JPS6067580A - Method for bonding antistaining sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming an antifouling layer for the purpose of preventing shellfish and algae from adhering to parts of ships, marine structures, etc. that come into contact with seawater.

In general, parts of ships, marine structures, etc. that come into contact with seawater are coated with a paint-type anti-corrosion coating and then overcoated with antifouling paint.
Prevents algae from attaching. However, this method
It is not a perfect method because of the toxicity of the antifouling agent itself and the scattering of organic solvents during painting.

Additionally, polyolefin-coated steel is often used in applications such as seawater intake pipes. Although this polyolefin coating has a sufficient anticorrosion effect, a large amount of shellfish, algae, etc. may adhere to the water-retaining parts of the pipe. Furthermore, polyolefin coatings have low surface energy and have weak adhesion even when overcoated with the above-mentioned antifouling paint, making it difficult to expect long-term durability.

The inventors have completed the present invention as a result of intensive studies on methods for preventing stains on ships and marine structures as described above.

That is, in forming an antifouling layer on the surface of the antifouling material, the present invention uses an antifouling sheet formed by forming an antifouling layer on one side of a polymer film in advance, and then applying the antifouling sheet to the surface of the antifouling material. A method of adhering the polymer film to the other surface of the sheet having an antifouling layer formed on one side or the surface of the antifouling material by dissolving or swelling the polymer film to make it sticky. A liquid material mainly composed of monomers and/or oligomers is applied, and at that time, either the polymer film or the liquid material contains a polymerization initiator and the other contains a polymerization accelerator, and this sheet A method for adhering an antifouling sheet, comprising: pressing onto the surface of the antifouling material such that the liquid material is interposed between the antifouling material and the polymer film, and polymerizing the liquid material. This is related to.

According to the above-mentioned method of the present invention, the polymer film in the antifouling sheet is dissolved or swollen by the liquid material and becomes sticky, and at the same time, the liquid material is polymerized by the action of the polymerization initiator and the polymerization accelerator. It cures and exhibits useful adhesion. In particular, according to the adhesion method of the present invention, although the reason is not clear, the antifouling material exhibits useful adhesion even to low-energy surfaces such as polyolefin coatings, which was previously thought to be impossible. This is completely new knowledge. The present invention will be explained in detail below.

First, in forming an antifouling layer on one side of a polymer film, which will be described later, in the antifouling sheet used in this invention, either the polymer film or the antifouling layer may be formed first. Of course, the present invention also includes a method in which an antifouling layer is formed on a base material such as a nonwoven fabric, or another type of plastic sheet, and a polymer film is formed on the back surface of this base material.

In addition, when applying this invention method to a polyolefin-coated surface, sanding, chromic acid mixture treatment, corona treatment, etc.
Known pretreatments such as hot air treatment, flame treatment, caging treatment, and ultraviolet treatment may be applied, or silicone resin, silane coupling agent, epoxy resin, organic titanium,
Polyethyleneimine, polyisocyanate, etc. may be applied as a primer, or such pretreatment and a primer may be used together.

Next, vinyl monomers and/or oligomers were selected as the main components of the liquid material used in this invention because they dissolve or swell the polymer film, make it sticky, and then harden it by hardening. It was selected because it is the most suitable material for the mechanism that leads to strong adhesion. The vinyl monomer and/or oligomer can be used regardless of whether it is -functional or polyfunctional, as long as it is polymerized by active radicals generated by decomposition of the polymerization initiator. Specific examples are as follows.

Monofunctional vinyl monomers; e.g. methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, alkyl or cycloalkyl acrylate or methacrylate such as lauryl (meth)acrylate;
(such as vinyl acetate, vinyl propionate, (meth)acrylonitrile, styrene, vinyltoluene, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate
Hydroxy ester of meth)acrylic acid, glycidyl (
meth)acrylate, diethylaminoethyl(meth)acrylate, etc.

Polyfunctional vinyl monomer; e.g. ethylene glycol di(
meth)acrylate, diethylene glycol di(meth)
acrylate, ethylene glycol or propylene glycol diester of (meth)acrylic acid such as triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, and the like.

- Functional oligomers; for example, polyester mono(meth)acrylates obtained by reaction of polyester resins with (meth)acrylic acid.

