WO2016088631A1 - Adhesive tape for preventing attachment of aquatic organisms - Google Patents

Adhesive tape for preventing attachment of aquatic organisms Download PDF

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Publication number
WO2016088631A1
WO2016088631A1 PCT/JP2015/083148 JP2015083148W WO2016088631A1 WO 2016088631 A1 WO2016088631 A1 WO 2016088631A1 JP 2015083148 W JP2015083148 W JP 2015083148W WO 2016088631 A1 WO2016088631 A1 WO 2016088631A1
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WIPO (PCT)
Prior art keywords
layer
adhesive tape
thickness
water vapor
sensitive adhesive
Prior art date
Application number
PCT/JP2015/083148
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French (fr)
Japanese (ja)
Inventor
太樹 末吉
内藤　友也
倉田　直記
量子 浅井
麻美 久保
昌嗣 東
鈴木　聡
平松　剛
Original Assignee
日東電工株式会社
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Publication of WO2016088631A1 publication Critical patent/WO2016088631A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/006—Presence of polysiloxane in the substrate

Definitions

  • the present invention relates to an aquatic organism adhesion preventing adhesive tape.
  • the present invention has aquatic organisms attached to underwater structures (ships, buoys, harbor facilities, offshore oilfield facilities, power plant cooling water channels, factory cooling water channels, floating floating channels, etc.).
  • the present invention relates to an aquatic organism adhesion prevention adhesive tape for preventing breeding.
  • Underwater structures such as ships are in contact with seawater, and aquatic organisms such as barnacles, oysters, mussels, hydra, cell plastics, squirts, bryozoans, Aosa, Aonori, and attached diatoms grow and increase fluid resistance. It causes unfavorable conditions such as deterioration of machine performance such as deterioration of thermal conductivity and diffusion of attached aquatic organisms overseas. In addition, the work for removing the attached aquatic organisms requires a large amount of labor and enormous time, and suffers an economic loss.
  • the hull made of fiber reinforced plastic (FRP) is overcoated with a gel coat layer to protect the FRP layer.
  • FRP fiber reinforced plastic
  • silicone-based ship bottom paints are known as means for preventing aquatic organisms from adhering to the ship bottom (see Patent Document 1).
  • silicone ship bottom paint has low water vapor barrier performance. For this reason, even if the antifouling coating film is formed by coating the bottom of the hull having a laminated structure of FRP layer / gel coat layer to form an antifouling coating film, seawater remains between the FRP layer and the gel coat layer in seawater. There is a problem that it penetrates and osmosis occurs.
  • ⁇ Osmosis suppression effect is also developed by using an epoxy primer as a primer for ship bottom paint.
  • an epoxy-based primer when used, it has to be applied to two layers using a ship bottom paint and a primer (primer), and there is a problem that it takes time, labor and cost, and an organic solvent (VOC) is used. Therefore, there is a problem that it volatilizes and adversely affects the work environment and the surrounding environment.
  • an aquatic organism adhesion prevention adhesive tape has recently been developed as a means for preventing adhesion of aquatic organisms to the bottom of the hull (see Patent Document 2).
  • An object of the present invention is to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that can effectively prevent aquatic organism adhesion and has a high osmosis-suppressing effect.
  • the aquatic organism adhesion preventing adhesive tape of the present invention is An antifouling layer, an adhesive layer (A), a water vapor barrier layer, and an adhesive layer (B) are included in this order.
  • the moisture permeability of the water vapor barrier layer is less than 800 g / m 2 ⁇ 24 hours when the thickness is converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • the moisture permeability is 50 g / m 2 ⁇ 24 hours or less.
  • the moisture permeability is 10 g / m 2 ⁇ 24 hours or less.
  • the material of the water vapor barrier layer is an organic polymer material.
  • the water vapor barrier layer has a thickness of 0.01 ⁇ m to 1000 ⁇ m.
  • the thickness is 0.1 ⁇ m to 500 ⁇ m.
  • the aquatic organism adhesion preventing adhesive tape of the present invention has an elastic modulus of 300 MPa or less.
  • a base material layer is provided between the antifouling layer and the pressure-sensitive adhesive layer (A).
  • an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that can effectively prevent adhesion of aquatic organisms and has a high effect of suppressing osmosis.
  • the aquatic organism adhesion prevention adhesive tape of this invention can fully ensure not only the high osmosis suppression effect but the adhesiveness of an antifouling layer and a base material layer sufficiently.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can preferably exhibit not only a high osmosis suppression effect but also a high curved surface followability.
  • the aquatic organism adhesion preventing adhesive tape of the present invention includes an antifouling layer, an adhesive layer (A), a water vapor barrier layer and an adhesive layer (B) in this order.
  • the pressure-sensitive adhesive layer (A) and the pressure-sensitive adhesive layer (B) may be the same type of pressure-sensitive adhesive layer or different types of pressure-sensitive adhesive layers.
  • the aquatic organism adhesion prevention adhesive tape of the present invention includes an antifouling layer, an adhesive layer (A), a water vapor barrier layer and an adhesive layer (B) in this order, the effects of the present invention are not impaired. It may have any other suitable layer.
  • the aquatic organism adhesion preventing adhesive tape of the present invention preferably has a base material layer between the antifouling layer and the adhesive layer.
  • the aquatic organism adhesion preventing adhesive tape of the present invention has a water vapor barrier layer and an adhesive layer (B) in this order on the side opposite to the antifouling layer of the adhesive layer (A).
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention preferably has not only a high osmosis suppression effect but also a base material layer, the antifouling layer and the base material layer. Adhesion can be sufficiently secured.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can preferably exhibit not only a high osmosis suppression effect but also a high curved surface followability.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has an elastic modulus of preferably 300 MPa or less, more preferably 1 MPa to 200 MPa, still more preferably 1 MPa to 150 MPa, particularly preferably 1 MPa to 100 MPa.
  • the pressure is preferably 1 MPa to 80 MPa.
  • 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, the adhesive layer (A) 4, the water vapor barrier layer 5, and the adhesive layer (B) 6 in this order.
  • a release film 1 may be provided on the surface of the antifouling layer 2 or the surface of the pressure-sensitive adhesive layer (B) 6.
  • the aquatic organism adhesion preventing adhesive tape of the present invention comprises an antifouling layer, a base material layer, an adhesive layer (A), a water vapor barrier layer and an adhesive.
  • the layers (B) are included in this order, and preferably, the antifouling layer, the base material layer, the pressure-sensitive adhesive layer (A), the water vapor barrier layer, and the pressure-sensitive adhesive layer (B) are directly laminated in this order.
  • the water vapor barrier layer has a moisture permeability of preferably less than 800 g / m 2 ⁇ 24 hours, more preferably 300 g / m 2 when the thickness is converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • m 2 ⁇ 24 hours or less more preferably 100 g / m 2 ⁇ 24 hours or less, particularly preferably 50 g / m 2 ⁇ 24 hours or less, and most preferably 10 g / m 2 ⁇ 24 hours or less.
  • the lower limit value of the moisture permeability of the water vapor barrier layer is preferably as low as possible, and is preferably 0 g / m 2 ⁇ 24 hours.
  • “converting the thickness to 25 ⁇ m” means, for example, in the case of a water vapor barrier layer having a thickness of L ⁇ m, the value of moisture permeability ⁇ (25 / L).
  • the aquatic organism adhesion prevention adhesive tape of this invention WHEREIN: By adjusting the water vapor permeability of the said water vapor
  • a water vapor barrier layer that is 10 g / m 2 ⁇ 24 hours or less and the lower limit is preferably 0 g / m 2 ⁇ 24 hours.
  • the thickness of the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention is set to any appropriate thickness within a range that does not impair the effects of the present invention, depending on the thickness of each layer included therein.
  • the thickness of the aquatic organism adhesion preventing adhesive tape of the present invention is preferably 10 ⁇ m to 2000 ⁇ m, more preferably 50 ⁇ m to 800 ⁇ m, and further preferably 100 ⁇ m to 500 ⁇ m.
  • the water vapor barrier layer may be a single layer or a laminate of two or more layers.
  • the laminate may be formed by, for example, a laminate or may be formed by coextrusion.
  • the moisture permeability is preferably less than 800 g / m 2 ⁇ 24 hours (more preferably 300 g) when the thickness is converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • / M 2 ⁇ 24 hours or less more preferably 100 g / m 2 ⁇ 24 hours or less, particularly preferably 50 g / m 2 ⁇ 24 hours or less, and most preferably 10 g / m 2 ⁇ 24 hours or less.
  • any lower limit value is preferably 0 g / m 2 ⁇ 24 hours).
  • the material of the water vapor barrier layer may be only one kind, or two or more kinds may be used in combination.
  • Examples of the material for the water vapor barrier layer include polyvinylidene chloride, copolymers of vinylidene chloride and vinyl chloride, acrylonitrile, and the like; polyvinyl chloride; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyethylene Polyolefin resin such as polypropylene, fluorine resin such as polytetrachloroethylene, polyacrylonitrile, copolymer of acrylonitrile and methyl acrylate, butadiene, etc., polyvinyl alcohol, copolymer of vinyl alcohol and ethylene, nylon 6, nylon Polyamide, such as 66; polyimide; polystyrene, styrene thermoplastic elastomer (for example, hydrogenated styrene / butadiene rubber (HSBR), styrene block copolymer (for example, , Styrene-butadiene-styrene copolymer (SBS),
  • the material for the water vapor barrier layer is preferably a film made of an organic polymer material such as polyvinylidene chloride, a copolymer of vinylidene chloride and vinyl chloride, acrylonitrile, or the like.
  • a film on which a metal oxide or a nonmetal inorganic oxide is deposited can also be used.
  • films include polyester films such as PET, low oligomer PET, PBT, PEN, PBN, polyolefin films such as LDPE, LLDPE, homo PP, random PP, EVA, polyvinyl chloride films, fluorine PVD methods such as vacuum deposition, ion plating, and sputtering, and CVD methods such as plasma CVD and microwave CVD, etc.
  • base materials such as film, polycarbonate film, polysulfone film, and poly (meth) acrylic film
  • a material in which a metal oxide or a nonmetal inorganic oxide is deposited examples include oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium.
  • Alkali metal and alkaline earth metal fluorides can also be used.
  • the base material used by the above may be used only 1 type, and may be used in combination of 2 or more type.
  • the thickness of the water vapor barrier layer any appropriate thickness can be adopted depending on the application or use environment of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the thickness of the water vapor barrier layer is preferably 0.01 ⁇ m to 1000 ⁇ m, more preferably 0.05 ⁇ m to 800 ⁇ m, and still more preferably 0.1 ⁇ m to 500 ⁇ m.
  • the moisture permeability of the water vapor barrier layer is preferably less than 800 g / m 2 ⁇ 24 hours (more preferably 300 g / m 2 ⁇ 24) when the thickness is converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • the thickness of the water vapor barrier layer in the above range can provide a higher aquatic biofouling adhesive tape osmosis inhibiting effect.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can be easily attached to sites other than flat surfaces such as curved surfaces and acute angle surfaces with good workability. It is possible to suppress appearance defects such as wrinkles and floats on the surface after sticking.
  • the base layer has an elastic modulus at 23 ° C. of preferably 0.1 MPa to 100 MPa. By adjusting the elastic modulus within the above range, an aquatic organism adhesion preventing adhesive tape having excellent adhesion between the antifouling layer and the base material layer can be provided.
  • the base material layer preferably has an elongation recovery rate at 23 ° C. of 70% or more.
  • an aquatic organism adhesion-preventing pressure-sensitive adhesive tape having excellent adhesion between the antifouling layer and the base material layer can be provided.
  • any appropriate base material layer can be adopted as long as the effects of the present invention are not impaired.
  • a material for the base material layer preferably, the main component of the base material layer (preferably 50% by weight or more in the base material layer, more preferably 70% by weight or more in the base material layer, more preferably the base material layer)
  • the resin is preferably 90% by weight or more, particularly preferably 95% by weight or more in the base material layer, and is preferably excellent in water resistance, strength, flexibility and tearability.
  • the material for the base material layer examples include polyurethane resin, polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.) ) And the like.
  • the material of such a base material layer may be only one type or two or more types.
  • polyurethane resin and polyester resin are particularly preferable, and polyurethane resin is more preferable.
  • polyurethane resins include ether-based polyurethanes, ester-based polyurethanes, carbonate-based polyurethanes, and carbonate-based polyurethanes are particularly preferred because they are excellent in durability and strength, and can sufficiently exhibit the effects of the present invention. preferable.
  • a grade of a polyurethane resin a non-yellowing grade and a non-yellowing grade are preferable, and a non-yellowing grade is more preferable.
  • polyester resin examples include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
  • the base material layer has an elongation at break of preferably 100% to 1000%, more preferably 150% to 900%, and further preferably 200% to 800%.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can follow the shape of various adherends well and can be applied to a flat surface.
  • it can be satisfactorily affixed to a curved surface portion, a 90-degree angle portion, an acute angle portion, or the like present on the surface of the hull.
  • the base material layer has a stress at break of preferably 20 MPa or more, more preferably 25 MPa to 200 MPa, still more preferably 30 MPa to 150 MPa, and particularly preferably 35 MPa to 100 MPa.
  • the elongation at break and the stress at break are, for example, in accordance with JIS 7161, JIS 7162, and JIS 7127, a tensile tester (AUTOGRAPH AGS-X, manufactured by Shimadzu Corporation) and analysis software (TRAPEZIUM X, Shimadzu Corporation). Can be used.
  • the base material layer may contain any appropriate additive as long as the effects of the present invention are not impaired.
  • 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 may contain 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.
  • the thickness of the base material layer is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 800 ⁇ m, and still more preferably 20 ⁇ m to 500 ⁇ m.
  • 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. It is possible to suppress appearance defects such as wrinkles and floats on the surface after wearing.
  • a primer may be applied to the base material layer in advance, or a silane coupling agent may be added in advance.
  • silane coupling agent 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.
  • the content ratio of the silane coupling agent in the base material layer is preferably 0.01% by weight to 10% by weight.
  • the antifouling layer contains a matrix resin capable of exhibiting an antifouling effect (hereinafter sometimes simply referred to as “matrix resin”).
  • matrix resin any appropriate resin can be adopted as long as it can exhibit an antifouling effect.
  • a silicone resin is preferably used as such a matrix resin.
  • Such matrix resin may be only one kind, or two or more kinds.
  • the content ratio of the matrix resin in the antifouling layer is preferably 30% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, still more preferably 45% by weight to 96% by weight, Particularly preferred is 50 to 95% by weight.
  • 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.
  • 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.
  • the silicone resin that can be used as the matrix resin is preferably a two-part silicone resin, more preferably a two-part heat addition type silicone resin.
  • two-pack heat addition type silicone resins include KE-1950-10 (A / B), KE-1950-20 (A / B), and KE-1950 manufactured by Shin-Etsu Chemical Co., Ltd.
  • 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 preferably contains an antifouling agent.
  • the antifouling agent examples include silicone oil, liquid paraffin, surfactant, liquid hydrocarbon, fluorinated oil, and antibacterial agent. These may be only one type or two or more types.
