the same manner as in Comparative Example 1. Comparative Example 3 Acrylic rubber with butyl acrylate-acrylonitrile copolymerized on one side of polyester woven fabric
An antifouling sheet was obtained by coating a mixture of 100 parts of polydimethylsiloxane and 15 parts of polydimethylsiloxane. This antifouling sheet was then attached to a steel plate using a two-component epoxy adhesive composition in the atmosphere. The initial adhesive strength, the adhesive strength after being immersed in the sea for one year, and the adhesion state of marine organisms were measured for the steel plates attached with the antifouling sheets of Examples 1 to 4 and Comparative Examples 1 to 3. The results in the table were obtained.

[Table] <Effects> From the above table, it can be seen that the antifouling sheet of the present invention has a shielding layer between the adhesive layer and the antifouling layer to prevent the antifouling component in the antifouling layer from migrating to the adhesive layer. Because it was interposed, the initial adhesive strength, the adhesive strength after being immersed in the sea for one year,
Both showed excellent values with no significant difference, and it was recognized that excellent antifouling properties were maintained even after one year.

Claims (1)

[Scope of Claims] 1. An antifouling agent characterized in that when adhering an antifouling layer to a portion to be antifouled using an adhesive, a shielding layer is provided between the adhesive and the antifouling layer. sheet. 2. The antifouling sheet according to claim 1, wherein the antifouling layer is a mixture of a moldable material and a substance that is essentially incompatible with the material and lowers the critical surface tension. . 3. Claim 1 or 2, characterized in that a porous layer is provided between the antifouling layer and the shielding layer.
Antifouling sheet as described in section. 4. The antifouling sheet according to claim 1, wherein the portion to be antifouled is an underwater structure, and the adhesive is made of an underwater curable epoxy resin.