Polyfunctional oligomers: for example, polyethylene glycol di(meth)acrylate, epoxy (meth)acrylate obtained by the reaction of an epoxy resin and (meth)acrylic acid, obtained by the reaction of a polyisocyanate compound and hydroxyacrylic (meth)acrylate Urethane (meth)acrylate, polyether di(meth)acrylate or polyester di(meth)acrylate obtained by reaction of polyester resin and (meth)acrylic acid
acrylate etc.

These liquid materials mainly composed of vinyl monomers and/or oligomers are composed of one or more of the above-mentioned vinyl monomers and/or oligomers, but their viscosity is determined in consideration of coating workability. , 0.01 to 100 poise, preferably adjusted to a range of 50 poise or less. Moreover, this liquid substance is applied to the interface between the polymer film and the antifouling material with a thickness of 1 to 500 μm based on the thickness of the polymer film of 100 μm. /m2, preferably 10-300
It is applied in the range of

Furthermore, at least the surface layer of the polymer film (or sheet) is activated by being dissolved or swollen in a liquid material mainly composed of the vinyl monomer and/or oligomer, such as natural rubber, impregnated rubber, etc. , rubbers such as chloroprene rubber, nitrile rubber, butadiene-styrene copolymer rubber, acrylic rubber, and/or polyester resins, chlorosulfonated polyethylene resins,
Processing of a film (or sheet) with a thickness of 5 to 5000 μm made of synthetic resin such as polybutyral resin, polyacrylic resin, polyether resin, polyamide resin, polyurethane resin, and the above-mentioned rubbers and/or synthetic resins. Examples include foam films, synthetic papers, non-woven fabrics, woven fabrics, etc. Particularly preferred are those selected from the group of polyester resins, chlorosulfonated polyethylene resins, and polyacrylic resins.

The polymerization initiator blended into either the liquid material or the polymer film decomposes through a redox reaction of the polymerization accelerator to generate active radicals and polymerizes the liquid material, for example: Ketone peroxides such as methyl ethyl ketone peroxide, hydroperoxides such as cumene hydroperoxide, diacyl peroxides such as benzoyl peroxide, organic peroxides such as peroxyketals, dialkyl peroxides, peroxyesters, peroxycarbonates, etc. can be given.

This polymerization initiator is added to either the liquid material or the polymer film in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl monomer and/or oligomer. It can be blended within a range.

In order to improve the storage stability of the system containing the polymerization initiator, hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, p-benzoquinone, catechol, phenoazine picrate, t-
A polymerization inhibitor such as butylcatechol, 2-butyl-4-hydroxyanisole, and 2,6-di-tert-butyl-p-cresol can be blended in an amount less than 1710% of the polymerization initiator.

Either the liquid material or the polymer film, which does not contain a polymerization initiator, contains a polymerization accelerator that decomposes the polymerization initiator through a redox reaction and facilitates the generation of active radicals, such as dimethylaniline, dimethyl- p-
) luidine, diethyl-p-toluidine, diisopropanol-p-toluidine, cobalt naphthenate, copper naphthenate, zinc naphthenate, thiourea, acetylthiourea, sodium ascorbate, condensate of n-butyraldehyde and aniline, pentoxide Vanadium or the like is usually blended in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer and/or oligomer. If it is less than 0.1 part by weight, there is no effect of adding it, and if it exceeds 10 parts by weight, the adhesive strength decreases, which is not preferable.

As the antifouling agent used to form the antifouling layer in the antifouling sheet of the present invention, a wide variety of commonly known antifouling agents can be used, including triphenyltin hydroxide, triphenyltin chloride, triphenyltin fluoride, and triphenyltin. Acetate, triphenyl compounds such as triphenyltin methacrylate copolymer, tributyl compounds such as tributyltin fluoride, bis(tributyltin) α/α dibromsuccinate, tributyltin methacrylate copolymer, cuprous oxide, etc. Examples include copper compounds and organic compounds such as tetramethylthiuram disulfide and zinc dimethyldiocarbamate.