  • the antifouling layer contains such an antifouling agent, the antifouling agent moves to the surface of the matrix resin and covers the surface with an antifouling substance, thereby suppressing the adhesion of aquatic organisms to the silicone resin surface. And the effect
  • an aquatic organism adhesion prevention adhesive tape that can maintain the antifouling effect for a long period of time, has little impact on the human body and the environment, is light in weight, can maintain stable quality, and can effectively prevent the attachment of aquatic organisms is provided. can do.
  • the content ratio of the antifouling agent to the matrix resin is preferably 1% by weight to 200% by weight, more preferably 2% by weight to 20% by weight.
  • any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired.
  • the silicone oil is preferably one that does not have reactivity with the matrix resin or self-condensation.
  • a silicone oil for example, when a silicone resin is used as a matrix resin, it is preferable that the silicone resin is incompatible with the organopolysiloxane contained in the silicone resin to a certain extent, and the antifouling effect can be maintained over a long period of time.
  • a silicone oil represented by the general formula (I) is preferable.
  • 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
  • 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
  • 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 number average molecular weight of the silicone oil represented by the general formula (I) is preferably 180 to 20000, and 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.
  • 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.
  • 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.
  • liquid paraffin any appropriate liquid paraffin can be adopted as long as the effects of the present invention are not impaired.
  • liquid paraffin include P-40, P-55, P-60, P-70, P-80, P-100, P-120, P-150, P-200, P manufactured by MORESCO. -260, P-350, hydrocarbon liquid paraffin manufactured by Wako Pure Chemical Industries, Ltd.
  • surfactant examples include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant.
  • anionic surfactant any appropriate anionic surfactant can be adopted as long as the effects of the present invention are not impaired.
  • anionic surfactants include, for example, alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, ⁇ -olefin sulfonates, ⁇ -sulfo fatty acid or ester salts, alkane sulfonates, Examples thereof include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. Only one type of anionic surfactant may be used, or two or more types may be used.
  • nonionic surfactant any appropriate nonionic surfactant can be adopted as long as the effects of the present invention are not impaired.
  • nonionic surfactants include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester. Examples thereof include esters and alkylamine oxides. Only one nonionic surfactant may be used, or two or more nonionic surfactants may be used.
  • amphoteric surfactant any appropriate amphoteric surfactant can be adopted as long as the effects of the present invention are not impaired.
  • amphoteric surfactants include carboxy type or sulfobetaine type amphoteric surfactants. Only one amphoteric surfactant may be used, or two or more amphoteric surfactants may be used.
  • any appropriate cationic surfactant can be adopted as long as the effects of the present invention are not impaired.
  • examples of such cationic surfactants include quaternary ammonium salts. Only one type of cationic surfactant may be used, or two or more types may be used.
  • liquid hydrocarbon any appropriate liquid hydrocarbon can be adopted as long as the effects of the present invention are not impaired.
  • liquid hydrocarbon any appropriate liquid hydrocarbon can be adopted as long as the effects of the present invention are not impaired. Examples thereof include hexane, heptane, benzene, toluene, xylene, 1-tetradecene and the like.
  • fluorinated oil any appropriate fluorinated oil can be adopted as the fluorinated oil as long as the effects of the present invention are not impaired.
  • fluorinated oils include perfluoropolyether, perfluorodecalin, perfluorooctane, and the like.
  • Perfluoropolyether is preferred in terms of chemical stability.
  • the perfluoropolyether for example, the structural formula: A- (C 3 F 6 O) x (CF 2 O) y (C 2 F 4 O) z-B (wherein the end group A is —F, —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF (CF 3 ) OCF 3 , —OF, —OCF 3 , —OC 2 F 5 , —OC 3 F 7 , —OCF (CF 3 )
  • the terminal group B is any of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF (CF 3 ) OCF 3
  • x, y, z are 0 or positive And x + y + z> 1 and the viscosity at 25 ° C.
  • perfluoropolyether is from 50 cs to 500,000 cs).
  • specific examples of the perfluoropolyether include, for example, CF 3 O— (CF 2 CF (CF 3 ) O) x (CF 2 O) y —CF 3 (wherein x and y are as described above). ), CF 3 O- (CF 2 O) y (C 2 F 4 O) z-CF 3 ( wherein, y, z are as defined above), CF 3 O- (CF 2 CF (CF 3) O) x-CF 3 (wherein x is as described above) and F- (CF 2 CF 2 CF 2 O) x-C 2 F 5 (wherein x is as described above) Etc.
  • antibacterial agent any appropriate antibacterial agent can be adopted as long as the effects of the present invention are not impaired.
  • antibacterial agents include so-called antibacterial agents and herbicides.
  • antibacterial agents include, for example, azoxystrobin, benalaxyl, benomyl, viteltanol, bromconazole, captahol, captan, carbendazim, quinomethionate, chlorothalonil, clozolinate, cyprozinyl, diclofluanide, diclofene, diclomedin, dichlorane, Dietofencarb, dimethomorph, diniconazole, dithianon, epoxiconazole, famoxadone, fenarimol, fenbuconazole, fenfram, fenpiclonil, fentin, fluazinam, fludioxonil, fluorimide, fluquinconazole, fursulfamide, flutolanil, holpet, hexachlorobenzene, hexaconazole, imi Benconazole, Ipoconazole, Iprodi
  • examples of natural antibacterial agents include Chinese herbal ingredients such as Soso bamboo extract, hinokitiol, garlic extract and licorice.
  • inorganic antibacterial agents such as silver, copper, zinc, tin, lead, and gold, are mentioned.
  • zeolites, hydroxyapatite, calcium carbonate, silica gel, aluminum calcium silicate, polysiloxane compounds, zirconium phosphate, zirconium sulfate, ion exchangers, zinc oxide, etc. are used as carriers for these inorganic antibacterial agents as necessary. it can.
  • Examples of the synthetic antibacterial agent include 2-pyridinethiol-1-oxide, p-chloro-m-cresol, polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkylpolyaminoethylglycine, benzisothiazoline, 5- And chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,2′-dithio-bis- (pyridine-1-oxide), and the like.
  • herbicides for example, bensulfuron methyl, pyrazosulfuron ethyl, imazosulfuron, cyclosulfamuron, ethoxysulfuron, flucetosulfuron, azimusulfuron, primissulfuron, prosulfuron, rimsulfuron, halosulfuron methyl, nicosulfuron , Thifensulfuron methyl, tritosulfuron, foramsulfuron, amidosulfuron, chlorosulfuron, iodosulfuron, metsulfuron methyl, sulfosulfuron, flazasulfuron, chlorimuron ethyl, triflusulfuron methyl, oxas Ruflon, sulfometuron methyl, trifloxysulfuron sodium, flupirsulfuron ethyl sodium, imazamox, imazetapill, imazaquin
  • any other appropriate antifouling agent can be adopted as long as the effects of the present invention are not impaired.
  • antifouling agents include waxes, petrolatum, animal fats, fatty acids, diatom adhesion inhibitors, agricultural chemicals, pharmaceuticals (such as medetomidine), enzyme activity inhibitors (such as alkylphenols and alkylresorcinols), biological repellents, and the like. Is mentioned.
  • 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.
  • examples of such other additives include a UV absorber as a weathering agent.
  • Specific examples of such ultraviolet absorbers include TINUVIN571, TINUVIN460, TINUVIN213, TINUVIN234, TINUVIN329, and TINUVIN326 made by BASF.
  • the addition amount of such an ultraviolet absorber is preferably 0.5% by weight or more and less than 10% by weight with respect to the matrix resin. By adjusting the addition amount of the ultraviolet absorber with respect to the matrix resin within the above range, the effect as a weathering agent can be sufficiently exhibited without inhibiting the curing reaction of the matrix resin.
  • a filler or the like can be added to improve the strength.
  • the filler include silica particles and diatomaceous earth.
  • grains by which the surface was hydrophobized from a dispersible viewpoint are preferable.
  • examples of such a surface treatment method include a surface treatment method using dimethylpolysiloxane, dimethyldichlorosilane, hexamethylenedisilazane, cyclic dimethylsiloxane, and the like.
  • the average particle size is preferably 5 nm to 300 nm.
  • the size of the particles whose surface has been subjected to hydrophobic treatment within the above range, sufficient strength can be imparted to the antifouling layer, and the particles can be uniformly dispersed in the antifouling layer. When an impact is applied to the antifouling layer, cracks can hardly occur.
  • the amount of such particles whose surface has been subjected to hydrophobic treatment is preferably 0.1% by weight to 10% by weight with respect to the matrix resin.
  • the added material such as a soiling agent can be uniformly dispersed, and when applied on the base material layer, it can be applied precisely.
  • the particles whose surface has been subjected to hydrophobic treatment include hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd., and specifically, AEROSIL (registered trademark) RX series (RX50, manufactured by Nippon Aerosil Co., Ltd.). RX200, RX300, etc.), AEROSIL (registered trademark) RY series (RY50, RY200, RY200S, etc.), AEROSIL (registered trademark) NY50, AEROSIL (registered trademark) NAX series, AEROSIL (registered trademark) R series, and the like.
  • adhesion between the antifouling layer and the aquatic organisms is preferably not more than 0.10 N / mm 2, more preferably less 0.08 N / mm 2, more preferably Is 0.05 N / mm 2 or less, particularly preferably 0.04 N / mm 2 or less.
  • the lower limit of the adhesion between the antifouling layer and the aquatic organism is preferably as small as possible. However, in consideration of materials and the like, in practice, it is preferably 0.005 N / mm 2 or more, more preferably 0. 0.001 N / mm 2 or more.
  • a measuring adapter mountain adapter on the extension rod
  • a digital force gauge manufactured by SHIMPO, FGN-50B
  • Select the adhesive tape with the barnacle attached measure the diameter of the barnacle with calipers, reset the measurement value of the measuring machine, and then gently touch the measuring adapter to the lower shell of the barnacle attached to the surface of the adhesive tape.
  • Slide the measuring instrument so that it is parallel to the surface of the adhesive tape, record the maximum load value (N) displayed on the measuring instrument when the barnacle is peeled off, and record the barnacle from the diameter of the barnacle previously measured.
  • Calculate the load area per unit area (N / mm 2 ) by calculating the adhesion area (mm 2 ) by the area formula of the circle and dividing the recorded maximum load value by the adhesion area. This was defined as adhesion.
  • 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 ⁇ m to 500 ⁇ m.
  • any appropriate pressure-sensitive adhesive layer can be adopted as the pressure-sensitive adhesive layer (A) and the pressure-sensitive adhesive layer (B) as long as the effects of the present invention are not impaired.
  • 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.
  • examples thereof include a pressure-sensitive adhesive and a silicone resin-based pressure-sensitive adhesive. There may be only one kind of material for such an adhesive layer, or two or more kinds.
  • the pressure-sensitive adhesive layer (A) and the pressure-sensitive adhesive layer (B) may be the same type of pressure-sensitive adhesive layer or different types of pressure-sensitive adhesive layers.
  • the pressure-sensitive adhesive layer (A) has a 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min, preferably a lower limit of 1 N / 20 mm or more, more preferably 3 N / 20 mm or more, and still more preferably 4 N / 20 mm or more.
  • the pressure-sensitive adhesive layer (B) has a 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min, preferably 30 N / 20 mm or less, more preferably 20 N / 20 mm or less, and even more preferably 15 N / 20 mm. It is as follows. By adjusting the 180-degree peel adhesive force of the pressure-sensitive adhesive layer (B) at 23 ° C. and a tensile speed of 300 mm / min within the above range, the aquatic organism adhesion preventing pressure-sensitive adhesive tape of the present invention can be easily peeled off from the adherend.
  • the lower limit of the 180-degree peel adhesive force at 23 ° C. and a tensile speed of 300 mm / min of the pressure-sensitive adhesive layer (B) is preferably 3 N / 20 mm or more from the viewpoint of maintaining sufficient adhesive force.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (A) in contact with seawater is the compression elasticity in the pressure-sensitive adhesive layer (A) before seawater contact.
  • the ratio is preferably 1.1 times or more, more preferably 1.2 times or more, and further preferably 1.5 times or more.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (A) in contact with seawater is the compression elastic modulus in the pressure-sensitive adhesive layer (A) before seawater contact. If it is 1.1 times or more, good adhesiveness can be expressed even in water.
  • the compression elastic modulus of the pressure-sensitive adhesive layer (A) before the seawater contact is the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (A) that is in contact with seawater.
  • the upper limit of the magnification is preferably 100 times or less from the viewpoint of handleability.
  • seawater here means the simulated seawater (artificial seawater) marketed.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (B) in contact with seawater is the compression elasticity in the pressure-sensitive adhesive layer (B) before seawater contact.
  • the ratio is preferably 1.1 times or more, more preferably 1.2 times or more, and further preferably 1.5 times or more.
  • the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (B) in contact with seawater is the compression elastic modulus of the pressure-sensitive adhesive layer (B) before seawater contact. If it is 1.1 times or more, good adhesiveness can be expressed even in water.
  • the compression elastic modulus of the pressure-sensitive adhesive layer (B) before seawater contact is the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (B) that is in contact with seawater.
  • the upper limit of the magnification is preferably 100 times or less from the viewpoint of handleability.
  • seawater here means the simulated seawater (artificial seawater) marketed.
  • the thickness of the pressure-sensitive adhesive layer (A) is preferably 10 ⁇ m or more from the viewpoint of adhesion to the water vapor barrier layer.
  • the upper limit of the thickness of the pressure-sensitive adhesive layer (A) is preferably 100 ⁇ m or less from the viewpoint of handleability.
  • the thickness of the pressure-sensitive adhesive layer (B) is preferably 10 ⁇ m or more from the viewpoint that it can sufficiently follow the shape of the adherend to secure a bonding area and can exhibit a sufficient adhesive force.
  • the upper limit of the thickness of the pressure-sensitive adhesive layer (B) is preferably 100 ⁇ m or less from the viewpoint of handleability.
  • the aquatic organism adhesion prevention adhesive tape of this invention can be manufactured by arbitrary appropriate methods.
  • a pressure-sensitive adhesive layer (A) forming material is applied to one surface of the base material layer to form a pressure-sensitive adhesive layer (A), and the surface of the base material layer opposite to the pressure-sensitive adhesive layer (A)
  • An antifouling layer-forming material is applied to form an antifouling layer, and a water vapor barrier layer is pasted on the surface of the pressure-sensitive adhesive layer (A) opposite to the base material layer.
  • 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 coater.
  • 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.
  • a precision coater such as a comma coater is used to apply the antifouling layer forming material onto the base material layer.
  • Moisture permeability (g / m 2 ⁇ 24h) (m / s) / t m: Mass increase in the last two weighing intervals (g) s; Moisture permeable area (m 2 ) t: Time of last two weighing intervals (h) / 24 (h) Evaluation was performed according to the following criteria.
  • ⁇ Moisture permeability exceeds 10 g / m 2 ⁇ 24 h and is 50 g / m 2 ⁇ 24 h or less.
  • X Moisture permeability exceeds 50 g / m 2 ⁇ 24 h.
  • test target adhesive tape was cut into 8 cm ⁇ 12 cm, and bonded with a hand roller so as to wrap a 3 cm ⁇ 10 cm FRP plate (having a gel coat layer on the surface). Furthermore, the excess part of the adhesive tape was tightly closed with an adhesive so that water did not enter.
  • the sample thus prepared was immersed in ion exchange water at 60 ° C. and allowed to stand for 10 days, and the presence or absence of osmosis was confirmed. Evaluation was performed according to the following criteria.
