WO2013146726A1

WO2013146726A1 - Adhesive tape for preventing adhesion of aquatic organisms

Info

Publication number: WO2013146726A1
Application number: PCT/JP2013/058676
Authority: WO
Inventors: 鈴木　聡; 内藤　友也; 太樹末吉; 倉田　直記
Original assignee: 日東電工株式会社
Priority date: 2012-03-29
Filing date: 2013-03-26
Publication date: 2013-10-03
Also published as: JP2013203924A

Abstract

Provided is an adhesive tape for preventing the adhesion of aquatic organisms, which has excellent impact resistance and can prevent the breakage or lack of a stain-proof layer caused by a collision object. The adhesive tape for preventing the adhesion of aquatic organisms according to the present invention comprises a stain-proof layer, a base layer and an adhesive layer in this order, wherein the stain-proof layer contains silica nanoparticles.

Description

Aquatic organism adhesion prevention adhesive tape

The present invention relates to an aquatic organism adhesion preventing adhesive tape. In detail, the present invention is that underwater organisms adhere to underwater structures (such as ships, buoys, harbor facilities, offshore oilfield facilities, waterways for power plant cooling water, waterways for factory cooling water, water floating passages, etc.). The present invention relates to an aquatic organism adhesion prevention adhesive tape for preventing breeding.

Underwater structures such as ships, where they come into contact with seawater, marine organisms such as barnacles, oysters, purple mussels, hydra, cell plastics, squirts, bryozoans, Aosa, Aonori, and attached diatoms grow and grow, increasing fluid resistance. It causes unfavorable conditions such as deterioration of equipment and machine performance such as deterioration of thermal conductivity and diffusion of attached marine organisms overseas. In addition, the work for removing the attached marine organisms requires a large amount of labor and enormous time, and suffers an economic loss.

In order to prevent such damage, antifouling paint has been conventionally applied to underwater structures. Antifouling paints have long contained toxic antifouling agents such as organotin compounds and now cuprous oxide. The adhesion growth of marine organisms can be almost suppressed by the toxicity of antifouling paints, but toxic antifouling agents such as organotin compounds and cuprous oxide have a considerable adverse effect on the human body and the environment. It becomes. Further, when the antifouling paint is dried after being applied, about 30% by weight of the organic solvent (VOC) is volatilized, which adversely affects the work environment and the surrounding environment. In spray coating, in addition to discharging VOC into the atmosphere, it is said that 10% to 20% by weight of the paint is scattered around by the wind. On the other hand, when repainting antifouling paints that have been used for many years, old antifouling paints are peeled off with sandblasting or a metal polishing machine, but at that time, toxic antifouling agents such as organotin compounds and cuprous oxide are removed. A large amount of the coated film pieces are scattered around and adversely affect the operator and the environment, and the peeled antifouling paint is treated as industrial waste, which is a big problem.

As an antifouling tape having an antifouling effect without using an antifouling paint, a sheet-like tape has been proposed in which a silicone elastomer is provided on a base material via a primer and an adhesive layer is provided on the opposite side of the base material. (See Patent Document 1). However, since the antifouling layer is inferior in mechanical strength, for example, when an object collides with the antifouling tape applied to the underwater structure under the use condition in the fluid, the antifouling layer may be damaged or missing. There is.

JP 2002-69246 A

An object of the present invention is to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that is excellent in impact resistance and can prevent the antifouling layer from being damaged or missing due to a collision object.

The aquatic organism adhesion preventing adhesive tape of the present invention is
An adhesive tape comprising an antifouling layer, a base material layer and an adhesive layer in this order,
The antifouling layer contains nano silica particles.

In a preferred embodiment, the content ratio of the nano silica particles in the antifouling layer is 0.01% by weight or more.

In a preferred embodiment, the base material layer contains an elastomer resin.

In a preferred embodiment, the elastomer resin is at least one selected from a polyurethane acrylic resin and a polyurethane resin.

In a preferred embodiment, the antifouling layer contains a silicone resin.

According to the present invention, it is possible to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that is excellent in impact resistance and can prevent the antifouling layer from being damaged or missing due to a collision object.

It is a schematic sectional drawing of an example of the aquatic organism adhesion prevention adhesive tape of this invention. It is a photograph figure which shows the state after the iron ball drop test of the adhesive tape (1) obtained in Example 1. FIG. It is a photograph figure which shows the state after the iron ball drop test of the adhesive tape (2) obtained in Example 2. FIG. It is a photograph figure which shows the state after the iron ball drop test of the adhesive tape (3) obtained in Example 3. FIG. It is a photograph figure which shows the state after the iron ball drop test of the adhesive tape (C1) obtained by the comparative example 1. FIG. It is a photograph figure which shows the state after the iron ball drop test of the adhesive tape (C2) obtained by the comparative example 2.

The aquatic organism adhesion preventing adhesive tape of the present invention comprises an antifouling layer, a base material layer and an adhesive layer in this order. The aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has any appropriate other layer as long as the antifouling layer, the base material layer, and the pressure-sensitive adhesive layer are included in this order, as long as the effects of the present invention are not impaired. May be. The thickness of the aquatic organism adhesion prevention adhesive tape of this invention is set to arbitrary appropriate thickness in the range which does not impair the effect of this invention by the thickness of each layer contained in it. The thickness of the aquatic organism adhesion preventing adhesive tape of the present invention is preferably 50 μm to 300 μm.