In addition to the above-mentioned antifouling agent, the material components for forming the antifouling layer include rosin, fatty acids, acrylic polymers, ethylene-vinyl acetate copolymers or partial suspensions thereof, polyester, etc., if necessary. One or more of vinyl chloride, styrene-butadiene rubber, chlorinated rubber, etc. can be used as the vehicle.

In this invention, the method for forming an antifouling layer containing the above-mentioned components on one side of the polymer film includes a method such as casting an antifouling layer forming material containing the above-mentioned components on one side of a previously prepared polymer film. Alternatively, the film may be formed into a sheet having a thickness of about 30 to 200 μm and then bonded to the polymer film using a suitable adhesive or not at all. In addition, when using a base material such as paper, nonwoven fabric, woven fabric, or plastic sheet as an intermediate layer, first form an antifouling layer on it as described above, and then apply it to the above-mentioned height by heating or other means. All you have to do is attach a molecular film l.

Further, depending on the case, a polymeric film-forming material may be formed into a film by a method such as casting on one side of the antifouling layer formed into a sheet.

In the method of the present invention, the liquid material is applied to the other side of the polymer film of an antifouling sheet having an antifouling layer formed on one side of the polymer film as described above. By this application, at least the surface layer of the polymer film dissolves or swells and becomes sticky. Then, in this state, the antifouling material is pressed and pasted onto the surface of the antifouling material so that the side to which the liquid material is applied is on the inside, that is, the liquid material is interposed between the antifouling material and the polymer film.

Here, the above-mentioned polymerization initiator and polymerization accelerator are separately contained between the liquid material and the polymer film, and these two components are combined during the above-mentioned application and pressure bonding to restore their original properties. It performs its functions and polymerizes liquid materials at room temperature and in some cases by adding thermal energy. Through this polymerization, the liquid material hardens, thereby firmly adhering and fixing the antifouling sheet to the surface of the antifouling material. That is, an antifouling layer is firmly bonded and formed on the surface of the antifouling material via the cured liquid and the polymer film.

In addition, in the above method, the liquid is applied to the other side of the polymer film on which the antifouling layer is formed on one side of the antifouling sheet, but instead of this application, the liquid is applied to the surface of the antifouling material. The liquid substance is applied between the polymer film of the antifouling sheet and the surface of the antifouling material in the same way as above, so that the side on which the antifouling layer is not formed is on the inside. As described above, the antifouling sheet may be pressure-bonded, and in this case as well, the same adhesive effect as described above can be obtained.

In summary, according to the method of the present invention, the following effects can be obtained.

(b) Since it uses an antifouling sheet with an antifouling layer formed on one side of a polymer film in advance to a uniform thickness, it requires skill to perform antifouling treatment to provide a uniform thickness for the material to be antifouled. You can do it without any problems.

(b) Since a useful adhesive force is obtained by polymerizing and curing the liquid, it becomes possible to perform antifouling treatment on materials to be antifouled, such as polyolefin-coated steel, which are difficult to be antifouled using conventional methods.

? Sai: The liquid dissolves or swells the polymer film and penetrates to the interface between the polymer film and the antifouling layer, improving the adhesion of the antifouling layer to the antifouling material, and the subsequent curing creates a strong bond. do.

B) Since the antifouling layer is a solid layer in advance, it can be applied during antifouling treatment without scattering a large amount of organic solvent as in conventional antifouling paints.

) The physical properties of the adhesive layer can be controlled by selecting the type of polymer film, vinyl monomer and/or oligomer, polymerization initiator, and polymerization accelerator.

Hereinafter, the effects of this invention will be explained in more detail using Examples. In addition, in the following, parts mean parts by weight.

EXAMPLE Steel plates subjected to the following three types of antifouling treatments: fal, fb), and (c) were manufactured.

(a) 15 parts of triphenyltin hydroxide and 100 parts of ethylene-vinyl acetate copolymer were mixed using a mixer and then extruded into a sheet having a thickness of 100 μm.

On the other hand, 100 parts of polyester resin, 3 parts of cumene hydroperoxide, methyl ethyl ketone:toluene = 1
4 (weight ratio) to make 40% by weight, and apply this on release paper so that the thickness after drying is 100 μm, 6
It was dried at 0° C. for 10 minutes to obtain a polyester resin film.

A molded sheet containing the antifouling agent was pressed onto one side of the polyester resin film at 130°C to obtain an antifouling sheet.