  • ⁇ The number of blisters is 5 to 9 / cm 2 .
  • X The number of blisters is 10 / cm 2 or more.
  • ⁇ Adhesion evaluation> The test target adhesive tape was cut into a width of 20 mm and a length of 150 mm, and the state of the antifouling layer was visually observed when the end (short side) was held and stretched by 10% by hand. Evaluation was performed according to the following criteria. ⁇ : The antifouling layer was in close contact with the base material layer. X: The antifouling layer was peeled off from the base material layer.
  • ⁇ Elastic modulus> The base material layer was cut to a width of 10 mm and a length of 100 mm, and installed so that the distance between chucks was 50 mm, and S was measured using a tensile tester (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation). -S test (temperature: 23 ° C., humidity: 65% RH, tensile speed: 300 mm / min) was performed. The elastic modulus was determined from the slope of the initial rise of the obtained SS curve. Evaluation was performed according to the following criteria. A: Elastic modulus is 100 MPa or less. ⁇ : The elastic modulus exceeds 100 MPa and is 500 MPa or less. X: The elastic modulus exceeds 500 MPa.
  • Silicone resin addition type liquid silicone resin (LIMS), trade name “KE-1950-50”, manufactured by Shin-Etsu Chemical Co., Ltd.): 100 parts by weight, silicone oil as antifouling agent (KF96-100cs, non-reactive silicone) Oil, manufactured by Shin-Etsu Chemical Co., Ltd.): 90 parts by weight, UV absorber (trade name “TINUVIN571”, manufactured by BASF): 2 parts by weight, nanosilica (trade name “Aerosil RX-300”, manufactured by Nippon Aerosil Co., Ltd.) ): 1 part by weight, liquid paraffin (manufactured by Kishida Chemical Co., Ltd.): 5 parts by weight, stirred using a homomixer to make a uniform liquid, defoamed, antifouling layer material liquid (1 ') Was obtained.
  • the antifouling layer material liquid (1 ′) is applied using an applicator and cured at 140 ° C. for 2 minutes to form an antifouling layer (1) having a thickness of 100 ⁇ m as the base material layer (1). ) Formed on top. As a result, a laminate of “antifouling layer (1) (thickness 100 ⁇ m) / base material layer (1) (thickness 100 ⁇ m)” was obtained.
  • the moisture permeability of the water vapor barrier layer (1) was 1 g / m 2 ⁇ 24 hours when the thickness was converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • the moisture permeability of the water vapor barrier layer (2) was 6 g / m 2 ⁇ 24 hours when the thickness was converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • Table 1 Table 1
  • Example 4 Except having replaced the water vapor
  • steam barrier layer (4) which is a PVC film (General soft PVC, the Sanvik Co., Ltd. make, thickness 130 micrometers), it carries out similarly to Example 1 and performs adhesive tape (4 )
  • the moisture permeability of the water vapor barrier layer (4) was 18 g / m 2 ⁇ 24 hours when the thickness was converted to 25 ⁇ m in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
  • Various evaluation results are shown in Table 1.
  • an adhesive layer (C1) having a thickness of 50 ⁇ m was obtained. It was 4.8 N / 20mm as a result of measuring the 180 degree
  • Example 2 On the water vapor barrier layer (4) used in Example 4, the antifouling layer material liquid (1 ′) used in Example 1 was applied using an applicator, cured at 140 ° C. for 2 minutes, and a thickness of 100 ⁇ m. An antifouling layer (1) was formed on the water vapor barrier layer (4). Next, the pressure-sensitive adhesive layer (1B) (thickness 50 ⁇ m) used in Example 1 was bonded to the opposite side of the water vapor barrier layer (4) to the antifouling layer (1) using a hand roller.
  • the pressure-sensitive adhesive layer (1B) thickness 50 ⁇ m
  • An adhesive tape (C2) consisting of (1) (thickness 100 ⁇ m) / water vapor barrier layer (4) (thickness 50 ⁇ m) / adhesive layer (1B) (thickness 50 ⁇ m) ”was obtained.
  • Various evaluation results are shown in Table 1.
  • 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.

Abstract

Provided is an adhesive tape for preventing the attachment of aquatic organisms, wherein the tape can effectively prevent the attachment of aquatic organisms and exhibits a high osmosis suppression effect. This adhesive tape for preventing attachment of aquatic organisms includes an anti-fouling layer, an adhesive layer (A), a water vapor barrier layer, and an adhesive layer (B), in that order.

Description

水生生物付着防止粘着テープAquatic organism adhesion prevention adhesive tape
　本発明は、水生生物付着防止粘着テープに関する。詳細には、本発明は、水中構造物（船舶、ブイ、港湾設備、海上油田設備、発電所冷却水用の水路、工場冷却水用の水路、水上浮遊通路など）に水生生物が付着して繁殖することを防止するための、水生生物付着防止粘着テープに関する。 The present invention relates to an aquatic organism adhesion preventing adhesive tape. In detail, the present invention has aquatic organisms attached to underwater structures (ships, buoys, harbor facilities, offshore oilfield facilities, power plant cooling water channels, factory cooling water channels, floating floating channels, etc.). The present invention relates to an aquatic organism adhesion prevention adhesive tape for preventing breeding.
　船舶などの水中構造物は、海水に接触する部分において、フジツボ、カキ、ムラサキイガイ、ヒドラ、セルプラ、ホヤ、コケムシ、アオサ、アオノリ、付着珪藻などの水生生物が付着して繁殖し、流体抵抗の増加や熱伝導性の低下といった設備機械性能の低下や、付着した水生生物の海外への拡散など、好ましくない状態を引き起こしている。また、付着した水生生物を除去する作業には大きな労力と膨大な時間が必要であり、経済的な損失を被っている。 Underwater structures such as ships are in contact with seawater, and aquatic organisms such as barnacles, oysters, mussels, hydra, cell plastics, squirts, bryozoans, Aosa, Aonori, and attached diatoms grow and increase fluid resistance. It causes unfavorable conditions such as deterioration of machine performance such as deterioration of thermal conductivity and diffusion of attached aquatic organisms overseas. In addition, the work for removing the attached aquatic organisms requires a large amount of labor and enormous time, and suffers an economic loss.
　繊維強化プラスチック（ＦＲＰ）で構成された船体には、ＦＲＰ層の保護のためにゲルコート層が上塗りされている。このような積層構造を有する船体を海水に浸けた場合、ＦＲＰ層とゲルコート層との間に水が浸透し、水泡状の膨らみが発生するという現象（オズモシスあるいはブリスターと呼ばれることがある）が生じてしまうという問題がある。 The hull made of fiber reinforced plastic (FRP) is overcoated with a gel coat layer to protect the FRP layer. When a hull having such a laminated structure is immersed in seawater, a phenomenon occurs in which water permeates between the FRP layer and the gel coat layer and a blister-like bulge occurs (sometimes called osmosis or blister). There is a problem that it ends up.
　他方、船体の船底への水生生物の付着を防止する手段として、シリコーン系船底塗料が知られている（特許文献１参照）。 On the other hand, silicone-based ship bottom paints are known as means for preventing aquatic organisms from adhering to the ship bottom (see Patent Document 1).
　しかし、シリコーン系船底塗料は、水蒸気バリア性能が低い。このため、ＦＲＰ層／ゲルコート層の積層構造を有する船体の船底にシリコーン系船底塗料を塗装して防汚塗膜を形成しても、海水中において、ＦＲＰ層とゲルコート層との間に海水が浸透してしまい、やはり、オズモシスが生じてしまうという問題がある。 However, silicone ship bottom paint has low water vapor barrier performance. For this reason, even if the antifouling coating film is formed by coating the bottom of the hull having a laminated structure of FRP layer / gel coat layer to form an antifouling coating film, seawater remains between the FRP layer and the gel coat layer in seawater. There is a problem that it penetrates and osmosis occurs.
　船底塗料の下塗り剤としてエポキシ系プライマーを用いることによってオズモシス抑制効果を発現させることも行われている。しかし、エポキシ系プライマーを用いると、船底塗料と下塗り剤（プライマー）を用いて２層に塗装しなければならず、時間と労力とコストがかかるという問題があり、また、有機溶剤（ＶＯＣ）を含むため、それが揮発して作業環境や周辺の環境に悪影響を与えるという問題がある。 オ Osmosis suppression effect is also developed by using an epoxy primer as a primer for ship bottom paint. However, when an epoxy-based primer is used, it has to be applied to two layers using a ship bottom paint and a primer (primer), and there is a problem that it takes time, labor and cost, and an organic solvent (VOC) is used. Therefore, there is a problem that it volatilizes and adversely affects the work environment and the surrounding environment.
　他方、最近、船体の船底への水生生物の付着を防止する手段として、水生生物付着防止粘着テープが開発されている（特許文献２参照）。 On the other hand, an aquatic organism adhesion prevention adhesive tape has recently been developed as a means for preventing adhesion of aquatic organisms to the bottom of the hull (see Patent Document 2).
特開２００６－７７０９５号公報JP 2006-77095 A 特開２０１３－１４７６２９号公報JP 2013-147629 A
　本発明の課題は、水生生物の付着を効果的に防止できるとともに、オズモシス抑制効果の高い、水生生物付着防止粘着テープを提供することにある。 An object of the present invention is to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that can effectively prevent aquatic organism adhesion and has a high osmosis-suppressing effect.
　本発明の水生生物付着防止粘着テープは、
　防汚層と粘着剤層（Ａ）と水蒸気バリア層と粘着剤層（Ｂ）をこの順に含む。 The aquatic organism adhesion preventing adhesive tape of the present invention is
An antifouling layer, an adhesive layer (A), a water vapor barrier layer, and an adhesive layer (B) are included in this order.
　好ましい実施形態においては、上記水蒸気バリア層の透湿度が、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、８００ｇ／ｍ２・２４時間未満である。 In a preferred embodiment, the moisture permeability of the water vapor barrier layer is less than 800 g / m 2 · 24 hours when the thickness is converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
　好ましい実施形態においては、上記透湿度が５０ｇ／ｍ２・２４時間以下である。 In a preferred embodiment, the moisture permeability is 50 g / m 2 · 24 hours or less.
　好ましい実施形態においては、上記透湿度が１０ｇ／ｍ２・２４時間以下である。 In a preferred embodiment, the moisture permeability is 10 g / m 2 · 24 hours or less.
　好ましい実施形態においては、上記水蒸気バリア層の材料が有機高分子材料である。 In a preferred embodiment, the material of the water vapor barrier layer is an organic polymer material.
　好ましい実施形態においては、上記水蒸気バリア層の厚みが０．０１μｍ～１０００μｍである。 In a preferred embodiment, the water vapor barrier layer has a thickness of 0.01 μm to 1000 μm.
　好ましい実施形態においては、上記厚みが０．１μｍ～５００μｍである。 In a preferred embodiment, the thickness is 0.1 μm to 500 μm.
　好ましい実施形態においては、本発明の水生生物付着防止粘着テープは、弾性率が３００ＭＰａ以下である。 In a preferred embodiment, the aquatic organism adhesion preventing adhesive tape of the present invention has an elastic modulus of 300 MPa or less.
　好ましい実施形態においては、上記防汚層と上記粘着剤層（Ａ）との間に基材層を有する。 In a preferred embodiment, a base material layer is provided between the antifouling layer and the pressure-sensitive adhesive layer (A).
　本発明によれば、水生生物の付着を効果的に防止できるとともに、オズモシス抑制効果の高い、水生生物付着防止粘着テープを提供することができる。また、本発明の水生生物付着防止粘着テープは、好ましくは、高いオズモシス抑制効果だけでなく、防汚層と基材層との密着性を十分に担保し得る。さらに、本発明の水生生物付着防止粘着テープは、好ましくは、高いオズモシス抑制効果だけでなく、高い曲面追従性を発現し得る。 According to the present invention, it is possible to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape that can effectively prevent adhesion of aquatic organisms and has a high effect of suppressing osmosis. Moreover, the aquatic organism adhesion prevention adhesive tape of this invention can fully ensure not only the high osmosis suppression effect but the adhesiveness of an antifouling layer and a base material layer sufficiently. Furthermore, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can preferably exhibit not only a high osmosis suppression effect but also a high curved surface followability.
本発明の水生生物付着防止粘着テープの一例の概略断面図である。It is a schematic sectional drawing of an example of the aquatic organism adhesion prevention adhesive tape of this invention.
　本発明の水生生物付着防止粘着テープは、防汚層と粘着剤層（Ａ）と水蒸気バリア層と粘着剤層（Ｂ）をこの順に含む。 The aquatic organism adhesion preventing adhesive tape of the present invention includes an antifouling layer, an adhesive layer (A), a water vapor barrier layer and an adhesive layer (B) in this order.
　本発明の水生生物付着防止粘着テープにおいて、粘着剤層（Ａ）と粘着剤層（Ｂ）は、同種の粘着剤層であっても良いし、異種の粘着剤層であっても良い。 In the aquatic organism adhesion preventing pressure-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive layer (A) and the pressure-sensitive adhesive layer (B) may be the same type of pressure-sensitive adhesive layer or different types of pressure-sensitive adhesive layers.
　本発明の水生生物付着防止粘着テープは、防汚層と粘着剤層（Ａ）と水蒸気バリア層と粘着剤層（Ｂ）をこの順に含んでいれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していても良い。 If the aquatic organism adhesion prevention adhesive tape of the present invention includes an antifouling layer, an adhesive layer (A), a water vapor barrier layer and an adhesive layer (B) in this order, the effects of the present invention are not impaired. It may have any other suitable layer.
　本発明の水生生物付着防止粘着テープは、好ましくは、防汚層と粘着剤層との間に基材層を有する。 The aquatic organism adhesion preventing adhesive tape of the present invention preferably has a base material layer between the antifouling layer and the adhesive layer.
　本発明の水生生物付着防止粘着テープは、粘着剤層（Ａ）の防汚層と反対側に、水蒸気バリア層と粘着剤層（Ｂ）をこの順に有する。本発明においては、特にこのような構成を採用することによって、オズモシス抑制効果の高い水生生物付着防止粘着テープを提供することができる。また、このような構成を採用することによって、本発明の水生生物付着防止粘着テープは、好ましくは、高いオズモシス抑制効果だけでなく、基材層を有する場合、防汚層と基材層との密着性を十分に担保し得る。さらに、このような構成を採用することによって、本発明の水生生物付着防止粘着テープは、好ましくは、高いオズモシス抑制効果だけでなく、高い曲面追従性を発現し得る。 The aquatic organism adhesion preventing adhesive tape of the present invention has a water vapor barrier layer and an adhesive layer (B) in this order on the side opposite to the antifouling layer of the adhesive layer (A). In the present invention, by adopting such a configuration in particular, it is possible to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape having a high osmosis suppression effect. In addition, by adopting such a configuration, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention preferably has not only a high osmosis suppression effect but also a base material layer, the antifouling layer and the base material layer. Adhesion can be sufficiently secured. Furthermore, by adopting such a configuration, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can preferably exhibit not only a high osmosis suppression effect but also a high curved surface followability.