FIG. 1 shows a schematic cross-sectional view of an example of the aquatic organism adhesion preventing adhesive tape of the present invention. The aquatic organism adhesion prevention adhesive tape 100 of this invention contains the antifouling layer 2, the base material layer 3, and the adhesion layer 4 in this order. As shown in FIG. 1, a release film 1 may be provided on the surface of the antifouling layer 2 or the surface of the adhesive layer 4.

The antifouling layer contains nano silica particles. When the antifouling layer contains nano silica particles, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention is excellent in impact resistance and can prevent the antifouling layer from being damaged or missing due to a collision object.

The nanosilica particles are particles having a primary average particle diameter of less than 1 μm and are composed of silicon dioxide (SiO ₂ ) particles or silicon dioxide (SiO ₂ ), for example, hydrophobic nanosilica particles or hydrophilic particles. Nanosilica particles. Examples of the nanosilica particles include particles having a hydrophobic surface and particles having a hydrophilic surface.

As the nanosilica particles, for example, Aerosil series (manufactured by Nippon Aerosil Co., Ltd.) is used. More specifically, in hydrophobicity, Aerosil R8200 (primary average particle size: 12 nm, hexamethyldisilazane treatment), Aerosil R104 (Primary average particle size: 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R972 (Primary average particle size: 16 nm, dimethyldichlorosilane treatment), Aerosil R974 (Primary average particle size: 12 nm, dimethyldichlorosilane treatment), Aerosil R812 (Primary average particle size: 7 nm, hexamethyldisilazane treatment), etc. Examples of hydrophilicity include Aerosil 200 (primary average particle size: 12 nm), Aerosil 300 (primary average particle size: 7 nm), and the like.

The content ratio of the nano silica particles in the antifouling layer is preferably 0.01% by weight or more, more preferably 0.01% by weight to 100% by weight, and further preferably 0.05% by weight to 50% by weight. More preferably, it is 0.1 to 30% by weight, particularly preferably 1 to 10% by weight, and most preferably 1 to 5% by weight. When the content ratio of the nanosilica particles in the antifouling layer is within the above range, the aquatic organism adhesion preventing adhesive tape of the present invention is further excellent in impact resistance, and the antifouling layer is more easily damaged or missing due to the impacting object. It can be effectively prevented.

The antifouling layer is a layer containing nanosilica particles, and any appropriate layer can be adopted as long as it can exhibit the effects of the present invention.

The antifouling layer is preferably a layer that can exhibit an antifouling effect without using an antifouling paint, and preferably contains any appropriate resin having an antifouling effect. As such a resin, Preferably, a silicone resin is mentioned.

When the antifouling layer contains a silicone resin, any appropriate content can be adopted as the content of the silicone resin in the antifouling layer depending on the content of other components such as an antifouling agent. When the antifouling layer contains a silicone resin, the content of the silicone resin in the antifouling layer is preferably 30% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, and still more preferably 45% by weight to It is 96% by weight, particularly preferably 50% to 95% by weight. When the content ratio of the silicone resin in the antifouling layer is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the mechanical characteristics of the antifouling layer can be sufficiently expressed. When the content ratio of the silicone resin in the antifouling layer is less than 30% by weight, the mechanical properties of the antifouling layer may be deteriorated. When the content ratio of the silicone resin in the antifouling layer exceeds 98% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited.

As the silicone resin, any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used. Such a silicone resin may be a silicone resin that is liquid at normal temperature, or may be a silicone resin that is solid at normal temperature. Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin. Such a silicone resin may be a one-component silicone resin that is dried alone, or a two-component silicone resin that contains a curing agent. In the present invention, among these, a one-component room temperature curable (RTV) resin and a two-component room temperature curable (RTV) resin are preferable. Examples of the one-component RTV resin include KE-3475, KE-45S, KE-445, KE-44, KE-441, KE-3497, and KE-4896 manufactured by Shin-Etsu Chemical Co., Ltd. . Examples of the two-component RTV resin include KE-106, KE-66, KE-1031, and KE-1800 manufactured by Shin-Etsu Chemical Co., Ltd.

In order to improve the easy removal of aquatic organisms in the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention, the silicone resin can be easily peeled off due to elastic deformation of the resin surface due to water pressure at the time of water washing removal. A silicone resin having such physical properties is preferred. Such a silicone resin has a 100% modulus (tensile stress) of the silicone resin of preferably 0.1 MPa to 10 MPa, more preferably 0.1 MPa to 6 MPa. Such silicone resin is preferably soluble in an organic solvent.

The antifouling layer may contain an antifouling agent. Only one type of antifouling agent may be used, or two or more types may be used. When the antifouling layer contains an antifouling agent, the antifouling agent migrates to the surface of the silicone resin as a matrix and covers the surface with an antifouling substance, thereby suppressing the adhesion of aquatic organisms to the silicone resin surface. Furthermore, since it is non-hydrolyzable, it can exhibit the effect of maintaining a high antifouling effect for a long period of time.