On the other hand, a liquid material consisting of 20 parts of polyester polymethacrylate, 60 parts of methyl methacrylate, 20 parts of ethyl acrylate, and 8 parts of dimethylaniline was prepared.

The above liquid material was uniformly applied to the surface of the antifouling sheet on which the antifouling layer of the polymer film was not provided, at a coating amount of 50 g/m2, to form an adhesive.

Steel plate (8QQmm x 100m) cleaned with Triclean in advance
The above adhesive antifouling sheet was attached to both sides of a steel sheet (mx 8 mm) with the side to which the liquid material was applied inside, the liquid material was cured at room temperature, and the steel plate was subjected to antifouling treatment.

(bl 100 parts of chlorosulfonated polyethylene resin,
5 parts of dimethyl-p-toluidine was added to 35 parts of dimethyl-p-toluidine using toluene.
% by weight, and place it on release paper to a thickness of 85 μm after drying.
The film was coated to give a coating film of m and dried at 50° C. for 12 minutes to obtain a chlorosulfonated polyethylene resin film.

On the other hand, with a monomer composition of 35 parts of tributyltin methacrylate, 35 parts of methyl methacrylate, and 30 parts of butyl methacrylate, 0 parts of azoisobutyronitrile was added in xylene.
．． After adding 30 parts of cuprous oxide and 5 parts of rosin to a polymer with a solid content of 35% by weight, which was polymerized using 5 parts of an initiator, the mixture was coated on release paper to a dry thickness of 110 μm to form a protective coating. A sheet-like material containing a staining agent was obtained. This was pressure-bonded to the chlorosulfonated polyethylene resin film at 120° C. to obtain an antifouling sheet.

On the other hand, a liquid material consisting of 80 parts of methyl methacrylate, 20 parts of ethyl acrylate, and 5 parts of benzoyl peroxide was prepared.

A polyolefin-coated steel plate (300 mm x 1
00mm x 8mm).
The surface of the antifouling sheet on which the antifouling layer was not provided was attached to this, and the antifouling sheet was cured at room temperature to obtain an antifouling-treated polyolefin-coated steel plate.

fcl A sheet-like material containing the same antifouling agent as above (bl) was applied to one side of the nonwoven fabric, and the same polymer film as fbl was pressure-bonded to the other side of the nonwoven fabric at 120°C.

On the other hand, a liquid material containing 70 parts of methyl methacrylate, 25 parts of butyl acrylate, 5 parts of ethyl acrylate, and 4 parts of benzoyl peroxide was prepared. This liquid material was applied to a thickness of 60 μm on the side of the antifouling sheet on which the antifouling layer of the polymer film was not provided, and the polyolefin-coated steel plate (800 mm
x 100 mm x 8 mm) and cured at room temperature to obtain an antifouling treated polyolefin coated steel plate.

The steel plates and polyolefin-coated steel plates obtained in steps [a) to fc) above that had been antifouled by the method of the present invention and the untreated polyolefin steel plates were immersed in the sea for two years.

As a result, there was no adhesion of shellfish or algae to the steel sheets and polyolefin-coated steel sheets obtained in (a) to (cl);
Some shellfish on untreated polyolefin steel plate.

Adhesion of algae was observed. From the above, it can be seen that the effects of the present invention are extremely significant.

Claims (2)

[Claims] (1) When forming an antifouling layer on the surface of the antifouling material, use an antifouling sheet made by forming an antifouling layer on one side of a polymer film in advance and adhere it to the surface of the antifouling material. A vinyl monomer that dissolves or swells the polymer film on the other surface of the sheet having an antifouling layer formed thereon or on the surface of the antifouling material to make it sticky. and/or a liquid material containing an oligomer as a product is applied, at which time either the polymer film or the liquid material contains a polymerization initiator and the other contains a polymerization accelerator, and this sheet is coated with the above-mentioned coated material. A method for adhering an antifouling sheet, which comprises pressing onto the surface of an antifouling material such that the liquid material is interposed between the antifouling material and a polymer film, and polymerizing the liquid material. (2) The method for adhering an antifouling sheet according to claim (1), wherein the antifouling material is polyolefin-coated steel.