　本発明の水生生物付着防止粘着テープは、弾性率が、好ましくは３００ＭＰａ以下であり、より好ましくは１ＭＰａ～２００ＭＰａであり、さらに好ましくは１ＭＰａ～１５０ＭＰａであり、特に好ましくは１ＭＰａ～１００ＭＰａであり、最も好ましくは１ＭＰａ～８０ＭＰａである。本発明の水生生物付着防止粘着テープの弾性率を上記範囲内に調整することにより、高い曲面追従性を発現し得る。 The aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has an elastic modulus of preferably 300 MPa or less, more preferably 1 MPa to 200 MPa, still more preferably 1 MPa to 150 MPa, particularly preferably 1 MPa to 100 MPa. The pressure is preferably 1 MPa to 80 MPa. By adjusting the elastic modulus of the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention within the above range, high curved surface followability can be expressed.
　図１に、本発明の水生生物付着防止粘着テープの一例の概略断面図を示す。図１において、本発明の水生生物付着防止粘着テープ１００は、防汚層２と基材層３と粘着剤層（Ａ）４と水蒸気バリア層５と粘着剤層（Ｂ）６をこの順に含む。図１に示すように、防汚層２の表面や、粘着剤層（Ｂ）６の表面には、剥離フィルム１が設けられていても良い。 FIG. 1 shows a schematic cross-sectional view of an example of the aquatic organism adhesion preventing adhesive tape of the present invention. In FIG. 1, the aquatic organism adhesion prevention adhesive tape 100 of this invention contains the antifouling layer 2, the base material layer 3, the adhesive layer (A) 4, the water vapor barrier layer 5, and the adhesive layer (B) 6 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 pressure-sensitive adhesive layer (B) 6.
　図１に示す本発明の水生生物付着防止粘着テープの一例においては、本発明の水生生物付着防止粘着テープは、防汚層と基材層と粘着剤層（Ａ）と水蒸気バリア層と粘着剤層（Ｂ）をこの順に含み、好ましくは、防汚層と基材層と粘着剤層（Ａ）と水蒸気バリア層と粘着剤層（Ｂ）がこの順に直接に積層されてなる。 In one example of the aquatic organism adhesion preventing adhesive tape of the present invention shown in FIG. 1, the aquatic organism adhesion preventing adhesive tape of the present invention comprises an antifouling layer, a base material layer, an adhesive layer (A), a water vapor barrier layer and an adhesive. The layers (B) are included in this order, and preferably, the antifouling layer, the base material layer, the pressure-sensitive adhesive layer (A), the water vapor barrier layer, and the pressure-sensitive adhesive layer (B) are directly laminated in this order.
　水蒸気バリア層は、その透湿度が、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、好ましくは８００ｇ／ｍ２・２４時間未満であり、より好ましくは３００ｇ／ｍ２・２４時間以下であり、さらに好ましくは１００ｇ／ｍ２・２４時間以下であり、特に好ましくは５０ｇ／ｍ２・２４時間以下であり、最も好ましくは１０ｇ／ｍ２・２４時間以下である。上記水蒸気バリア層の透湿度の下限値は、低ければ低いほどよく、好ましくは０ｇ／ｍ２・２４時間である。ここで、「厚みを２５μｍに換算」とは、例えば、厚みがＬμｍの水蒸気バリア層の場合は、透湿度の値×（２５／Ｌ）とすることを意味する。 The water vapor barrier layer has a moisture permeability of preferably less than 800 g / m 2 · 24 hours, more preferably 300 g / m 2 when the thickness is converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH. m 2 · 24 hours or less, more preferably 100 g / m 2 · 24 hours or less, particularly preferably 50 g / m 2 · 24 hours or less, and most preferably 10 g / m 2 · 24 hours or less. . The lower limit value of the moisture permeability of the water vapor barrier layer is preferably as low as possible, and is preferably 0 g / m 2 · 24 hours. Here, “converting the thickness to 25 μm” means, for example, in the case of a water vapor barrier layer having a thickness of L μm, the value of moisture permeability × (25 / L).
　本発明の水生生物付着防止粘着テープにおいて、上記水蒸気バリア層の透湿度を上記のような特定の範囲内に調整することにより、オズモシス抑制効果のより高い水生生物付着防止粘着テープを提供し得る。すなわち、本発明においては、より高いオズモシス抑制効果を発揮させるために、透湿度が、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、好ましくは８００ｇ／ｍ２・２４時間未満（より好ましくは３００ｇ／ｍ２・２４時間以下であり、さらに好ましくは１００ｇ／ｍ２・２４時間以下であり、特に好ましくは５０ｇ／ｍ２・２４時間以下であり、最も好ましくは１０ｇ／ｍ２・２４時間以下であり、下限値が好ましくは０ｇ／ｍ２・２４時間である）となるような水蒸気バリア層を選択することが好ましい。 The aquatic organism adhesion prevention adhesive tape of this invention WHEREIN: By adjusting the water vapor permeability of the said water vapor | steam barrier layer in the above specific ranges, the aquatic organism adhesion prevention adhesive tape with a higher osmosis suppression effect can be provided. That is, in the present invention, in order to exert a higher osmosis suppression effect, when the thickness is converted to 25 μm in an atmosphere having a temperature of 40 ° C. and a humidity of 90% RH, preferably 800 g / m 2. Less than 24 hours (more preferably 300 g / m 2 · 24 hours or less, more preferably 100 g / m 2 · 24 hours or less, particularly preferably 50 g / m 2 · 24 hours or less, most preferably It is preferable to select a water vapor barrier layer that is 10 g / m 2 · 24 hours or less and the lower limit is preferably 0 g / m 2 · 24 hours.
　本発明の水生生物付着防止粘着テープの厚みは、それに含まれる各層の厚みによって、本発明の効果を損なわない範囲で、任意の適切な厚みに設定される。本発明の水生生物付着防止粘着テープの厚みは、好ましくは１０μｍ～２０００μｍであり、より好ましくは５０μｍ～８００μｍであり、さらに好ましくは１００μｍ～５００μｍである。本発明の水生生物付着防止粘着テープの厚みを上記範囲内に調整することにより、十分な強度を有するとともに貼付施工性の良好な水生生物付着防止粘着テープを提供し得る。 The thickness of the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention is set to any appropriate thickness within a range that does not impair the effects of the present invention, depending on the thickness of each layer included therein. The thickness of the aquatic organism adhesion preventing adhesive tape of the present invention is preferably 10 μm to 2000 μm, more preferably 50 μm to 800 μm, and further preferably 100 μm to 500 μm. By adjusting the thickness of the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention within the above range, it is possible to provide an aquatic organism adhesion-preventing pressure-sensitive adhesive tape having sufficient strength and good application workability.
　水蒸気バリア層は、１層のみであっても良いし、２層以上の積層体であっても良い。水蒸気バリア層が２層以上の積層体である場合は、該積層体は、例えば、ラミネートで成形しても良いし、共押出しによって成形しても良い。 The water vapor barrier layer may be a single layer or a laminate of two or more layers. When the water vapor barrier layer is a laminate of two or more layers, the laminate may be formed by, for example, a laminate or may be formed by coextrusion.
　水蒸気バリア層の材料としては、その透湿度が、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、好ましくは８００ｇ／ｍ２・２４時間未満（より好ましくは３００ｇ／ｍ２・２４時間以下であり、さらに好ましくは１００ｇ／ｍ２・２４時間以下であり、特に好ましくは５０ｇ／ｍ２・２４時間以下であり、最も好ましくは１０ｇ／ｍ２・２４時間以下であり、下限値が好ましくは０ｇ／ｍ２・２４時間である）であれば、任意の適切な材料を採用し得る。 As a material for the water vapor barrier layer, the moisture permeability is preferably less than 800 g / m 2 · 24 hours (more preferably 300 g) when the thickness is converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH. / M 2 · 24 hours or less, more preferably 100 g / m 2 · 24 hours or less, particularly preferably 50 g / m 2 · 24 hours or less, and most preferably 10 g / m 2 · 24 hours or less. And any lower limit value is preferably 0 g / m 2 · 24 hours).
　水蒸気バリア層の材料は、１種のみであっても良いし、２種以上を併用しても良い。 The material of the water vapor barrier layer may be only one kind, or two or more kinds may be used in combination.
　このような水蒸気バリア層の材料としては、例えば、ポリ塩化ビニリデン、塩化ビニリデンと塩化ビニル、アクリロニトリル等との共重合体；ポリ塩化ビニル；ポリエチレンテレフタラート、ポリブチレンテレフタラートなどのポリエステル系樹脂；ポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂；ポリテトラクロロエチレンなどのフッ素系樹脂；ポリアクリロニトリル；アクリロニトリルとメチルアクリレート、ブタジエン等との共重合体；ポリビニルアルコール；ビニルアルコールとエチレン等との共重合体；ナイロン６、ナイロン６６等のポリアミド系ポリマー；ポリイミド；ポリスチレン、スチレン系熱可塑性エラストマー（例えば、水添スチレン・ブタジエンゴム（ＨＳＢＲ）、スチレン系ブロック共重合体（例えば、スチレン・ブタジエン・スチレン共重合体（ＳＢＳ）、スチレン・イソプレン・スチレン共重合体（ＳＩＳ）等のスチレン系ＡＢＡ型ブロック共重合体（トリブロック共重合体）；スチレン・ブタジエン・スチレン・ブタジエン共重合体（ＳＢＳＢ）、スチレン・イソプレン・スチレン・イソプレン共重合体（ＳＩＳＩ）等のスチレン系ＡＢＡＢ型ブロック共重合体（テトラブロック共重合体）；スチレン・ブタジエン・スチレン・ブタジエン・スチレン共重合体（ＳＢＳＢＳ）、スチレン・イソプレン・スチレン・イソプレン・スチレン共重合体（ＳＩＳＩＳ）等のスチレン系ＡＢＡＢＡ型ブロック共重合体（ペンタブロック共重合体）；これ以上のＡＢ繰り返し単位を有するスチレン系ブロック共重合体；など）、スチレン系ブロック共重合体の水添物（例えば、スチレン・エチレン－ブチレン共重合体・スチレン共重合体（ＳＥＢＳ）、スチレン・エチレン－プロピレン共重合体・スチレン共重合体（ＳＥＰＳ）、スチレン・エチレン－ブチレン共重合体・スチレン・エチレン－ブチレン共重合体の共重合体（ＳＥＢＳＥＢ）；など）などのスチレン系ポリマー；ポリアクリレート；ポリエーテルスルフォン；ポリスルホン；などの有機高分子材料からなるフィルムが挙げられる。 Examples of the material for the water vapor barrier layer include polyvinylidene chloride, copolymers of vinylidene chloride and vinyl chloride, acrylonitrile, and the like; polyvinyl chloride; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyethylene Polyolefin resin such as polypropylene, fluorine resin such as polytetrachloroethylene, polyacrylonitrile, copolymer of acrylonitrile and methyl acrylate, butadiene, etc., polyvinyl alcohol, copolymer of vinyl alcohol and ethylene, nylon 6, nylon Polyamide, such as 66; polyimide; polystyrene, styrene thermoplastic elastomer (for example, hydrogenated styrene / butadiene rubber (HSBR), styrene block copolymer (for example, , Styrene-butadiene-styrene copolymer (SBS), styrene-based ABA block copolymer (triblock copolymer) such as styrene-isoprene-styrene copolymer (SIS); styrene-butadiene-styrene-butadiene copolymer Styrenic ABAB type block copolymer (tetrablock copolymer) such as polymer (SBSB), styrene / isoprene / styrene / isoprene copolymer (SISI); styrene / butadiene / styrene / butadiene / styrene copolymer ( SBSBS), styrene-based ABABA block copolymers (pentablock copolymers) such as styrene / isoprene / styrene / isoprene / styrene copolymers (SISIS); styrene block copolymers having more AB repeating units ;), Styrene block Hydrogenated copolymer (for example, styrene / ethylene / butylene copolymer / styrene copolymer (SEBS), styrene / ethylene / propylene copolymer / styrene copolymer (SEPS), styrene / ethylene / butylene copolymer) Examples thereof include a styrene polymer such as a polymer, a styrene / ethylene-butylene copolymer (SEBSEB), and the like; a film made of an organic polymer material such as a polyacrylate, a polyether sulfone, a polysulfone, and the like.
　このような水蒸気バリア層の材料としては、好ましくは、ポリ塩化ビニリデン、塩化ビニリデンと塩化ビニル、アクリロニトリル等との共重合体などの有機高分子材料からなるフィルムが挙げられる。 The material for the water vapor barrier layer is preferably a film made of an organic polymer material such as polyvinylidene chloride, a copolymer of vinylidene chloride and vinyl chloride, acrylonitrile, or the like.
　水蒸気バリア層の材料としては、金属酸化物や非金属無機酸化物が蒸着されたフィルムを使用することもできる。このようなフィルムとしては、例えば、ＰＥＴ、低オリゴマーＰＥＴ、ＰＢＴ、ＰＥＮ、ＰＢＮなどのポリエステル系フィルム、ＬＤＰＥ、ＬＬＤＰＥ、ホモＰＰ、ランダムＰＰ、ＥＶＡなどのポリオレフィン系フィルム、ポリ塩化ビニル系フィルム、フッ素系フィルム、ポリカーボネート系フィルム、ポリスルホン系フィルム、ポリ（メタ）アクリル系フィルムなどの基材上に、真空蒸着、イオンプレーティング、スパッタリングなどのＰＶＤ方式や、プラズマＣＶＤ、マイクロウェーブＣＶＤなどのＣＶＤ方式を用いて、金属酸化物や非金属無機酸化物が蒸着されたものが使用できる。蒸着に用いられる金属酸化物や非金属無機酸化物としては、例えば、ケイ素、アルミニウム、マグネシウム、カルシウム、カリウム、スズ、ナトリウム、ホウ素、チタン、鉛、ジルコニウム、イットリウムなどの酸化物が使用できる。また、アルカリ金属、アルカリ土類金属のフッ化物なども使用することができる。また、上記で用いる基材は、１種のみ用いても良いし、２種以上を組み合わせて用いても良い。 As a material for the water vapor barrier layer, a film on which a metal oxide or a nonmetal inorganic oxide is deposited can also be used. Examples of such films include polyester films such as PET, low oligomer PET, PBT, PEN, PBN, polyolefin films such as LDPE, LLDPE, homo PP, random PP, EVA, polyvinyl chloride films, fluorine PVD methods such as vacuum deposition, ion plating, and sputtering, and CVD methods such as plasma CVD and microwave CVD, etc. on base materials such as film, polycarbonate film, polysulfone film, and poly (meth) acrylic film It is possible to use a material in which a metal oxide or a nonmetal inorganic oxide is deposited. Examples of the metal oxide and non-metal inorganic oxide used for vapor deposition include oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. Alkali metal and alkaline earth metal fluorides can also be used. Moreover, the base material used by the above may be used only 1 type, and may be used in combination of 2 or more type.