When the antifouling layer contains an antifouling agent, the content of the antifouling agent with respect to the silicone resin in the antifouling layer is preferably 2% by weight or more, more preferably 2% by weight to 200% by weight, and even more preferably 3% by weight. % To 150% by weight, particularly preferably 4% to 120% by weight, most preferably 5% to 100% by weight. When the content ratio of the antifouling agent to the silicone resin is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the appearance characteristics and mechanical characteristics of the antifouling layer can be sufficiently expressed. When the content ratio of the antifouling agent to the silicone resin is less than 2% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited. When the content of the antifouling agent relative to the silicone resin exceeds 200% by weight, the appearance of the final molded product or the film may be deteriorated, and the antifouling layer strength is lowered and the antifouling property cannot be maintained. There is a fear.

As the antifouling agent, any appropriate antifouling agent can be adopted as long as the effects of the present invention are not impaired. Examples of such an antifouling agent include silicone oil, liquid paraffin, surfactant, wax, petrolatum, animal fats, fatty acids and the like. In the present invention, the antifouling agent is preferably at least one selected from silicone oil, liquid paraffin, and surfactant.

The silicone oil is preferably one that does not have reactivity with the silicone resin or self-condensation. As such a silicone oil, any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired. Such a silicone oil is preferably incompatible with the organopolysiloxane contained in the silicone resin to some extent, and is represented by, for example, the general formula (I) in that the antifouling effect can be maintained over a long period of time. Silicone oil is preferred.

In general formula (I), R ¹ is the same or different and represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a fluoroalkyl group, a polyether group, or a hydroxyl group, and R ² is the same or Differently, it represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a polyether group or a fluoroalkyl group, and n represents an integer of 0 to 150.

R ¹ in the general formula (I) is preferably a methyl group, a phenyl group, or a hydroxyl group. R ² in the general formula (I) is preferably a methyl group, a phenyl group, or a 4-trifluorobutyl group.

The silicone oil represented by the general formula (I) has a number average molecular weight of preferably 180 to 20000, more preferably 1000 to 10,000.

The viscosity of the silicone oil represented by the general formula (I) is preferably 10 centistokes to 10000 centistokes, more preferably 100 centistokes to 5000 centistokes.

As the silicone oil represented by the general formula (I), specifically, for example, terminal hydroxyl group-containing dimethyl silicone oil R ¹ at both ends or one end is a hydroxyl group, all of R ¹ and R ² is a methyl group And dimethyl silicone oils in which some of the methyl groups of these dimethyl silicone oils are substituted with phenyl groups.

Examples of commercially available silicone oils represented by the general formula (I) include KF96L, KF96, KF69, KF99, KF50, KF54, KF410, KF412, KF414, FL, Toray Dow Corning manufactured by Shin-Etsu Chemical Co., Ltd. BY16-846, SF8416, SH200, SH203, SH230, SF8419, FS1265, SH510, SH550, SH710, FZ-2110, and FZ-2203 manufactured by Corporation may be mentioned.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.

As antifouling agents, diatomaceous adhesion inhibitors, agricultural chemicals, pharmaceuticals (such as medetomidine), enzyme activity inhibitors (such as alkylphenols and alkylresorcinol), and biological repellents may be used. By using these antifouling agents, the adhesion preventing effect of aquatic organisms such as diatoms and barnacles is further improved.

The antifouling layer may contain any appropriate other additive as long as the effects of the present invention are not impaired.

The thickness of the antifouling layer may be any appropriate thickness depending on the application or use environment of the aquatic organism adhesion preventing adhesive tape of the present invention. The thickness of the antifouling layer is preferably 5 μm to 500 μm. When the thickness of the antifouling layer is within the above range, the antifouling effect is effective for a sufficiently long time, and the handling property is excellent. When the thickness of the antifouling layer is less than 5 μm, the period during which the antifouling effect is effective is shortened and may not be practical. If the antifouling layer is thicker than 500 μm, the aquatic organism adhesion-preventing adhesive tape of the present invention becomes thick and increases in weight, resulting in poor handling, large irregularities at the joints of the tape, and dirt. There is a fear.

As the base material layer, a base material layer made of any appropriate material can be adopted as long as the effects of the present invention are not impaired. Such a base material layer preferably contains an elastomer resin. As the elastomer resin, any appropriate elastomer resin can be adopted as long as the effects of the present invention are not impaired. Examples of such elastomer resins include vulcanized rubber and thermoplastic elastomer. Examples of the thermoplastic elastomer include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like. When the base material layer contains an elastomer resin, the content of the elastomer resin in the base material layer is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, and still more preferably 70% by weight. It is ˜99% by weight, particularly preferably 80% by weight to 98% by weight, and most preferably 90% by weight to 97% by weight.

When the base material layer contains an elastomer resin, the elastomer resin in the base material layer may be only one kind or two or more kinds. By including the elastomer resin in the base material layer, it is possible to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that is more excellent in impact resistance and can prevent the antifouling layer from being damaged or missing due to a collision object.

When the substrate layer contains an elastomer resin, the elastomer resin preferably includes a urethane elastomer and a styrene elastomer, and more preferably a urethane elastomer. By adopting urethane-based elastomer as the elastomer resin, the aquatic organism adhesion preventing adhesive tape of the present invention is more excellent in impact resistance, and can more effectively prevent damage and omission of the antifouling layer due to impacting objects.

