JPS61126002A - Aquatic antifouling laminate - Google Patents

Abstract

PURPOSE:To provide the titled laminate capable of preventing the adhesion of aquatic adhesive life especially to the ship, marine construction, water- channel, etc., for a long period, and applicable easily to a construction to be treated, by laminating an adhesive layer to a surface of a polymer sheet or tape, and applying an aquatic antifouling layer to the other surface of the sheet, etc. CONSTITUTION:One surface of a sheet or a tape of a polymer such as ethylene- propylene-diene rubber is coated with a layer of a pressure-sensitive adhesive composed of a rubber or a synthetic resin, or an activating adhesive, and if necessary, covered with a releasing paper. The other surface of the sheet, etc., is coated with an aquatic antifouling layer containing an active antifouling component having the constituent unit of formula -SnR3 (R is 1-10C hydrocarbon group) in the layer for suppressing (or preventing) the adhesion of aquatic life such as barnacle, agar, etc. EFFECT:The laminate can be applied easily, and has excellent antifouling effect. It can be bonded firmly and used in the construction or the part to be protected from the adhesion of aquatic life in the sea, river, lake, and various circulating water systems.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an underwater antifouling multi-layered product, particularly for the purpose of preventing the adhesion of aquatic sessile organisms that adhere to ships, the sea, structures using seawater, and waterways. Related to antifouling multilayered materials.

[Conventional technology]

Examples of harm caused by biofouling in the ocean include a decrease in ship speed and an increase in fuel consumption due to an increase in the resistance of the thick part of the ship's hull.

In addition, in structures that use seawater, the corrosion protection film is destroyed due to the ingestion of living organisms, and this leads to the promotion of rust. Furthermore, in waterways, waterways are clogged due to adhesion of aquatic periphyton.

In the past, various antifouling paints have been developed for the purpose of preventing the adhesion of aquatic fouling organisms to ships, underwater or seawater-using structures, rough spots, and waterways. I am doing it.

However, since antifouling paint uses a solvent, it takes time to dry after painting. In particular, additional time is required when applying a coat to provide long-term stain resistance.

Furthermore, it has the disadvantage that the working environment is limited due to the risk of ignition or poisoning due to the solvent during painting.

[Problem that the invention seeks to solve]

An object of the present invention is to eliminate the above-mentioned drawbacks, to provide an underwater antifouling waste material that is easy to install and has excellent antifouling performance.

Other objects and novel features of the present invention will become apparent from the entire description of this specification.

c. Means for Solving Problems] The underwater antifouling multilayer product of the present invention is provided with an adhesive layer on one side of a polymeric sheet or tape, and if necessary, a release paper is attached to the surface of the adhesive layer. The other surface of the sheet or tape is provided with an underwater antifouling layer that suppresses (prevents) the adhesion of the above-mentioned aquatic sessile organisms such as Fujibo and seaweed.

The polymeric sheet or tape used in the present invention is, for example, one or two types of rubber such as ethylene-propylene-diene rubber, butyl rubber, chlorinated polyethylene rubber, ethylene-vinyl copolymer rubber, silicone rubber, and urethane rubber. and/or polyvinyl chloride, polyethylene, ethylene-vinyl acetate, ethylene-methyl methacrylate, ethylene-maleic anhydride, ethylene-
Copolymers such as methacrylic acid-maleic anhydride, ionomers, polyethylene modified with maleic anhydride or glycidyl methacrylate, polypropylene, propylene-ethylene copolymers, modified polypropylene with maleic anhydride, polyesters such as polyethylene-terephthalate, etc. , 6-nylon, polyamide such as 6.6-nylon, or synthetic resin such as aramid, etc. Sheets or tapes with a thickness of 0.05 to 5 mm, including: A reinforcing base material such as nonwoven fabric, paper, cloth, metal sheet, or plastic film is fixed to or interposed on the surface or in the middle of the sheet or tape-like material, Rurui, silica, Merck, magnesium carbonate, mica, carbon black, Fillers such as glass fiber can be added to make various products.

The adhesive layer provided on one side of the polymeric sheet or tape may be made of, for example, a rubber-based or synthetic resin-based pressure-sensitive adhesive, an activation-type adhesive, or a hot-melt adhesive. configured.