　水蒸気バリア層の厚みは、本発明の水生生物付着防止粘着テープの用途や使用環境などによって、任意の適切な厚みを採用し得る。水蒸気バリア層の厚みは、好ましくは０．０１μｍ～１０００μｍであり、より好ましくは０．０５μｍ～８００μｍであり、さらに好ましくは０．１μｍ～５００μｍである。水蒸気バリア層の透湿度を、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、好ましくは８００ｇ／ｍ２・２４時間未満（より好ましくは３００ｇ／ｍ２・２４時間以下であり、さらに好ましくは１００ｇ／ｍ２・２４時間以下であり、特に好ましくは５０ｇ／ｍ２・２４時間以下であり、最も好ましくは１０ｇ／ｍ２・２４時間以下であり、下限値が好ましくは０ｇ／ｍ２・２４時間である）とするとともに、水蒸気バリア層の厚みを上記範囲内に調整することにより、オズモシス抑制効果のより高い水生生物付着防止粘着テープを提供し得る。また、水蒸気バリア層の厚みを上記範囲内に調整することにより、本発明の水生生物付着防止粘着テープを、曲面や鋭角面など、平面以外の部位にも容易に作業性良く貼着し得るとともに、貼着後の表面にしわや浮きなどの外観不良が生じることを抑制し得る。 As the thickness of the water vapor barrier layer, any appropriate thickness can be adopted depending on the application or use environment of the aquatic organism adhesion preventing adhesive tape of the present invention. The thickness of the water vapor barrier layer is preferably 0.01 μm to 1000 μm, more preferably 0.05 μm to 800 μm, and still more preferably 0.1 μm to 500 μm. The moisture permeability of the water vapor barrier layer is preferably less than 800 g / m 2 · 24 hours (more preferably 300 g / m 2 · 24) when the thickness is converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH. Or less, more preferably 100 g / m 2 · 24 hours or less, particularly preferably 50 g / m 2 · 24 hours or less, most preferably 10 g / m 2 · 24 hours or less, and the lower limit is preferably as well as to be 0g / m 2 · 24 hours), by adjusting the thickness of the water vapor barrier layer in the above range can provide a higher aquatic biofouling adhesive tape osmosis inhibiting effect. In addition, by adjusting the thickness of the water vapor barrier layer within the above range, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can be easily attached to sites other than flat surfaces such as curved surfaces and acute angle surfaces with good workability. It is possible to suppress appearance defects such as wrinkles and floats on the surface after sticking.
　基材層は、その２３℃における弾性率が、好ましくは０．１ＭＰａ～１００ＭＰａである。上記弾性率を上記範囲内に調整することによって、防汚層と基材層との密着性に優れた水生生物付着防止粘着テープを提供し得る。 The base layer has an elastic modulus at 23 ° C. of preferably 0.1 MPa to 100 MPa. By adjusting the elastic modulus within the above range, an aquatic organism adhesion preventing adhesive tape having excellent adhesion between the antifouling layer and the base material layer can be provided.
　基材層は、その２３℃における伸長回復率が、好ましくは７０％以上である。上記伸長回復率を上記範囲内に調整することによって、防汚層と基材層との密着性に優れた水生生物付着防止粘着テープを提供し得る。 The base material layer preferably has an elongation recovery rate at 23 ° C. of 70% or more. By adjusting the elongation recovery rate within the above range, an aquatic organism adhesion-preventing pressure-sensitive adhesive tape having excellent adhesion between the antifouling layer and the base material layer can be provided.
　基材層としては、本発明の効果を損なわない範囲で、任意の適切な基材層を採用し得る。このような基材層の材料（好ましくは、基材層の主成分（好ましくは基材層中に５０重量％以上、より好ましくは基材層中に７０重量％以上、さらに好ましくは基材層中に９０重量％以上、特に好ましくは基材層中に９５重量％以上）である樹脂）としては、好ましくは、耐水性、強度、柔軟性、裂け性に優れるものである。このような基材層の材料としては、例えば、ポリウレタン樹脂、ポリウレタンアクリル樹脂、ゴム系樹脂、塩化ビニル樹脂、ポリエステル樹脂、シリコーン樹脂、エラストマー類、フッ素樹脂、ポリアミド樹脂、ポリオレフィン樹脂（ポリエチレン、ポリプロピレンなど）などが挙げられる。このような基材層の材料は、１種のみであっても良いし、２種以上であっても良い。 As the base material layer, any appropriate base material layer can be adopted as long as the effects of the present invention are not impaired. Such a material for the base material layer (preferably, the main component of the base material layer (preferably 50% by weight or more in the base material layer, more preferably 70% by weight or more in the base material layer, more preferably the base material layer) The resin) is preferably 90% by weight or more, particularly preferably 95% by weight or more in the base material layer, and is preferably excellent in water resistance, strength, flexibility and tearability. Examples of the material for the base material layer include polyurethane resin, polyurethane acrylic resin, rubber resin, vinyl chloride resin, polyester resin, silicone resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.) ) And the like. The material of such a base material layer may be only one type or two or more types.
　基材層の材料としては、特に、ポリウレタン樹脂、ポリエステル樹脂が好ましく、ポリウレタン樹脂がより好ましい。 As the material for the base material layer, polyurethane resin and polyester resin are particularly preferable, and polyurethane resin is more preferable.
　ポリウレタン樹脂としては、例えば、エーテル系ポリウレタン、エステル系ポリウレタン、カーボネート系ポリウレタンなどが挙げられ、耐久性や強度に優れる点、および、本発明の効果を十分に発現できる点から、カーボネート系ポリウレタンが特に好ましい。また、ポリウレタン樹脂のグレードとしては、難黄変グレードと無黄変グレードが好ましく、無黄変グレードがより好ましい。 Examples of polyurethane resins include ether-based polyurethanes, ester-based polyurethanes, carbonate-based polyurethanes, and carbonate-based polyurethanes are particularly preferred because they are excellent in durability and strength, and can sufficiently exhibit the effects of the present invention. preferable. Moreover, as a grade of a polyurethane resin, a non-yellowing grade and a non-yellowing grade are preferable, and a non-yellowing grade is more preferable.
　ポリエステル樹脂としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）などが挙げられる。 Examples of the polyester resin include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
　基材層は、その破断伸びが、好ましくは１００％～１０００％であり、より好ましくは１５０％～９００％であり、さらに好ましくは２００％～８００％である。基材層の破断伸びを上記範囲内に調整することによって、本発明の水生生物付着防止粘着テープは、様々な被着体の形状に良好に追従し得、平面に良好に貼付し得るだけでなく、船体表面に存在するような曲面部分、９０度角の部分、鋭角部分などにも良好に貼付し得る。 The base material layer has an elongation at break of preferably 100% to 1000%, more preferably 150% to 900%, and further preferably 200% to 800%. By adjusting the elongation at break of the base material layer within the above range, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention can follow the shape of various adherends well and can be applied to a flat surface. In addition, it can be satisfactorily affixed to a curved surface portion, a 90-degree angle portion, an acute angle portion, or the like present on the surface of the hull.
　基材層は、その破断点応力が、好ましくは２０ＭＰａ以上であり、より好ましくは２５ＭＰａ～２００ＭＰａであり、さらに好ましくは３０ＭＰａ～１５０ＭＰａであり、特に好ましくは３５ＭＰａ～１００ＭＰａである。基材層の破断点応力を上記範囲内に調整することによって、使用済みの本発明の水生生物付着防止粘着テープを被着体から剥がす際に基材層が切断されることを抑制し得る。 The base material layer has a stress at break of preferably 20 MPa or more, more preferably 25 MPa to 200 MPa, still more preferably 30 MPa to 150 MPa, and particularly preferably 35 MPa to 100 MPa. By adjusting the breaking stress of the base material layer within the above range, the base material layer can be prevented from being cut when the used aquatic organism adhesion preventing adhesive tape of the present invention is peeled off from the adherend.
　なお、上記破断伸びおよび破断点応力は、例えば、ＪＩＳ７１６１、ＪＩＳ７１６２、ＪＩＳ７１２７に準じて、引っ張り試験機（ＡＵＴＯＧＲＡＰＨ　ＡＧＳ－Ｘ、（株）島津製作所製）および解析ソフト（ＴＲＡＰＥＺＩＵＭ　Ｘ、（株）島津製作所製）を用いて測定することができる。 The elongation at break and the stress at break are, for example, in accordance with JIS 7161, JIS 7162, and JIS 7127, a tensile tester (AUTOGRAPH AGS-X, manufactured by Shimadzu Corporation) and analysis software (TRAPEZIUM X, Shimadzu Corporation). Can be used.
　基材層は、本発明の効果を損なわない範囲で、任意の適切な添加剤を含んでいても良い。このような添加剤としては、例えば、オレフィン系樹脂、シリコーン系ポリマー、液状アクリル系共重合体、粘着付与剤、老化防止剤、ヒンダードアミン系光安定剤、紫外線吸収剤、酸化防止剤、帯電防止剤、ポリエチレンイミン、脂肪酸アミド、脂肪酸エステル、リン酸エステル、滑剤、界面活性剤、充填剤や顔料（例えば、酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛、酸化チタン、カーボンブラックなど）などが挙げられる。 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.).
　基材層は、紫外線吸収剤を含んでいても良い。基材層が紫外線吸収剤を含むことにより、本発明の水生生物付着防止粘着テープの耐候性が向上する。 The base material layer may contain 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.
　基材層の厚みは、本発明の水生生物付着防止粘着テープの用途や使用環境などによって、任意の適切な厚みを採用し得る。基材層の厚みは、好ましくは１μｍ～１０００μｍであり、より好ましくは１０μｍ～８００μｍであり、さらに好ましくは２０μｍ～５００μｍである。基材層の厚みを上記範囲内に調整することにより、本発明の水生生物付着防止粘着テープは、曲面や鋭角面など、平面以外の部位にも容易に作業性良く貼着し得るとともに、貼着後の表面にしわや浮きなどの外観不良が生じることを抑制し得る。 Any appropriate thickness can be adopted as the thickness of the base material layer depending on the application and use environment of the aquatic organism adhesion preventing adhesive tape of the present invention. 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 adjusting 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. It is possible to suppress appearance defects such as wrinkles and floats on the surface after wearing.
　基材層には、防汚層との密着性を向上させるために、プライマーをあらかじめ塗工しておいても良いし、シランカップリング剤をあらかじめ添加しておいても良い。 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.
　シランカップリング剤は、１種のみであっても良いし、２種以上であっても良い。市販されている具体的なシランカップリング剤としては、例えば、信越化学工業（株）製のＫＢＭ５１０３、ＫＢＭ１００３、ＫＢＭ９０３、ＫＢＭ４０３、ＫＢＭ８０２などが挙げられる。 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.
　基材層にシランカップリング剤が含まれる場合、基材層中のシランカップリング剤の含有割合は、好ましくは０．０１重量％～１０重量％である。基材層中のシランカップリング剤の含有割合を上記範囲内に調整することにより、基材層が硬くなり過ぎることを抑制し得るとともに、基材層と防汚層との間に十分な密着性を発現し得る。 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 adjusting the content ratio of the silane coupling agent in the base material layer within the above range, the base material layer can be prevented from becoming too hard, and sufficient adhesion is provided between the base material layer and the antifouling layer. Sex can be expressed.
　防汚層は、防汚効果を発現し得るマトリックス樹脂（以下、単に「マトリックス樹脂」と称することがある）を含む。このようなマトリックス樹脂としては、防汚効果を発現し得るものであれば、任意の適切な樹脂を採用し得る。このようなマトリックス樹脂としては、好ましくは、シリコーン樹脂が挙げられる。このようなマトリックス樹脂は、１種のみであっても良いし、２種以上であっても良い。 The antifouling layer contains a matrix resin capable of exhibiting an antifouling effect (hereinafter sometimes simply referred to as “matrix resin”). As such a matrix resin, any appropriate resin can be adopted as long as it can exhibit an antifouling effect. As such a matrix resin, a silicone resin is preferably used. Such matrix resin may be only one kind, or two or more kinds.
　防汚層中のマトリックス樹脂の含有割合は、本発明の効果を損なわない範囲で、任意の適切な含有割合を採用し得る。防汚層中のマトリックス樹脂の含有割合は、好ましくは３０重量％～９８重量％であり、より好ましくは４０重量％～９７重量％であり、さらに好ましくは４５重量％～９６重量％であり、特に好ましくは５０重量％～９５重量％である。防汚層中のマトリックス樹脂の含有割合を上記範囲内に調整することにより、防汚層の防汚効果を十分に発現し得るとともに、防汚層の機械的特性を十分に発現し得る。 Any appropriate content ratio can be adopted as the content ratio of the matrix resin in the antifouling layer as long as the effects of the present invention are not impaired. The content ratio of the matrix resin in the antifouling layer is preferably 30% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, still more preferably 45% by weight to 96% by weight, Particularly preferred is 50 to 95% by weight. By adjusting the content ratio of the matrix resin in the antifouling layer within the above range, the antifouling effect of the antifouling layer can be sufficiently expressed, and the mechanical characteristics of the antifouling layer can be sufficiently expressed.
　マトリックス樹脂として用い得るシリコーン樹脂としては、本発明の効果を損なわない範囲で、任意の適切なシリコーン樹脂を採用し得る。シリコーン樹脂は、１種のみであっても良いし、２種以上であっても良い。このようなシリコーン樹脂としては、常温で液状のシリコーン樹脂であっても良いし、常温で固体状のシリコーン樹脂であっても良い。また、このようなシリコーン樹脂としては、縮合型のシリコーン樹脂であっても良いし、付加型のシリコーン樹脂であっても良い。また、このようなシリコーン樹脂としては、単独で乾燥させる１液型のシリコーン樹脂であっても良いし、硬化剤を配合する２液型のシリコーン樹脂であっても良い。 As the silicone resin that can be used as the matrix 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.
　本発明においては、マトリックス樹脂として用い得るシリコーン樹脂としては、上記の中でも、２液型のシリコーン樹脂が好ましく、２液型の加熱付加型シリコーン樹脂がより好ましい。このような２液型の加熱付加型シリコーン樹脂としては、例えば、信越化学工業（株）製のＫＥ－１９５０－１０（Ａ／Ｂ）、ＫＥ－１９５０－２０（Ａ／Ｂ）、ＫＥ－１９５０－３０（Ａ／Ｂ）、ＫＥ－１９５０－３５（Ａ／Ｂ）、ＫＥ－１９５０－４０（Ａ／Ｂ）、ＫＥ－１９５０－５０（Ａ／Ｂ）、ＫＥ－１９５０－６０（Ａ／Ｂ）、ＫＥ－１９５０－７０（Ａ／Ｂ）、ＫＥ－１９８７（Ａ／Ｂ）、ＫＥ－１９８８（Ａ／Ｂ）、旭化成ワッカーシリコーン（株）製のＬＲ７６６５シリーズ、ＬＲ３０３３シリーズ、モメンティブ（株）製のＴＳＥ３０３２シリーズなどが挙げられる。 In the present invention, the silicone resin that can be used as the matrix resin is preferably a two-part silicone resin, more preferably a two-part heat addition type silicone resin. Examples of such two-pack heat addition type silicone resins include KE-1950-10 (A / B), KE-1950-20 (A / B), and KE-1950 manufactured by Shin-Etsu Chemical Co., Ltd. -30 (A / B), KE-1950-35 (A / B), KE-1950-40 (A / B), KE-1950-50 (A / B), KE-1950-60 (A / B) ), KE-1950-70 (A / B), KE-1987 (A / B), KE-1988 (A / B), LR7665 series, LR3033 series, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., manufactured by Momentive Co., Ltd. And the TSE3032 series.