The urethane elastomer is preferably at least one selected from a polyurethane acrylic resin and a polyurethane resin. Examples of the polyurethane resin include ester polyurethane and ether polyurethane.

Examples of the styrene elastomer include styrene / butadiene copolymer (SB), styrene / isoprene copolymer (SI), styrene / ethylene-butylene copolymer (SEB), and styrene / ethylene-propylene copolymer (SEP). AB type diblock polymers such as styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene-butylene copolymer / styrene copolymer ( SEBS), ABA type triblock or ABAB type tetrablock or more multiblock polymer such as styrene / ethylene-propylene copolymer / styrene (SEPS); styrene / butadiene rubber copolymer Styrene random copolymers such as (SBR); Styrene Eth Down - butylene copolymer, olefin crystal (SEBC) A-B-C type styrene-crystalline olefin based block polymers and the like; and the like.

Polyurethane acrylic resin has an acrylic component and a urethane component. More specifically, the polyurethane acrylic resin is a composite polymer containing a (meth) acrylic polymer and a urethane polymer. The weight ratio of (meth) acrylic polymer to urethane polymer in the polyurethane acrylic resin is preferably (meth) acrylic polymer / urethane polymer = 1/99 to 80/20. When the weight ratio of the (meth) acrylic polymer to the urethane polymer in the polyurethane acrylic resin is within the above range, the increase in the viscosity of the precursor mixture can be suppressed and workability can be maintained well, and the polyurethane acrylic resin can be maintained. Can provide excellent flexibility and excellent strength. If the (meth) acrylic polymer / urethane polymer is less than 1/99, the viscosity of the precursor mixture may be high and workability may be deteriorated. If it exceeds 80/20, flexibility and strength as a polyurethane acrylic resin may be obtained. May not be obtained.

In the present invention, “(meth) acryl” means acrylic and / or methacrylic.

The (meth) acrylic polymer in the polyurethane acrylic resin is preferably a polymer obtained using a monomer component containing a (meth) acrylic acid monomer and a monofunctional (meth) acrylic monomer. The (meth) acrylic polymer in the polyurethane acrylic resin is a polymer obtained by using a monomer component including a monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of a homopolymer of 0 ° C. or higher. Is preferred. The (meth) acrylic polymer in the polyurethane acrylic resin has a glass transition temperature (Tg) of the homopolymer in addition to the monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of the homopolymer of 0 ° C. or higher. ) Is more preferably a polymer obtained by using a monomer component containing a monofunctional (meth) acrylic monomer having a temperature of less than 0 ° C.

(Meth) acrylic acid monomer is a (meth) acrylic monomer having a carboxyl group. Examples of the (meth) acrylic acid monomer include acrylic acid, methacrylic acid, maleic acid, crotonic acid and the like. A preferable example of the (meth) acrylic acid-based monomer is acrylic acid in that the effects of the present invention can be further exhibited.

The content ratio of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin is preferably 1% by weight to 15% by weight, and more preferably 2% by weight to 10% by weight. When the content ratio of the (meth) acrylic acid monomer in the monomer component that is the raw material of the polyurethane acrylic resin falls within the above range, the synthesis reaction of the polyurethane acrylic resin can be smoothly advanced, and it is sufficient for the polyurethane acrylic resin. High strength and water resistance. If the content of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin is less than 1% by weight, the polyurethane acrylic resin may take a long time for the synthesis reaction, and the polyurethane acrylic resin has sufficient strength. May not have. When the content ratio of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin exceeds 15% by weight, the water absorption of the polyurethane acrylic resin increases, which may cause a problem in water resistance. . The (meth) acrylic acid monomer greatly affects the compatibility between the urethane component and the acrylic component in the polyurethane acrylic resin.

Examples of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher include acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and lauryl acrylate. The monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher may be only one type or two or more types.

The monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher is preferably at least one selected from acryloylmorpholine, isobornyl acrylate, and dicyclopentanyl acrylate in that the effects of the present invention can be further exhibited. More preferably, isobornyl acrylate is used.

The content ratio of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is preferably 20% by weight to 99% by weight, More preferably, it is 30 to 98% by weight. It is sufficient for polyurethane acrylic resin because the content ratio of monofunctional (meth) acrylic monomer having Tg of 0 ° C. or more in the monomer component constituting (meth) acrylic polymer in polyurethane acrylic resin is within the above range. In addition to imparting high strength, it is possible to suppress an excessive increase in rigidity of the polyurethane acrylic resin. When the content ratio of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is less than 20% by weight, the polyurethane acrylic resin is sufficient. May not have strength. When the content of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin exceeds 99% by weight, the rigidity of the polyurethane acrylic resin is increased. May rise and become brittle.

Examples of monofunctional (meth) acrylic monomers having a Tg of less than 0 ° C. include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofluorofuryl acrylate, Examples include phenoxyethyl acrylate, ethoxyethyl acrylate, and 3-methoxybutyl acrylate. The monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. may be only one type or two or more types.

The monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. is preferably n-butyl acrylate, from the viewpoint that the effects of the present invention can be further exhibited.