The underwater antifouling layer used in the present invention is a layer that has the effect of suppressing the adhesion of aquatic sessile organisms such as Fujibo, seaweed, and slime, and contains a conventionally known antifouling agent as an active ingredient. It can be formed using

That is, examples of inorganic antifouling agents include cuprous oxide and copper rhodan. N as an organic antifouling agent
-(chlorophenyl) α, α' dibromosuccinimide, tetrachloroisophtanitrile, 5-chloro-4-phenyl-1,2-dithiol-5-one, 2,5,5.
Examples of the organometallic antifouling agent include 6-titrachloro-4-(methylsulfonyl)hyridine and organotin compounds. To explain in more detail, the following formula (
+1 S n f'+ 3 ... (contains a structural unit represented by 11 (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms)).

Preferred examples of the active ingredients of the underwater antifouling layer of the present invention are as follows.

That is, preferably -8n shown in the above formula (1)
The R3 structural unit is in the form of -COO8nFl=・=-T2+ in the polymer,
It is present in an amount of 50% or more of the amount of tin.

More preferably, -COO8 represented by the above formula (2)
n Rs is ■ C=Q OS n Rs (however, K represents H or CH3) or XO019n Rs (however, X represents H, 5nR3, or an alkyl group or aryl group having 1 to 16 carbon atoms, -OH .

-8) J, x -? It may have layer bonds, halogen, carbonyl, ester, or amide bonds. ).

Particularly preferably, considering the bending resistance during sheet or tape winding, the ethylene structural unit and -COOSn
For example, /l//f:, +cH2-cH2+constituent unit and (3
1 or (4), where +CH2-cH2÷constituent unit is 60~
It is preferable that the structural units represented by formula (3) or (4) account for 98 mol% and 40 to 2 mol%, but it is not necessarily necessary that all of the latter structural units are substituted, for example. , R'H.

The above active ingredients include talc powder, barium sulfate, Bengara, zinc oxide, bentonite, titanium white, phthalocyanine blue,
Pigments such as silica powder Polyvinyl chloride, polyvinyl acetate, acrylic resin, polyethylene, ethylene vinyl acetate, ethylene-methyl methacrylate, ethylene-maleic anhydride copolymers, ionomers, maleic anhydride or glycidyl meta-modification of polyethylene Polypropylene, propylene-ethylene copolymers, modified products of polypropylene such as maleic anhydride, resins such as polyesters and polyamides, mica, carbon black, fillers such as glass fibers, etc. may be used in combination. The amount of active ingredient used is at least 30 parts by weight, preferably 50 parts by weight. .

Furthermore, when the active ingredient is used in combination with suboxide steel, the effect of preventing the adhesion of aquatic fouling organisms is enhanced and is even more effective. The amount of cuprous oxide used is 60/40 to 5/5 in terms of the weight ratio of the active ingredient.
97 (cuprous oxide/the active ingredient).

To provide the above antifouling agent as an underwater antifouling layer on a polymer sheet or tape, vinyl chloride, vinyl acetate, epoxy resin, synthetic rubber, etc. may be used as a paint, or thermoplastic resin may be used. It may also be mixed with and melt-molded to form a film or sheet, and then laminated onto a polymeric sheet or cheese.

Alternatively, the resin constituting the polymeric sheet or tape and the above-mentioned antifouling agent may be coextruded to form an underwater antifouling multilayer molded product having an antifouling layer. Various other methods can be adopted.

Underwater antifouling layer lamps are installed on the opposite side of the adhesive layer through a polymer sheet or cheap adhesive, and during construction, the adhesive layer can be applied directly to various structures requiring antifouling by peeling off the release paper or directly applying the adhesive layer. It is attached to objects or ships, and the outermost antifouling layer is brought into contact with seawater (river water), etc.

〔Example〕

Next, the present invention will be explained based on examples.

Example 1 A mixture of 70 parts of ethylene-chloropyrene rubber (parts by weight, the same applies hereinafter) and 50 parts of butyl rubber was molded with a calender roll to a thickness of 1.0 mm and a width of +000 mm L, +s.
oc' and AI heating for 25 minutes to obtain a polymer sheet.