　本発明の水生生物付着防止粘着テープにおける水生生物の易除去性を向上させるために、シリコーン樹脂としては、水洗除去時の水圧などによって樹脂表面が弾性変形することにより付着物の剥離が容易になるような物性を有するシリコーン樹脂が好ましい。このようなシリコーン樹脂は、該シリコーン樹脂の１００％モジュラス（引張応力）が、好ましくは０．１ＭＰａ～１０ＭＰａであり、より好ましくは０．１ＭＰａ～６ＭＰａである。また、このようなシリコーン樹脂は、有機溶剤に可溶であるものが好ましい。 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.
　防汚層は、好ましくは、防汚剤を含む。 The antifouling layer preferably contains an antifouling agent.
　防汚剤としては、例えば、シリコーンオイル、流動パラフィン、界面活性剤、液状炭化水素、フッ化オイル、抗菌剤などが挙げられる。これらは、１種のみであっても良いし、２種以上であっても良い。防汚層が、このような防汚剤を含む場合、該防汚剤は、マトリックス樹脂の表面に移行し、表面を防汚物質で覆うことによって、水生生物のシリコーン樹脂表面への付着を抑制し、高い防汚効果を長期間維持する作用を発現することができる。したがって、長期間にわたって防汚効果を持続でき、人体や環境に対する負荷が少なく、重量が軽く、安定した品質を維持でき、水生生物の付着を効果的に防止できる、水生生物付着防止粘着テープを提供することができる。 Examples of the antifouling agent include silicone oil, liquid paraffin, surfactant, liquid hydrocarbon, fluorinated oil, and antibacterial agent. These may be only one type or two or more types. When the antifouling layer contains such an antifouling agent, the antifouling agent moves to the surface of the matrix resin and covers the surface with an antifouling substance, thereby suppressing the adhesion of aquatic organisms to the silicone resin surface. And the effect | action which maintains a high antifouling effect for a long period of time can be expressed. Therefore, an aquatic organism adhesion prevention adhesive tape that can maintain the antifouling effect for a long period of time, has little impact on the human body and the environment, is light in weight, can maintain stable quality, and can effectively prevent the attachment of aquatic organisms is provided. can do.
　防汚層中、マトリックス樹脂に対する防汚剤の含有割合は、好ましくは１重量％～２００重量％であり、より好ましくは２重量％～２０重量％である。上記の含有割合を上記範囲内に調整することにより、防汚層の防汚効果を十分に発現し得るとともに、防汚層の外観特性や機械的特性を十分に発現し得る。 In the antifouling layer, the content ratio of the antifouling agent to the matrix resin is preferably 1% by weight to 200% by weight, more preferably 2% by weight to 20% by weight. By adjusting the above content ratio 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.
　シリコーンオイルとしては、本発明の効果を損なわない範囲で任意の適切なシリコーンオイルを採用し得る。シリコーンオイルとしては、マトリックス樹脂との反応性や自己縮合性を有さないものが好ましい。このようなシリコーンオイルとしては、例えば、マトリックス樹脂としてシリコーン樹脂を用いる場合は、該シリコーン樹脂に含まれるオルガノポリシロキサンとある程度不相溶であるものが好ましく、長期間にわたって防汚効果を持続できる点で、例えば、一般式（Ｉ）で表されるシリコーンオイルが好ましい。 As the silicone oil, any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired. The silicone oil is preferably one that does not have reactivity with the matrix resin or self-condensation. As such a silicone oil, for example, when a silicone resin is used as a matrix resin, it is preferable that the silicone resin is incompatible with the organopolysiloxane contained in the silicone resin to a certain extent, and the antifouling effect can be maintained over a long period of time. For example, a silicone oil represented by the general formula (I) is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　一般式（Ｉ）中、Ｒ１は、同一または異なって、炭素数１～１０のアルキル基、アリール基、アラルキル基、フルオロアルキル基、ポリエーテル基、または水酸基を表し、Ｒ２は、同一または異なって、炭素数１～１０のアルキル基、アリール基、アラルキル基、ポリエーテル基、フルオロアルキル基を表し、ｎは０～１５０の整数を表す。一般式（Ｉ）中のＲ１としては、好ましくは、メチル基、フェニル基、水酸基である。一般式（Ｉ）中のＲ２としては、好ましくは、メチル基、フェニル基、４－トリフルオロブチル基である。 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.
　一般式（Ｉ）で表されるシリコーンオイルは、数平均分子量が、好ましくは１８０～２００００であり、より好ましくは１０００～１００００である。 The number average molecular weight of the silicone oil represented by the general formula (I) is preferably 180 to 20000, and more preferably 1000 to 10,000.
　一般式（Ｉ）で表されるシリコーンオイルは、粘度が、好ましくは１０センチストークス～１００００センチストークスであり、より好ましくは１００センチストークス～５０００センチストークスである。 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.
　一般式（Ｉ）で表されるシリコーンオイルとしては、具体的には、例えば、両末端または片末端のＲ１が水酸基である末端水酸基含有ジメチルシリコーンオイル、Ｒ１およびＲ２の全てがメチル基であるジメチルシリコーンオイル、これらのジメチルシリコーンオイルのメチル基の一部がフェニル基に置換されたフェニルメチルシリコーンオイルなどが挙げられる。 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.
　一般式（Ｉ）で表されるシリコーンオイルの市販品としては、例えば、信越化学工業（株）製のＫＦ９６Ｌ、ＫＦ９６、ＫＦ６９、ＫＦ９９、ＫＦ５０、ＫＦ５４、ＫＦ４１０、ＫＦ４１２、ＫＦ４１４、ＦＬ、東レダウコーニング株式会社製のＢＹ１６－８４６、ＳＦ８４１６、ＳＨ２００、ＳＨ２０３、ＳＨ２３０、ＳＦ８４１９、ＦＳ１２６５、ＳＨ５１０、ＳＨ５５０、ＳＨ７１０、ＦＺ－２１１０、ＦＺ－２２０３が挙げられる。 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.
　流動パラフィンとしては、本発明の効果を損なわない範囲で任意の適切な流動パラフィンを採用し得る。流動パラフィンとしては、例えば、（株）ＭＯＲＥＳＣＯ製のＰ－４０、Ｐ－５５、Ｐ－６０、Ｐ－７０、Ｐ－８０、Ｐ－１００、Ｐ－１２０、Ｐ－１５０、Ｐ－２００、Ｐ－２６０、Ｐ－３５０、和光純薬工業（株）製の炭化水素系流動パラフィンなどが挙げられる。 As the liquid paraffin, any appropriate liquid paraffin can be adopted as long as the effects of the present invention are not impaired. Examples of liquid paraffin include P-40, P-55, P-60, P-70, P-80, P-100, P-120, P-150, P-200, P manufactured by MORESCO. -260, P-350, hydrocarbon liquid paraffin manufactured by Wako Pure Chemical Industries, Ltd.
　界面活性剤としては、例えば、アニオン系界面活性剤、ノニオン系界面活性剤、両性界面活性剤、カチオン系界面活性剤、などが挙げられる。 Examples of the surfactant include an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant.
　アニオン界面活性剤としては、本発明の効果を損なわない範囲で任意の適切なアニオン界面活性剤を採用し得る。このようなアニオン界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキルまたはアルケニルエーテル硫酸塩、アルキルまたはアルケニル硫酸塩、α－オレフィンスルホン酸塩、α－スルホ脂肪酸またはエステル塩、アルカンスルホン酸塩、飽和または不飽和脂肪酸塩、アルキルまたはアルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、Ｎ－アシルアミノ酸型界面活性剤、アルキルまたはアルケニルリン酸エステルまたはその塩などが挙げられる。アニオン界面活性剤は、１種のみであっても良いし、２種以上であっても良い。 As the anionic surfactant, any appropriate anionic surfactant can be adopted as long as the effects of the present invention are not impaired. Such anionic surfactants include, for example, alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acid or ester salts, alkane sulfonates, Examples thereof include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. Only one type of anionic surfactant may be used, or two or more types may be used.
　ノニオン界面活性剤としては、本発明の効果を損なわない範囲で任意の適切なノニオン界面活性剤を採用し得る。このようなノニオン界面活性剤としては、例えば、ポリオキシアルキレンアルキルまたはアルケニルエーテル、ポリオキシエチレンアルキルフェニルエーテル、高級脂肪酸アルカノールアミドまたはそのアルキレンオキサイド付加物、ショ糖脂肪酸エステル、アルキルグリコキシド、脂肪酸グリセリンモノエステル、アルキルアミンオキサイドなどが挙げられる。ノニオン界面活性剤は、１種のみであっても良いし、２種以上であっても良い。 As the nonionic surfactant, any appropriate nonionic surfactant can be adopted as long as the effects of the present invention are not impaired. Examples of such nonionic surfactants include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester. Examples thereof include esters and alkylamine oxides. Only one nonionic surfactant may be used, or two or more nonionic surfactants may be used.
　両性界面活性剤としては、本発明の効果を損なわない範囲で任意の適切な両性界面活性剤を採用し得る。このような両性界面活性剤としては、例えば、カルボキシ型またはスルホベタイン型両性界面活性剤などが挙げられる。両性界面活性剤は、１種のみであっても良いし、２種以上であっても良い。 As the amphoteric surfactant, any appropriate amphoteric surfactant can be adopted as long as the effects of the present invention are not impaired. Examples of such amphoteric surfactants include carboxy type or sulfobetaine type amphoteric surfactants. Only one amphoteric surfactant may be used, or two or more amphoteric surfactants may be used.
　カチオン界面活性剤としては、本発明の効果を損なわない範囲で任意の適切なカチオン界面活性剤を採用し得る。このようなカチオン界面活性剤としては、例えば、第４級アンモニウム塩などが挙げられる。カチオン界面活性剤は、１種のみであっても良いし、２種以上であっても良い。 As the cationic surfactant, any appropriate cationic surfactant can be adopted as long as the effects of the present invention are not impaired. Examples of such cationic surfactants include quaternary ammonium salts. Only one type of cationic surfactant may be used, or two or more types may be used.
　液状炭化水素としては、本発明の効果を損なわない範囲で任意の適切な液状炭化水素を採用し得る。例えば、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、１－テトラデセンなどが挙げられる。 As the liquid hydrocarbon, any appropriate liquid hydrocarbon can be adopted as long as the effects of the present invention are not impaired. Examples thereof include hexane, heptane, benzene, toluene, xylene, 1-tetradecene and the like.
　フッ化オイルとしては、本発明の効果を損なわない範囲で任意の適切なフッ化オイルを採用し得る。このようなフッ化オイルとしては、例えば、パーフルオロポリエーテル、パーフルオロデカリン、パーフルオロオクタン等が挙げられる。化学的安定性の点でパーフルオロポリエーテルが好ましい。パーフルオロポリエーテルとしては、例えば、構造式：Ａ－（Ｃ３Ｆ６Ｏ）ｘ（ＣＦ２Ｏ）ｙ（Ｃ２Ｆ４Ｏ）ｚ―Ｂ（式中、末端基Ａは、－Ｆ、－ＣＦ３、－Ｃ２Ｆ５、－Ｃ３Ｆ７、－ＣＦ（ＣＦ３）ＯＣＦ３、－ＯＦ、－ＯＣＦ３、－ＯＣ２Ｆ５、－ＯＣ３Ｆ７、－ＯＣＦ（ＣＦ３）ＯＣＦ３のいずれかあり、末端基Ｂは、－ＣＦ３、－Ｃ２Ｆ５、－Ｃ３Ｆ７、－ＣＦ（ＣＦ３）ＯＣＦ３のいずれかあり、ｘ、ｙ、ｚは０または正の整数であり、ｘ＋ｙ＋ｚ＞１であって、２５℃における粘度が５０ｃｓ～５０００００ｃｓである。）で表される化合物が挙げられる。パーフルオロポリエーテルの具体例としては、例えば、ＣＦ３Ｏ－（ＣＦ２ＣＦ（ＣＦ３）Ｏ）ｘ（ＣＦ２Ｏ）ｙ－ＣＦ３（式中、ｘ、ｙは上記の通りである。）、ＣＦ３Ｏ－（ＣＦ２Ｏ）ｙ（Ｃ２Ｆ４Ｏ）ｚ－ＣＦ３（式中、ｙ、ｚは上記の通りである）、ＣＦ３Ｏ－（ＣＦ２ＣＦ（ＣＦ３）Ｏ）ｘ－ＣＦ３（式中、ｘは上記の通りである）、及び、Ｆ－（ＣＦ２ＣＦ２ＣＦ２Ｏ）ｘ－Ｃ２Ｆ５（式中、ｘは上記の通りである）などが挙げられる。 Any appropriate fluorinated oil can be adopted as the fluorinated oil as long as the effects of the present invention are not impaired. Examples of such fluorinated oils include perfluoropolyether, perfluorodecalin, perfluorooctane, and the like. Perfluoropolyether is preferred in terms of chemical stability. As the perfluoropolyether, for example, the structural formula: A- (C 3 F 6 O) x (CF 2 O) y (C 2 F 4 O) z-B (wherein the end group A is —F, —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF (CF 3 ) OCF 3 , —OF, —OCF 3 , —OC 2 F 5 , —OC 3 F 7 , —OCF (CF 3 ) One of OCF 3 , the terminal group B is any of —CF 3 , —C 2 F 5 , —C 3 F 7 , —CF (CF 3 ) OCF 3 , and x, y, z are 0 or positive And x + y + z> 1 and the viscosity at 25 ° C. is from 50 cs to 500,000 cs). Specific examples of the perfluoropolyether include, for example, CF 3 O— (CF 2 CF (CF 3 ) O) x (CF 2 O) y —CF 3 (wherein x and y are as described above). ), CF 3 O- (CF 2 O) y (C 2 F 4 O) z-CF 3 ( wherein, y, z are as defined above), CF 3 O- (CF 2 CF (CF 3) O) x-CF 3 (wherein x is as described above) and F- (CF 2 CF 2 CF 2 O) x-C 2 F 5 (wherein x is as described above) Etc.
　抗菌剤としては、本発明の効果を損なわない範囲で任意の適切な抗菌剤を採用し得る。このような抗菌剤としては、いわゆる抗菌剤、除草剤などが挙げられる。 As the antibacterial agent, any appropriate antibacterial agent can be adopted as long as the effects of the present invention are not impaired. Examples of such antibacterial agents include so-called antibacterial agents and herbicides.