The content ratio of the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is preferably 50% by weight or less, more preferably 45% by weight or less. It is sufficient for polyurethane acrylic resin because the content ratio of monofunctional (meth) acrylic monomer with Tg of less than 0 ° C in the monomer component constituting (meth) acrylic polymer in polyurethane acrylic resin is within the above range. Can provide a high strength. When the content of the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin exceeds 50% by weight, the polyurethane acrylic resin May not have sufficient strength.

(Meth) acrylic monomers such as (meth) acrylic acid monomers and monofunctional (meth) acrylic monomers contained in the raw material monomers for (meth) acrylic polymers in polyurethane acrylic resins are compatible with urethane, In consideration of the polymerizability at the time of photocuring such as radiation and the characteristics of the high molecular weight substance to be obtained, the type, combination, amount used and the like are appropriately determined.

The raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin may contain any appropriate other monomer as long as the effects of the present invention are not impaired. Examples of such other monomers include vinyl acetate, vinyl propionate, styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, derivatives thereof, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, N, N— Dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, 2-hydroxypropyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, imide acrylate, N-vinylpyrrolidone, oligoester acrylate, ε-caprolactone Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxylated cyclododecatriene acrylate, methoxy Chill acrylate, and the like. One other monomer may be used, or two or more other monomers may be used. The type and amount of other monomers can be appropriately selected according to the purpose.

The raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin may contain other polyfunctional monomers as long as the effects of the present invention are not impaired. Examples of such polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate and the like. As such a polyfunctional monomer, trimethylolpropane tri (meth) acrylate is preferably used in that the effects of the present invention can be further exhibited.

When other polyfunctional monomers are contained in the raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin, the content is preferably 1 weight with respect to the (meth) acrylic monomer in the raw material monomer. % To 20% by weight. If the content ratio is 1% by weight or more, the cohesive force of the polyurethane acrylic resin can be maintained sufficiently high, and if the content ratio is 20% by weight or less, the elastic modulus of the polyurethane acrylic resin becomes too high. And is excellent in impact resistance and can follow the unevenness of the adherend surface well.

The urethane polymer in the polyurethane acrylic resin is preferably obtained by reacting a diol with a diisocyanate. A catalyst may be used for the reaction between the hydroxyl group of the diol and the isocyanate.

Examples of the low molecular weight diol include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol.

Examples of the high molecular weight diol include polyether polyols obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, and the like; divalent alcohols described above, 1,4-butanediol, 1,6-hexanediol, and the like Examples include polyester polyols composed of polycondensates of alcohols with divalent basic acids such as adipic acid, azelaic acid, and sebacic acid; acrylic polyols; carbonate polyols; epoxy polyols; caprolactone polyols; Among these, as the high molecular weight diol, polyoxytetramethylene glycol (PTMG) and polyalkylene carbonate diol (PCD) are preferable because the effects of the present invention can be further exhibited.

Examples of the acrylic polyol include a copolymer of a hydroxyl group-containing monomer and a (meth) acrylic monomer, in addition to a copolymer of a monomer having a hydroxyl group.

Examples of the epoxy polyol include amine-modified epoxy resins.

When producing the urethane polymer in the polyurethane acrylic resin, only one kind of the diol may be used in consideration of solubility in the (meth) acrylic monomer, reactivity with isocyanate, etc. Two or more kinds may be used. In order to improve the strength of the polyurethane acrylic resin, it is effective to increase the amount of the urethane hard segment by the low molecular weight diol. When importance is attached to the elongation of the polyurethane acrylic resin, it is effective to use a diol having a large molecular weight alone. Polyether polyols are generally inexpensive and have good water resistance. The polyester polyol can improve the strength of the polyurethane acrylic resin.

Examples of the diisocyanate include aromatic, aliphatic, and alicyclic diisocyanates; dimers and trimers of these diisocyanates; polyphenylmethane diisocyanate; and the like. Only one diisocyanate may be used, or two or more diisocyanates may be used.

Examples of aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate (HXDI), isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanate methyl) Cyclohexane, methylcyclohexane diisocyanate, m- tetramethylxylylene diisocyanate, and the like.

Examples of the trimer of aromatic, aliphatic and alicyclic diisocyanates include isocyanurate type, burette type and allophanate type.

The diisocyanate is preferably hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4-diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI) in that the effects of the present invention can be further exhibited. ), Hydrogenated xylene diisocyanate (HXDI).

The ratio of the diol component and diisocyanate component used to form the urethane polymer is preferably NCO / OH (equivalent ratio) of 1.1 to 2.0, more preferably 1.15 to 1.35. . When NCO / OH (equivalent ratio) falls within the above range, the polyurethane acrylic resin can be provided with excellent strength, sufficient elongation, and sufficient flexibility. When NCO / OH (equivalent ratio) is less than 1.1, the strength of the polyurethane acrylic resin may be reduced. If NCO / OH (equivalent ratio) exceeds 2.0, the polyurethane acrylic resin may not be sufficiently stretched and flexible.

