JPS61118231A - Dirt free sheet - Google Patents

Abstract

PURPOSE:To prevent adhesive properties to the surface of an article to be freed from dirt from deteriorating, by providing a shielding layer preventing transfer of an ingredient of a dirt preventive agent in a dirt preventive layer to an adhesive agent side between the adhesive agent of a dirt free sheet and said dirt preventive layer. CONSTITUTION:As for a dirt preventive agent, a mixture of a molding material such as oligomer cold-setting silicon rubber and substance having the low critical surface tension such as silicon oil is used and the same is molded into a sheet or filmlike state. As for an adhesive agent, a material having an adhesive function such as an adhesive agent liquid such as epoxy resin or heat-setting or chemical-reaction-setting type adhesive film is made to interpose. As for a shielding layer to be formed between an adhesive agent layer and a dirt preventive layer to prevent an ingredient of a dirt preventive agent in a dirt preventive layer from transferring to an adhesive agent side, it is good if it is a material hard to be dissolved into or soaked by the substance having the low critical surface tension and a metallic foil such as aluminum and a film made of polyester or polyamide whose glass point is high or resin are used.

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. It is something.

<Conventional technology> Conventionally, in ships, marine structures, equipment that uses seawater, and industries that use seawater that come into contact with seawater, Fujibushi, liverworts, Serpura, sea squirts, etc. adhere to surfaces that come in contact with seawater. In order to grow, these 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 the painting work and the risk of organic solvent scattering, so it cannot be said to be a complete prevention method.

Also known is the use of oligomer room-temperature curing silicone rubber alone or silicone rubber and a low critical surface tension substance as a non-toxic antifouling agent, but this is also a paint and is the same as the toxic antifouling agents mentioned above. It has problems such as the complexity of painting work 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 to solve problems〉, *qmisuigomsw*o"11"06
As a result of intensive studies to solve the problems or drawbacks, we succeeded in effectively preventing the deterioration of the adhesion of the antifouling sheet to the adhesive, leading to the present invention.

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. A shielding layer is provided to prevent the components from migrating to the adhesive side, and this device is intended to effectively prevent the deterioration of the adhesion of the antifouling sheet to the surface of the object to be antifouled. .

Function> Although conventional antifouling agent compositions containing tin compounds and copper compounds can be used as the antifouling agent in the present invention, it is more preferable to use moldable materials and materials that are essentially incompatible therewith. and mixtures with substances that lower the critical surface tension, i.e., oligomeric cold-curing silicone rubber, polyethylene, polypropylene, polyvinyl chloride, chlorosulfonated polyethylene,
Saturated polyester, natural rubber, butyl rubber, srs, s
BS, ethylene-propylene terpolymer (EP
Using a mixture of molding materials such as ``Ding'' and low critical surface tension substances such as silicone oil, liquid paraffin, petrolactam, petrolatum, and low molecular weight terfluoroethylene,
It can be obtained by forming these into a sheet or film.

As the adhesive, known adhesive liquid such as epoxy resin,
It is sufficient to use a material with an adhesive function such as a heat-curing or chemical reaction-curing adhesive film, but if the surface to be antifouled is an underwater structure, it is possible to use a material that can be used underwater and has a bonding function. Therefore, an adhesive made of a water-curable epoxy resin composition is suitable.

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 layer 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.

Example of implementation This invention will be explained below with reference to Examples.

Example 1 100 parts of addition reaction type silicone rubber and 20 parts of liquid paraffin
The composition consisting of 2 parts 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 cured at 100°C for 15 minutes to form 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 N film treated with N oxidation 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 in the atmosphere via a two-component engineered poxy adhesive composition.

Example 3 A shielding layer was created by laminating glass cloth on both sides of a thermally active polyamide resin.

Separately, on one side of water-soluble polyvinyl alcohol, a mixture of 100 parts of oligomeric room-temperature curing silicone rubber and 16 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, add 15 parts of polydimethylsiloxane to 100 parts of acrylic rubber copolymerized with butyl acrylate and acrylonitrile.
A film containing the above-mentioned mixture was formed 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 in the atmosphere using an acrylic adhesive containing a polymerization initiator by polymerization through a redox reaction.

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. was attached to a steel plate in seawater via an underwater curing epoxy adhesive composition.

Comparative Example 2 An antifouling sheet was prepared by applying a composition consisting of 100 parts of addition-reactive silicone rubber and 20 parts of liquid paraffin to one side of a water-soluble polyvinyl alcohol film and curing at 100° C. for 15 minutes.

This antifouling sheet was then attached to a steel plate in the same manner as in Comparative Example 1.

Comparative Example 3 One side of a polyester woven fabric was coated with a blend of 100 parts of acrylic rubber copolymerized with butyl acrylate-acrylonitrile and 15 parts of polydimethylsiloxane to obtain an antifouling sheet.

This antifouling sheet was then attached to a steel plate using a two-component engineered poxy 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 1 (Effects) From the table above, 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. As a result, both the initial adhesive strength and the adhesive strength after being immersed in the sea for one year showed excellent values with no significant difference, and it was also confirmed that it maintained excellent antifouling properties even after one year. Ta.

Claims (4)

[Claims] (1) An antifouling sheet characterized in that, when the antifouling layer is adhered to a portion to be antifouled using an adhesive, a shielding layer is provided between the adhesive and the antifouling layer. (2) 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. Dirty sheet. (3) The antifouling sheet according to claim 1 or 2, characterized in that a porous layer is provided between the antifouling layer and the shielding layer. (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.