　いわゆる抗菌剤としては、例えば、アゾキシストロビン、ベナラキシル、ベノミル、ビテルタノール、ブロムコナゾール、キャプタホール、キャプタン、カルベンダジム、キノメチオネート、クロロタロニル、クロゾリナート、シプロジニル、ジクロフルアニド、ジクロフェン、ジクロメジン、ジクロラン、ジエトフェンカルブ、ジメトモルフ、ジニコナゾール、ジチアノン、エポキシコナゾール、ファモキサドン、フェナリモル、フェンブコナゾール、フェンフラム、フェンピクロニル、フェンチン、フルアジナム、フルジオキソニル、フルオルイミド、フルキンコナゾール、フルスルファミド、フルトラニル、ホルペット、ヘキサクロロベンゼン、ヘキサコナゾール、イミベンコナゾール、イポコナゾール、イプロジオン、クレソキシムメチル、マンゼブ、マンネブ、メパニピリム、メプロニル、メトコナゾール、メチラム、ニッケルビス（ジメチルジチオカルバメート）、ヌアリモル、オキシン銅、オキソリン酸、ペンシクロン、フタリド、プロシミドン、プロピネブ、キントゼン、硫黄、テブコナゾール、テクロフタラム、テクナゼン、チフルザミド、チオフェネートメチル、チラム、トルクロホスメチル、トリルフルアニド、トリアジメホン、トリアジメノール、トリアゾキシド、トリホリン、トリチコナゾール、ビンクロゾリン、ジネブ、ジラムなどが挙げられる。また、天然物の抗菌剤として、例えば、孟宗竹抽出物、ヒノキチオール、ニンニクエキス、カンゾウなどの漢方成分が挙げられる。また、銀、銅、亜鉛、錫、鉛、金などの無機抗菌剤が挙げられる。また、必要に応じて、これら無機抗菌剤の担体として、ゼオライト、ヒドロキシアパタイト、炭酸カルシウム、シリカゲル、ケイ酸アルミニウムカルシウム、ポリシロキサン化合物、リン酸ジルコニウム、硫酸ジルコニウム、イオン交換体、酸化亜鉛などが使用できる。合成物の抗菌剤としては、例えば、２－ピリジンチオール－１－オキサイド、ｐ－クロロ－ｍ－クレゾール、ポリヘキサメチレンヒグアナイド、ハイドロクロライド、塩化ベンゼトニウム、アルキルポリアミノエチルグリシン、ベンズイソチアゾリン、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、１，２－ベンズイソチアゾリン－３－オン、２，２’－ジチオ－ビス－（ピリジン－１－オキサイド）などが挙げられる。 So-called antibacterial agents include, for example, azoxystrobin, benalaxyl, benomyl, viteltanol, bromconazole, captahol, captan, carbendazim, quinomethionate, chlorothalonil, clozolinate, cyprozinyl, diclofluanide, diclofene, diclomedin, dichlorane, Dietofencarb, dimethomorph, diniconazole, dithianon, epoxiconazole, famoxadone, fenarimol, fenbuconazole, fenfram, fenpiclonil, fentin, fluazinam, fludioxonil, fluorimide, fluquinconazole, fursulfamide, flutolanil, holpet, hexachlorobenzene, hexaconazole, imi Benconazole, Ipoconazole, Iprodione, Cresoxy Methyl, manzeb, mannebu, mepanipyrim, mepronyl, metconazole, methylam, nickel bis (dimethyldithiocarbamate), nuarimol, copper oxolinic acid, pencyclon, phthalide, prosimidone, propineb, quintozene, sulfur, tebuconazole, teclophthalam, technazen, tifluzamide Examples include thiophenate methyl, thiram, tolcrofosmethyl, tolylfluanid, triadimethone, triadimenol, triazoxide, triphorin, triticonazole, vinclozolin, dineb, dilam and the like. In addition, examples of natural antibacterial agents include Chinese herbal ingredients such as Soso bamboo extract, hinokitiol, garlic extract and licorice. Moreover, inorganic antibacterial agents, such as silver, copper, zinc, tin, lead, and gold, are mentioned. In addition, zeolites, hydroxyapatite, calcium carbonate, silica gel, aluminum calcium silicate, polysiloxane compounds, zirconium phosphate, zirconium sulfate, ion exchangers, zinc oxide, etc. are used as carriers for these inorganic antibacterial agents as necessary. it can. Examples of the synthetic antibacterial agent include 2-pyridinethiol-1-oxide, p-chloro-m-cresol, polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkylpolyaminoethylglycine, benzisothiazoline, 5- And chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,2′-dithio-bis- (pyridine-1-oxide), and the like.
　除草剤としては、例えば、ベンスルフロンメチル、ピラゾスルフロンエチル、イマゾスルフロン、シクロスルファムロン、エトキシスルフロン、フルセトスルフロン、アジムスルフロン、プリミスルフロン、プロスルフロン、リムスルフロン、ハロスルフロンメチル、ニコスルフロン、チフェンスルフロンメチル、トリトスルフロン、ホラムスルフロン、アミドスルフロン、クロルスルフロン、ヨードスルフロン、メトスルフロンメチル、スルホスルフロン、フラザスルフロン、クロリムロンエチル、トリフルスルフロンメチル、オキサスルフロン、スルホメツロンメチル、トリフロキシスルフロンナトリウム、フルピルスルフロンエチルナトリウム、イマザモックス、イマゼタピル、イマザキン、イマザピル、イマザピック、フルカルバゾンナトリウム、プロポキシカルバゾンナトリウム、ビスピリバックナトリウム、ピリフタリド、ピリミノバックメチル、ピリミスルファン、ピリチオバックナトリウム、フルメツラム、ペノキススラム、メトスラム、メタゾスルフロン、プロピリスルフロン、ベンタゾン、アトラジン、シマジン、ジメタメトリン、ピリデート、ピリダホル、テルブチラジン、テルブトリン、ブロモキシニル、アイオキシニル、メトリブジン、レナシル、ブロマシル、デスメディファム、フェンメディファム、メタミトロン、シメトリン、プロメトリン、ジウロン、イソウロン、リニュロン、シデュロン、クロロトルロン、ベンゾフェナップ、ピラゾレート、ピラゾキシフェン、ベンゾビシクロン、イソキサフルトール、テフリルトリオン、テンボトリオン、イソキサクロルトール、メソトリオン、スルコトリオン、ベンゾイルヘキサジオン、プラチラクロール、ブタクロール、カフェンストロール、フェントラザミド、メフェナセット、エトベンザニド、テニルクロール、フルフェナセット、インダノファン、アニロホス、メトラクロール、メタザクロール、アラクロール、プロパクロール、ピペロホス、ジメテナミド、アセトクロール、ナプロパミド、チオベンカルブ、モリネート、ベンフレセート、ピリブチカルブ、エトフメセート、エスプロカルブ、プロスルホカルブ、ダラポン、ブチレート、ペントキサゾン、ピラクロニル、オキサジアゾン、オキサジアルギル、ピラゾジル、オキシフルオルフェン、アシフルオルフェン、ビフェノックス、ピラフルフェンエチル、フルアゾレート、フルチアセットメチル、ブタフェナシル、ベンズフェンジゾン、カルフェントラゾンエチル、スルフェントラゾン、フルミオキサジン、アクトニフェン、フルミクロラック、プロフェキサジノン、セトキシジム、クレソジム、テプラロキシジム、アロキシジム、フェノキサプロップ－Ｐ－エチル、ジクロホップメチル、フルアジホップ－Ｐ－ブチル、キザロホップ－Ｐ－エチル、シハロホップブチル、グルホシネート、グルホシネートＰ、ビアラホス、グリホサート、グリホサートイソプロピルアミン、スルホサート、ピクロラム、トリクロピル、クロメプロップ、ＭＣＰＢ、２，４－Ｄ，ＭＣＰＡ、ジカンバ、キンクロラック、メコプロップ、ジクロルクロップ、ジフルフェニカン、フルルタモン、ピコリナフェン、フルリドン、ノルフルラゾン、ベンフルブタミド、フルロクロリドン、パラコート、ジクワット、ブタミホス、ペンディメタリン、トリフルラリン、ジチオピル、チアゾピル、アミプロホスメチル、ブロモブチド、クミルロン、ダイムロン、イソキサベン、ジクロベニル、フルポキサム、クロルチアミド、オキサジクロメホン、イプフェンカルバゾン、フェノキサスルホン、ＳＷ－０６５、ペラルゴン酸、クロマゾン、およびその塩などが挙げられる。 As herbicides, for example, bensulfuron methyl, pyrazosulfuron ethyl, imazosulfuron, cyclosulfamuron, ethoxysulfuron, flucetosulfuron, azimusulfuron, primissulfuron, prosulfuron, rimsulfuron, halosulfuron methyl, nicosulfuron , Thifensulfuron methyl, tritosulfuron, foramsulfuron, amidosulfuron, chlorosulfuron, iodosulfuron, metsulfuron methyl, sulfosulfuron, flazasulfuron, chlorimuron ethyl, triflusulfuron methyl, oxas Ruflon, sulfometuron methyl, trifloxysulfuron sodium, flupirsulfuron ethyl sodium, imazamox, imazetapill, imazaquin, imazapyr, imazapic, fullcarba Sodium, propoxycarbazone sodium, bispyribac sodium, pyriftalide, pyriminobac-methyl, pyrimisoruban, pyrithiobac sodium, flumethram, penoxsulam, methotram, metazosulfuron, propyrisulfuron, bentazone, atrazine, simazine, dimetamethrin, pyridate , Pyridahol, terbutyrazine, terbutridine, bromoxynyl, ioxinyl, metribudine, lenacyl, bromacil, desmedifam, fenmedifam, metamitron, simethrin, promethrin, diuron, isouron, linuron, ciduron, chlorotoluron, benzophenap, benzol, benzol Bicyclon, isoxaflutole, tefryltrione, tembotrione Isoxachlortol, mesotrione, sulcotrione, benzoylhexadione, platilachlor, butachlor, caffefentrol, fentrazamide, mefenacet, etobenzanide, tenylchlor, flufenacet, indanophan, anilophos, metolachlor, metazachlor, alachlor, propachlor, Piperophos, dimethenamide, acetochlor, napropamide, thiobencarb, molinate, benfrate, beributicarb, etofumesate, esprocarb, prosulfocarb, dalapon, butyrate, pentoxazone, pyraclonyl, oxadiazone, oxadialgyl, pyrazodyl, oxyfluorfen, bifluoroflufen Phenethyl, fluazolate, full Thiaset methyl, butaphenacyl, benzphendizone, carfentrazone ethyl, sulfentrazone, flumioxazin, actonifene, full microlac, profexazinone, cetoxydim, cresodymium, tepraloxydim, aroxidim, phenoxaprop-P -Ethyl, diclohop methyl, fluazihop-P-butyl, quizalofop-P-ethyl, cihalohop butyl, glufosinate, glufosinate P, bialaphos, glyphosate, glyphosate isopropylamine, sulfosate, picloram, triclopyr, clomeprop, MCPB, 2,4 -D, MCPA, dicamba, quinclolac, mecoprop, dichlor crop, diflufenican, flurtamone, picolinafene, fluridone, norflurazo , Benfurbutamide, flurochloridone, paraquat, diquat, butamifos, pendimethalin, trifluralin, dithiopyr, thiazopyr, amiprophosmethyl, bromobutide, cumyluron, diimron, isoxaben, diclobenil, flupoxam, chlorthiamid, oxadiclomephone, ipfencarbazone, phenoxy Examples include sasulfone, SW-065, pelargonic acid, clomazone, and salts thereof.
　防汚剤としては、本発明の効果を損なわない範囲で、他の任意の適切な防汚剤を採用し得る。このような防汚剤としては、例えば、ワックス、ペトロラタム、動物脂類、脂肪酸、珪藻付着防止剤、農薬、医薬品（メデトミジンなど）、酵素活性阻害剤（アルキルフェノール、アルキルレゾルシノールなど）、生物忌避剤などが挙げられる。これらの防汚剤を用いることにより、珪藻やフジツボなどの水生生物の付着防止効果がより一層向上する。 As the antifouling agent, any other appropriate antifouling agent can be adopted as long as the effects of the present invention are not impaired. Examples of such antifouling agents include waxes, petrolatum, animal fats, fatty acids, diatom adhesion inhibitors, agricultural chemicals, pharmaceuticals (such as medetomidine), enzyme activity inhibitors (such as alkylphenols and alkylresorcinols), biological repellents, and the like. Is mentioned. By using these antifouling agents, the adhesion preventing effect of aquatic organisms such as diatoms and barnacles is further improved.
　防汚層は、本発明の効果を損なわない範囲で、任意の適切な他の添加剤を含んでいても良い。このような他の添加剤としては、例えば、耐候剤として紫外線吸収剤が挙げられる。このような紫外線吸収剤としては、具体的には、例えば、ＢＡＳＦ製のＴＩＮＵＶＩＮ５７１、ＴＩＮＵＶＩＮ４６０、ＴＩＮＵＶＩＮ２１３、ＴＩＮＵＶＩＮ２３４、ＴＩＮＵＶＩＮ３２９、ＴＩＮＵＶＩＮ３２６などが挙げられる。このような紫外線吸収剤の添加量は、マトリックス樹脂に対して、好ましくは０．５重量％以上１０重量％未満である。マトリックス樹脂に対する紫外線吸収剤の添加量を上記範囲内に調整することにより、マトリックス樹脂の硬化反応を阻害することなく耐候剤としての効果を十分に発現し得る。 The antifouling layer may contain any appropriate other additive as long as the effects of the present invention are not impaired. Examples of such other additives include a UV absorber as a weathering agent. Specific examples of such ultraviolet absorbers include TINUVIN571, TINUVIN460, TINUVIN213, TINUVIN234, TINUVIN329, and TINUVIN326 made by BASF. The addition amount of such an ultraviolet absorber is preferably 0.5% by weight or more and less than 10% by weight with respect to the matrix resin. By adjusting the addition amount of the ultraviolet absorber with respect to the matrix resin within the above range, the effect as a weathering agent can be sufficiently exhibited without inhibiting the curing reaction of the matrix resin.
　防汚層には、強度を向上させるために、フィラーなどを添加させることができる。フィラーとしては、例えば、シリカ粒子、珪藻土などが挙げられる。また、フィラーとしては、分散性の観点から、表面が疎水性処理された粒子が好ましい。このような表面処理方法としては、ジメチルポリシロキサン、ジメチルジクロロシラン、ヘキサメチレンジシラザン、環状ジメチルシロキサンなどで表面処理する方法が挙げられる。このような表面が疎水性処理された粒子の大きさとしては、好ましくは、平均粒径が５ｎｍ～３００ｎｍである。このような表面が疎水性処理された粒子の大きさを上記範囲内に調整することにより、防汚層に十分な強度を付与し得るとともに、防汚層中に該粒子が均一に分散し得、防汚層に衝撃が加わった際にクラックが生じにくくなり得る。このような表面が疎水性処理された粒子の添加量は、マトリックス樹脂に対して、好ましくは０．１重量％～１０重量％である。このような表面が疎水性処理された粒子の添加量を上記範囲内に調整することにより、防汚層に十分な強度を付与し得るとともに、防汚層形成材料の粘度を抑制し得、防汚剤など添加した材料を均一に分散し得、基材層上に塗工する場合、精密に塗工し得る。このような表面が疎水性処理された粒子としては、例えば、日本アエロジル社製の疎水性フュームドシリカが挙げられ、具体的には、日本アエロジル社製のＡＥＲＯＳＩＬ（登録商標）ＲＸシリーズ（ＲＸ５０、ＲＸ２００、ＲＸ３００など）、ＡＥＲＯＳＩＬ（登録商標）ＲＹシリーズ（ＲＹ５０、ＲＹ２００、ＲＹ２００Ｓなど）、ＡＥＲＯＳＩＬ（登録商標）ＮＹ５０、ＡＥＲＯＳＩＬ（登録商標）ＮＡＸシリーズ、ＡＥＲＯＳＩＬ（登録商標）Ｒシリーズなどが挙げられる。 In the antifouling layer, a filler or the like can be added to improve the strength. Examples of the filler include silica particles and diatomaceous earth. Moreover, as a filler, the particle | grains by which the surface was hydrophobized from a dispersible viewpoint are preferable. Examples of such a surface treatment method include a surface treatment method using dimethylpolysiloxane, dimethyldichlorosilane, hexamethylenedisilazane, cyclic dimethylsiloxane, and the like. As the size of the particles whose surface is subjected to hydrophobic treatment, the average particle size is preferably 5 nm to 300 nm. By adjusting the size of the particles whose surface has been subjected to hydrophobic treatment within the above range, sufficient strength can be imparted to the antifouling layer, and the particles can be uniformly dispersed in the antifouling layer. When an impact is applied to the antifouling layer, cracks can hardly occur. The amount of such particles whose surface has been subjected to hydrophobic treatment is preferably 0.1% by weight to 10% by weight with respect to the matrix resin. By adjusting the addition amount of the particles whose surface has been subjected to hydrophobic treatment within the above range, the antifouling layer can be provided with sufficient strength, and the viscosity of the antifouling layer forming material can be suppressed. The added material such as a soiling agent can be uniformly dispersed, and when applied on the base material layer, it can be applied precisely. Examples of the particles whose surface has been subjected to hydrophobic treatment include hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd., and specifically, AEROSIL (registered trademark) RX series (RX50, manufactured by Nippon Aerosil Co., Ltd.). RX200, RX300, etc.), AEROSIL (registered trademark) RY series (RY50, RY200, RY200S, etc.), AEROSIL (registered trademark) NY50, AEROSIL (registered trademark) NAX series, AEROSIL (registered trademark) R series, and the like.