A hydroxyl group-containing (meth) acrylic monomer may be added to the urethane polymer. By adding a hydroxyl group-containing (meth) acrylic monomer to the urethane polymer, a (meth) acryloyl group can be introduced at the molecular terminal of the urethane prepolymer, and the copolymerization with the (meth) acrylic monomer is possible. As a result, compatibility between the urethane component and the acrylic component is increased, and SS characteristics such as breaking strength can be improved. The amount of the hydroxyl group-containing (meth) acrylic monomer used is preferably 0.1% by weight to 10% by weight and more preferably 1% by weight with respect to the urethane polymer in that the effect of the present invention can be further exhibited. ~ 5% by weight.

Examples of the hydroxyl group-containing (meth) acrylic monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.

The polyurethane acrylic resin preferably has a heterogeneous network structure in which a (meth) acrylic polymer and a urethane polymer are bonded to each other by a graft structure or a crosslinked structure. IPN structure (interpenetrating polymer network layer) in which (meth) acrylic polymer and urethane polymer each independently have a crosslinked structure, or one of (meth) acrylic polymer and urethane polymer has a crosslinked structure. In the case of a semi-IPN structure in which one of these has a linear polymer chain and penetrates into the cross-linked structure, the stress at the time of expansion of the polyurethane acrylic resin may be difficult to develop.

When a polyurethane acrylic resin is included as an elastomer resin in the base material layer, for example, the base material layer includes a (meth) acrylic monomer as a diluent, and a diol and a diisocyanate in the (meth) acrylic monomer. Reaction is performed to form a urethane polymer, and a mixture containing (meth) acrylic monomer and urethane polymer as main components is applied onto a substrate (exfoliated if necessary), and photopolymerization is started. Depending on the type of agent, etc., it is cured by irradiation with ionizing radiation such as α-rays, β-rays, γ-rays, neutrons, electron beams, ultraviolet rays, visible light, etc., and then the substrate is peeled off. By removing, a base material layer can be formed. Or it can also obtain in the form by which the base material layer was laminated | stacked on the base material etc., without peeling and removing a base material etc.

When a polyurethane acrylic resin is contained as an elastomer resin in the base material layer, more specifically, the base material layer is prepared by, for example, adding a diisocyanate after dissolving a diol in a (meth) acrylic monomer. The viscosity is adjusted by reacting with a diol, and this is applied to a support or the like, or, if necessary, applied to a release-treated surface of a support or the like, and then cured by using a low-pressure mercury lamp or the like. Can do. In this method, the (meth) acrylic monomer may be added all at once during the urethane synthesis or may be added in several divided portions. Further, after the diisocyanate is dissolved in the (meth) acrylic monomer, the diol may be reacted. According to this method, the molecular weight is not limited and a high molecular weight polyurethane can be produced, so that the molecular weight of the finally obtained urethane can be designed to an arbitrary size. In order to prevent polymerization inhibition due to oxygen, a release-treated sheet (separator, etc.) may be put on the mixture coated on a support or the like to block oxygen, or in a container filled with an inert gas. A base material may be added to lower the oxygen concentration.

¡The type of radiation and the type of lamp used for irradiation can be selected as appropriate. Examples of such lamps include low-pressure lamps such as fluorescent chemical lamps, black lights, and sterilization lamps; high-pressure lamps such as metal halide lamps and high-pressure mercury lamps.

Irradiation amounts such as ultraviolet rays can be arbitrarily set according to the characteristics of the base material layer. Generally, the dose of ultraviolet rays is preferably ^{100mJ / cm 2 ~ 5000mJ / cm} 2, more preferably ^{1000mJ / cm 2 ~ 4000mJ / cm} 2, more preferably 2000mJ ^/ cm 2 ~ 3000mJ ^/ cm ² . By keeping the amount of ultraviolet irradiation within the above range, a sufficient polymerization rate can be obtained without deterioration. When the dose of ultraviolet ray is less than 100 mJ / cm ^2, it might not provide a sufficient rate of polymerization, and is larger than 5000 mJ / cm ^2, which may cause deterioration. The temperature at the time of irradiation with ultraviolet rays or the like can be set to any appropriate temperature depending on the purpose. If the temperature at the time of irradiation with ultraviolet rays or the like is too high, a stop reaction due to polymerization heat tends to occur, which tends to cause deterioration of characteristics. For this reason, the temperature at the time of irradiating with ultraviolet rays or the like is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 30 ° C. or lower.

In preparing a polyurethane acrylic resin, a mixture containing at least a urethane polymer (for example, a mixture containing (meth) acrylic monomer and urethane polymer as main components) preferably contains a photopolymerization initiator.

Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether; substituted benzoin ethers such as anisole methyl ether; 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone. Substituted alpha-ketols such as substituted acetophenone, 1-hydroxycyclohexyl, phenyl ketone, 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; 1-phenyl-1,1-propanedione-2 And photoactive oximes such as-(o-ethoxycarbonyl) -oxime.

The base material layer may contain any appropriate additive as long as the effects of the present invention are not impaired. Examples of such additives include olefin resins, silicone polymers, liquid acrylic copolymers, tackifiers, anti-aging agents, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, and antistatic agents. , Polyethyleneimine, fatty acid amide, fatty acid ester, phosphate ester, lubricant, surfactant, filler and pigment (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, carbon black, etc.).