In addition, 90 parts of maleic anhydride was added to 500 parts of Russia,
The reaction was carried out at 200C for 2 hours to obtain a reaction product (Al. The above reaction product (AI + 00 parts) was dissolved in 100 parts of xylene and 50 parts of inopropyl alcohol, and 200 parts of bis(tributyltin) oxide was stirred into the solution. A viscous liquid (Bl was obtained). This liquid (B) was applied to the above polymer sheet at a thickness of 150μ to obtain an antifouling sheet (C1). A pressure sensitive adhesive consisting of 100 parts of butyl rubber, 100 parts of calcium carbonate, 40 parts of polyterpene resin, 50 parts of asphalt and 40 parts of polybutene was applied to this sheet (at) on the back side of the surface to which the liquid (BJ was applied). 05 fin.

It was coated thickly to obtain a multilayered underwater stain resistant material.

Examples 2 to 7 Ethylene and acrylic acid copolymer (Mz=so
o, containing 12 mol% of acrylic acid > + S and xylene 10
After charging 0J3 and melting at 100C with stirring, +8j
After adding 20 ky of tributyltin compound (Bu3Sn) and 6 kg of cuprous oxide and holding at the boiling point for 5 hours to distill off about 50-e of xylene, 1002 xylene was added and the mixture was heated again at the xylene boiling point for 4 hours. Approximately 100
After distilling off the xylene, about 50 g of xylene was added to lower the temperature to 50 C. Next, 250 g of acetone solvent was added to the xylene solution to precipitate a red polymer. After removing the supernatant, acetone was added again, and after thorough washing with acetone, the mixture was dried under reduced pressure at 40C to obtain 54 kg of polymer.

The Sn content in the obtained polymer was analyzed using an atomic absorber, and the result was 16.5% by weight. IR measurement result Based on acrylic acid + 700 cm-' ν (C=0
) disappeared, and a new absorption was observed at +640 cm-1. As a result, it was confirmed that the acrylic acid group K ) IJ was bonded to dibutyltin.

This polymer was pelletized using a 30 mm diameter twin-screw extrusion system with a vent, and then the pellet was 41]+a++φT-
It was molded into a film with a thickness of 150 μm and a width of 50 cm using a gooey molding machine.

The T-Gui film was laminated to the polymer sheets or tapes shown in Table 1 below by dry lamination.

The adhesive layer was formed by applying the pressure-sensitive adhesive used in Example 1 to obtain an underwater stain-resistant multilayer product.

Table 1 Example 8 The tin-containing polymer in Example 2 was molded into ethylene-methyl methacrylate (MMA)-maleic anhydride (MAR) copolymer (yMA7wt%, M
AHL, containing 0 wt%), each thickness 0.50
．． A sheet of 1-5 ya was molded.

The pressure-sensitive adhesive used in Example 1 was applied to a thickness of 0.511II++ on the copolymer surface of the sheet to obtain an underwater antifouling sheet.

The underwater antifouling multilayer materials shown in Examples 1 to 8 were adhered to marine structures near the sea surface (range from 2 m below the sea surface at low tide to 2,711 m above the sea surface at high tide) to reduce the adhesion of aquatic organisms to 6. Although it was observed for several months, no aquatic fouling organisms were observed at all, indicating effective underwater antifouling properties.It was also easy to adhere to structures and was strong.

〔Effect of the invention〕

According to the present invention, as shown in the examples, it is not a foolproof method that can prevent the staining of structures due to the attachment of aquatic sessile organisms over a long period of time, and it is easy to adhere to structures. It was able to adhere firmly, was easy to apply, and solved various drawbacks found in antifouling paints. The underwater antifouling multi-layered material according to the present invention is useful not only in the ocean but also in rivers, lakes, and various types of circulating water, where structures and parts where adhesion of aquatic sessile organisms is a problem, are used frequently.

Claims (1)

[Scope of Claims] 1. An underwater antifouling multilayer product characterized by having an adhesive layer provided on one side of a polymeric sheet or tape and an underwater antifouling layer provided on the other side. 2. The underwater antifouling multilayer product according to claim 1, wherein a release paper is attached to the surface of the adhesive layer.