The base material layer preferably contains an ultraviolet absorber. The weather resistance of the aquatic organism adhesion prevention adhesive tape of this invention improves because a base material layer contains a ultraviolet absorber. When the base material layer does not contain an ultraviolet absorber, the base material is likely to be deteriorated by sunlight during outdoor use, and it may be difficult to maintain the initial base material strength. When the base material deteriorates, the base material layer is frequently cut when the used aquatic organism adhesion preventing adhesive tape of the present invention is peeled off from the adherend, and the work efficiency may be significantly deteriorated. There is.

Any appropriate thickness can be adopted as the thickness of the base material layer according to the purpose. The thickness of the base material layer is preferably 1 μm to 1000 μm, more preferably 10 μm to 800 μm, and still more preferably 20 μm to 500 μm. By keeping the thickness of the base material layer within the above range, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can be easily attached to a portion other than a flat surface such as a curved surface or an acute angle surface with good workability. Appearance defects such as wrinkles and floats are unlikely to occur on the surface.

In order to improve adhesion to the antifouling layer, a primer may be applied to the base material layer in advance, or a silane coupling agent may be added in advance. When the antifouling layer contains a silicone resin, adhesion to the base material layer may be low due to the low surface energy that is a characteristic of the silicone resin. If the adhesion between the antifouling layer and the base material layer is low, the antifouling layer that exhibits the antifouling effect peels off from the base material layer due to impact or physical damage during use, and the original antifouling effect continues. It may not be possible. Therefore, a primer is applied to the surface of the base material layer in advance to improve the adhesion to the antifouling layer, or silanol groups and alkoxysilane groups that react with the silicone resin are introduced into the base material layer with a silane coupling agent. The adhesion can be improved by performing a condensation reaction with a reactive group on the base material layer during application of the condensation type silicone resin.

Only one type of silane coupling agent may be used, or two or more types may be used. Specific examples of commercially available silane coupling agents include KBM5103, KBM1003, KBM903, KBM403, and KBM802 manufactured by Shin-Etsu Chemical Co., Ltd.

When the silane coupling agent is contained in the base material layer, the content ratio of the silane coupling agent in the base material layer is preferably 0.01% by weight to 10% by weight. By keeping the content ratio of the silane coupling agent in the base material layer within the above range, it is possible to suppress the base material layer from becoming too hard, and there is sufficient adhesion between the base material layer and the antifouling layer. It can be expressed. When the content rate of the silane coupling agent in a base material layer exceeds 10 weight%, there exists a possibility that a silane coupling agent may become a crosslinking point and a base material layer may become hard. When the content rate of the silane coupling agent in a base material layer is less than 0.01 weight%, there exists a possibility that sufficient adhesiveness cannot be expressed between a base material layer and an antifouling layer.

As the adhesive layer, any appropriate adhesive layer can be adopted as long as the effects of the present invention are not impaired. Examples of the material for such an adhesive layer include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (vinyl acetate polymers, etc.) adhesives, and curable acrylic resin adhesives. Agents, silicone resin adhesives, and the like. The material of the adhesive layer may be only one type or two or more types.

As the thickness of the adhesive layer, any appropriate thickness can be adopted depending on the application and use environment of the aquatic organism adhesion preventing adhesive tape of the present invention. The thickness of the adhesive layer is preferably 10 μm or more. When the thickness of the pressure-sensitive adhesive layer is within the above range, the shape of the adherend can be sufficiently followed, the adhesion area can be sufficiently secured, and sufficient adhesive force can be expressed. When the thickness of the pressure-sensitive adhesive layer is less than 10 μm, it is impossible to sufficiently follow the shape of the adherend, the adhesion area is reduced, and there is a possibility that sufficient pressure-sensitive adhesive force cannot be expressed. The upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 300 μm or less from the viewpoint of handleability.

The aquatic organism adhesion preventing adhesive tape of the present invention can be produced by any appropriate method. Examples of such a method include, for example, a method of forming an antifouling layer by applying an antifouling layer forming material on the base material layer after pasting a separately prepared base material layer and an adhesive layer, and one of the base material layers. A method of forming an adhesive layer by applying an adhesive layer forming material on the surface and forming an antifouling layer by applying an antifouling layer forming material to the other surface of the base material layer, the base layer forming material and the adhesive layer For example, a method of forming the antifouling layer by applying the antifouling layer forming material on the base material layer after co-extrusion of the forming material to form a base material layer / adhesive layer laminate.

Examples of the method for applying the antifouling layer forming material on the base material layer include spraying, brushing, roller, curtain flow, roll, dip and the like. The antifouling layer-forming material is applied onto the base material layer by these methods, and the antifouling layer is formed, for example, by drying at a temperature from room temperature to 250 ° C. (preferably from room temperature to 180 ° C.). can do.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

<Iron ball drop test>
The tape to be tested was sampled to a size of 3 cm × 3 cm and affixed to a 5 cm × 5 cm × 1 cm acrylic plate and fixed. A 100 g iron ball (diameter 3 cm) was dropped from a height of 1 m onto the antifouling layer side of the tape on the acrylic plate, and the state of the antifouling layer was observed.

[Example 1]
(Adhesive layer)
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 2-ethylhexyl acrylate (2EHA, manufactured by Toagosei Co., Ltd.) as a (meth) acrylic monomer: 90 parts by weight, acrylic acid (AA ): 10 parts by weight, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator: 0.1 parts by weight are added and dispersed. Then, UV irradiation was performed from above in a nitrogen stream while stirring to convert a part of the monomer into a polymer to adjust the viscosity so that it could be applied to obtain a (meth) acrylic monomer mixture. To this (meth) acrylic monomer mixture, 1,6-hexanediol diacrylate (HDDA): 0.08 part by weight is added as a crosslinking agent, and this is added to a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.). , 50 μm thick) with an applicator, and a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., 38 μm thick) is bonded with a hand roller, and ultraviolet rays are emitted from an ultraviolet lamp (BL type). Irradiation (ultraviolet light illuminance: 3.4 mW / cm ² , cumulative irradiation amount: 2000 mJ / cm ² ) gave an adhesive layer (1-A) having a thickness of 50 μm.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight: trimethylolpropane triacrylate ( TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator: 0.25 parts by weight, UV absorber (product) The name “TINUVIN123” (manufactured by BASF): 1.25 parts by weight and antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight were added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is bonded onto this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm ² , cumulative irradiation amount: 2000 mJ / cm ² ) to obtain a base material layer (1-B).
(Adhesive tape)
The obtained adhesive layer (1-A) and substrate layer (1-B) were bonded together with a hand roller to obtain a tape. And on the base material layer (1-B) of this tape, a condensation type silicone elastomer (KE-445, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) A mixed solution obtained by mixing nanosilica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) at 100: 30: 1.5 (weight ratio) was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (1).
The structure of the adhesive tape (1) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state after the iron ball drop test of an adhesive tape (1) was shown in FIG.

[Example 2]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (2-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin substrate (XUS2098, manufactured by Seadam Co., Ltd.) was used to form a substrate layer (2-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (2-A) and substrate layer (2-B) were bonded together with a hand roller to obtain a tape. On the base material layer (2-B) of this tape, a condensation type silicone elastomer (KE-445, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) A mixed solution in which nano silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) was mixed at 100: 30: 1.5 (weight ratio) was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (2).
The structure of the adhesive tape (2) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state after the iron ball drop test of an adhesive tape (2) was shown in FIG.

Example 3
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (3-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin base material (DUS451, manufactured by Seadam Co., Ltd.) was used to form a base material layer (3-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (3-A) and substrate layer (3-B) were bonded together with a hand roller to obtain a tape. On the base material layer (3-B) of this tape, an addition type silicone elastomer (KE-106, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) A mixed solution in which nano silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) was mixed at 100: 50: 1.5 (weight ratio) was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (3).
The configuration of the adhesive tape (3) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state after the iron ball drop test of an adhesive tape (3) was shown in FIG.

[Comparative Example 1]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (C1-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight: trimethylolpropane triacrylate ( TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator: 0.25 parts by weight, UV absorber (product) The name “TINUVIN123” (manufactured by BASF): 1.25 parts by weight and antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight were added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm ² , cumulative irradiation amount: 2000 mJ / cm ² ) to obtain a base material layer (C1-B).
(Adhesive tape)
The obtained adhesive layer (C1-A) and substrate layer (C1-B) were bonded together with a hand roller to obtain a tape. On the base material layer (C1-B) of this tape, a condensation type silicone elastomer (KE-445, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone oil (KF 96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) A mixed solution mixed at 100: 30 (weight ratio) was applied by an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C1).
The configuration of the adhesive tape (C1) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state after the iron ball drop test of an adhesive tape (C1) was shown in FIG.

[Comparative Example 2]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (C2-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin base material (DUS451, manufactured by Seadam Co., Ltd.) was used to form a base material layer (C2-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (C2-A) and substrate layer (C2-B) were bonded together with a hand roller to obtain a tape. Then, an addition type silicone elastomer (KE-106, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) are applied on the base material layer (C2-B) of the tape. A mixed solution mixed at 100: 50 (weight ratio) was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C2).
The structure of the adhesive tape (C2) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state after the iron ball drop test of an adhesive tape (C2) was shown in FIG.

Since the aquatic organism adhesion preventing adhesive tape of the present invention can prevent aquatic organisms from adhering and breeding, underwater structures (ships, buoys, port facilities, offshore oilfield facilities, waterways for power plant cooling water, factory cooling) It can be suitably used for water channels and floating passages.

DESCRIPTION OF SYMBOLS 1 Release film 2 Antifouling layer 3 Base material layer 4 Adhesive layer 100 Aquatic organism adhesion prevention adhesive tape

Claims

An adhesive tape comprising an antifouling layer, a base material layer and an adhesive layer in this order,
The antifouling layer comprises nano silica particles;
Aquatic organism adhesion prevention adhesive tape.
The aquatic organism adhesion prevention adhesive tape according to claim 1, wherein a content ratio of the nano silica particles in the antifouling layer is 0.01% by weight or more.
The aquatic organism adhesion preventing adhesive tape according to claim 1 or 2, wherein the base material layer contains an elastomer resin.
The aquatic organism adhesion prevention adhesive tape according to claim 3, wherein the elastomer resin is at least one selected from a polyurethane acrylic resin and a polyurethane resin.
The aquatic organism adhesion prevention adhesive tape in any one of Claim 1 to 4 in which the said antifouling layer contains a silicone resin.