　本発明の水生生物付着防止粘着テープにおいて、防汚層と水生生物との付着力は、好ましくは０．１０Ｎ／ｍｍ２以下であり、より好ましくは０．０８Ｎ／ｍｍ２以下であり、さらに好ましくは０．０５Ｎ／ｍｍ２以下であり、特に好ましくは０．０４Ｎ／ｍｍ２以下である。防汚層と水生生物との付着力の下限値は、小さければ小さいほど良いが、材料等を考慮して、現実的には、好ましくは０．００５Ｎ／ｍｍ２以上であり、より好ましくは０．００１Ｎ／ｍｍ２以上である。防汚層と水生生物との付着力を上記範囲内に調整することにより、本発明の水生生物付着防止粘着テープは、水生生物の付着をきわめて効果的に防止し得る。 In aquatic adhesion preventing pressure-sensitive adhesive tape of the present invention, adhesion between the antifouling layer and the aquatic organisms is preferably not more than 0.10 N / mm 2, more preferably less 0.08 N / mm 2, more preferably Is 0.05 N / mm 2 or less, particularly preferably 0.04 N / mm 2 or less. The lower limit of the adhesion between the antifouling layer and the aquatic organism is preferably as small as possible. However, in consideration of materials and the like, in practice, it is preferably 0.005 N / mm 2 or more, more preferably 0. 0.001 N / mm 2 or more. By adjusting the adhesion between the antifouling layer and the aquatic organisms within the above range, the aquatic organism adhesion preventing adhesive tape of the present invention can very effectively prevent the aquatic organisms from adhering.
　なお、防汚層と水生生物との付着力の測定方法としては、例えば、デジタルフォースゲージ（ＳＨＩＭＰＯ製、ＦＧＮ－５０Ｂ）本体に計測用アダプタ（延長棒に山形アダプタ）を取り付けて測定機とし、フジツボの付着した粘着テープを選び、フジツボの直径をノギスで測定し、測定機の測定値をリセットした後、粘着テープの表面に付着したフジツボの外殻下部に測定用アダプタを静かに接触させ、粘着テープの表面と平行になるように測定機をスライドさせ、フジツボを剥離したときに測定機に表示される最大負荷値（Ｎ）を記録し、先に測定しておいたフジツボの直径からフジツボの付着面積（ｍｍ２）を円の面積公式によって計算し、記録した最大負荷値を付着面積で除して、単位面積あたりの負荷（Ｎ／ｍｍ２）を計算で求め、これを、付着力とした。 In addition, as a method for measuring the adhesion between the antifouling layer and aquatic organisms, for example, a measuring adapter (mountain adapter on the extension rod) is attached to the main body of a digital force gauge (manufactured by SHIMPO, FGN-50B). Select the adhesive tape with the barnacle attached, measure the diameter of the barnacle with calipers, reset the measurement value of the measuring machine, and then gently touch the measuring adapter to the lower shell of the barnacle attached to the surface of the adhesive tape. Slide the measuring instrument so that it is parallel to the surface of the adhesive tape, record the maximum load value (N) displayed on the measuring instrument when the barnacle is peeled off, and record the barnacle from the diameter of the barnacle previously measured. Calculate the load area per unit area (N / mm 2 ) by calculating the adhesion area (mm 2 ) by the area formula of the circle and dividing the recorded maximum load value by the adhesion area. This was defined as adhesion.
　防汚層の厚みは、本発明の水生生物付着防止粘着テープの用途や使用環境などによって、任意の適切な厚みを採用し得る。防汚層の厚みは、好ましくは５μｍ～５００μｍである。防汚層の厚みを上記範囲内に調整することにより、防汚効果が十分に長く有効に働き得るとともに、ハンドリング性に優れ得、テープのつなぎ目部分の凹凸が小さくなり得、汚れが付き難くなり得る。 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. By adjusting the thickness of the antifouling layer within the above range, the antifouling effect can work effectively long enough, it can be excellent in handling properties, the unevenness of the joint part of the tape can be reduced, and dirt is difficult to adhere obtain.
　粘着剤層（Ａ）および粘着剤層（Ｂ）としては、本発明の効果を損なわない範囲で、任意の適切な粘着剤層を採用し得る。このような粘着剤層の材料としては、例えば、アクリル樹脂系粘着剤、エポキシ樹脂系粘着剤、アミノ樹脂系粘着剤、ビニル樹脂（酢酸ビニル系重合体など）系粘着剤、硬化型アクリル樹脂系粘着剤、シリコーン樹脂系粘着剤などが挙げられる。このような粘着剤層の材料は、１種のみであっても良いし、２種以上であっても良い。なお、粘着剤層（Ａ）と粘着剤層（Ｂ）は、同種の粘着剤層であっても良いし、異種の粘着剤層であっても良い。 Any appropriate pressure-sensitive adhesive layer can be adopted as the pressure-sensitive adhesive layer (A) and the pressure-sensitive adhesive layer (B) 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. Examples thereof include a pressure-sensitive adhesive and a silicone resin-based pressure-sensitive adhesive. There may be only one kind of material for such an adhesive layer, or two or more kinds. The pressure-sensitive adhesive layer (A) and the pressure-sensitive adhesive layer (B) may be the same type of pressure-sensitive adhesive layer or different types of pressure-sensitive adhesive layers.
　粘着剤層（Ａ）は、その２３℃で引張速度３００ｍｍ／ｍｉｎにおける１８０度ピール接着力が、好ましくは下限値が１Ｎ／２０ｍｍ以上であり、より好ましくは３Ｎ／２０ｍｍ以上であり、さらに好ましくは４Ｎ／２０ｍｍ以上である。粘着剤層（Ａ）の２３℃で引張速度３００ｍｍ／ｍｉｎにおける１８０度ピール接着力を上記範囲内に調整することにより、水蒸気バリア層との密着性が向上する。 The pressure-sensitive adhesive layer (A) has a 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min, preferably a lower limit of 1 N / 20 mm or more, more preferably 3 N / 20 mm or more, and still more preferably 4 N / 20 mm or more. By adjusting the 180 degree peel adhesive force of the pressure-sensitive adhesive layer (A) at 23 ° C. at a tensile speed of 300 mm / min within the above range, the adhesion with the water vapor barrier layer is improved.
　粘着剤層（Ｂ）は、その２３℃で引張速度３００ｍｍ／ｍｉｎにおける１８０度ピール接着力が、好ましくは３０Ｎ／２０ｍｍ以下であり、より好ましくは２０Ｎ／２０ｍｍ以下であり、さらに好ましくは１５Ｎ／２０ｍｍ以下である。粘着剤層（Ｂ）の２３℃で引張速度３００ｍｍ／ｍｉｎにおける１８０度ピール接着力を上記範囲内に調整することにより、本発明の水生生物付着防止粘着テープを被着体から剥がし易くし得る。粘着剤層（Ｂ）の２３℃で引張速度３００ｍｍ／ｍｉｎにおける１８０度ピール接着力の下限は、十分な粘着力を維持できる観点から、好ましくは３Ｎ／２０ｍｍ以上である。 The pressure-sensitive adhesive layer (B) has a 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min, preferably 30 N / 20 mm or less, more preferably 20 N / 20 mm or less, and even more preferably 15 N / 20 mm. It is as follows. By adjusting the 180-degree peel adhesive force of the pressure-sensitive adhesive layer (B) at 23 ° C. and a tensile speed of 300 mm / min within the above range, the aquatic organism adhesion preventing pressure-sensitive adhesive tape of the present invention can be easily peeled off from the adherend. The lower limit of the 180-degree peel adhesive force at 23 ° C. and a tensile speed of 300 mm / min of the pressure-sensitive adhesive layer (B) is preferably 3 N / 20 mm or more from the viewpoint of maintaining sufficient adhesive force.
　粘着剤層（Ａ）は、海水に接触させた際に、該粘着剤層（Ａ）における海水に接触させた部分の圧縮弾性率が、海水接触前の該粘着剤層（Ａ）における圧縮弾性率に対して、好ましくは１．１倍以上であり、より好ましくは１．２倍以上であり、さらに好ましくは１．５倍以上である。粘着剤層（Ａ）を海水に接触させた際に、該粘着剤層（Ａ）における海水に接触させた部分の圧縮弾性率が、海水接触前の該粘着剤層（Ａ）における圧縮弾性率の１．１倍以上であれば、水中においても良好な接着性を発現できる。粘着剤層（Ａ）を海水に接触させた際の、該粘着剤層（Ａ）における海水に接触させた部分の圧縮弾性率の、海水接触前の該粘着剤層（Ａ）における圧縮弾性率に対する倍率の上限は、取扱性の観点から、好ましくは１００倍以下である。なお、ここにいう海水とは、市販されている模擬海水（人工海水）のことを意味する。 When the pressure-sensitive adhesive layer (A) is brought into contact with seawater, the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (A) in contact with seawater is the compression elasticity in the pressure-sensitive adhesive layer (A) before seawater contact. The ratio is preferably 1.1 times or more, more preferably 1.2 times or more, and further preferably 1.5 times or more. When the pressure-sensitive adhesive layer (A) is brought into contact with seawater, the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (A) in contact with seawater is the compression elastic modulus in the pressure-sensitive adhesive layer (A) before seawater contact. If it is 1.1 times or more, good adhesiveness can be expressed even in water. When the pressure-sensitive adhesive layer (A) is contacted with seawater, the compression elastic modulus of the pressure-sensitive adhesive layer (A) before the seawater contact is the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (A) that is in contact with seawater. The upper limit of the magnification is preferably 100 times or less from the viewpoint of handleability. In addition, seawater here means the simulated seawater (artificial seawater) marketed.
　粘着剤層（Ｂ）は、海水に接触させた際に、該粘着剤層（Ｂ）における海水に接触させた部分の圧縮弾性率が、海水接触前の該粘着剤層（Ｂ）における圧縮弾性率に対して、好ましくは１．１倍以上であり、より好ましくは１．２倍以上であり、さらに好ましくは１．５倍以上である。粘着剤層（Ｂ）を海水に接触させた際に、該粘着剤層（Ｂ）における海水に接触させた部分の圧縮弾性率が、海水接触前の該粘着剤層（Ｂ）における圧縮弾性率の１．１倍以上であれば、水中においても良好な接着性を発現できる。粘着剤層（Ｂ）を海水に接触させた際の、該粘着剤層（Ｂ）における海水に接触させた部分の圧縮弾性率の、海水接触前の該粘着剤層（Ｂ）における圧縮弾性率に対する倍率の上限は、取扱性の観点から、好ましくは１００倍以下である。なお、ここにいう海水とは、市販されている模擬海水（人工海水）のことを意味する。 When the pressure-sensitive adhesive layer (B) is brought into contact with seawater, the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (B) in contact with seawater is the compression elasticity in the pressure-sensitive adhesive layer (B) before seawater contact. The ratio is preferably 1.1 times or more, more preferably 1.2 times or more, and further preferably 1.5 times or more. When the pressure-sensitive adhesive layer (B) is contacted with seawater, the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (B) in contact with seawater is the compression elastic modulus of the pressure-sensitive adhesive layer (B) before seawater contact. If it is 1.1 times or more, good adhesiveness can be expressed even in water. When the pressure-sensitive adhesive layer (B) is contacted with seawater, the compression elastic modulus of the pressure-sensitive adhesive layer (B) before seawater contact is the compression elastic modulus of the portion of the pressure-sensitive adhesive layer (B) that is in contact with seawater. The upper limit of the magnification is preferably 100 times or less from the viewpoint of handleability. In addition, seawater here means the simulated seawater (artificial seawater) marketed.
　粘着剤層（Ａ）の厚みは、本発明の水生生物付着防止粘着テープの用途や使用環境などによって、任意の適切な厚みを採用し得る。粘着剤層（Ａ）の厚みは、水蒸気バリア層との密着性の点で、好ましくは１０μｍ以上である。粘着剤層（Ａ）の厚みの上限は、取扱性の観点から、好ましくは１００μｍ以下である。 Any appropriate thickness can be adopted as the thickness of the pressure-sensitive adhesive layer (A) depending on the application and use environment of the aquatic organism adhesion preventing pressure-sensitive adhesive tape of the present invention. The thickness of the pressure-sensitive adhesive layer (A) is preferably 10 μm or more from the viewpoint of adhesion to the water vapor barrier layer. The upper limit of the thickness of the pressure-sensitive adhesive layer (A) is preferably 100 μm or less from the viewpoint of handleability.
　粘着剤層（Ｂ）の厚みは、本発明の水生生物付着防止粘着テープの用途や使用環境などによって、任意の適切な厚みを採用し得る。粘着剤層（Ｂ）の厚みは、被着体の形状に十分に追従できて接着面積を確保し得るとともに十分な粘着力を発現し得る点で、好ましくは１０μｍ以上である。粘着剤層（Ｂ）の厚みの上限は、取扱性の観点から、好ましくは１００μｍ以下である。 Any appropriate thickness can be adopted as the thickness of the pressure-sensitive adhesive layer (B) depending on the application or use environment of the aquatic organism adhesion preventing pressure-sensitive adhesive tape of the present invention. The thickness of the pressure-sensitive adhesive layer (B) is preferably 10 μm or more from the viewpoint that it can sufficiently follow the shape of the adherend to secure a bonding area and can exhibit a sufficient adhesive force. The upper limit of the thickness of the pressure-sensitive adhesive layer (B) is preferably 100 μm or less from the viewpoint of handleability.
　本発明の水生生物付着防止粘着テープは、任意の適切な方法によって製造し得る。このような方法としては、例えば、
（１）基材層の一方の面に粘着剤層（Ａ）形成材料を塗布して粘着剤層（Ａ）を形成し、該基材層の該粘着剤層（Ａ）の反対側の面上に防汚層形成材料を塗布して防汚層を形成し、該粘着剤層（Ａ）の該基材層の反対側の面上に水蒸気バリア層を貼付し、該水蒸気バリア層の該粘着剤層（Ａ）の反対側の面上に粘着剤層（Ｂ）形成材料を塗布して粘着剤層（Ｂ）を形成する方法、
（２）基材層形成材料と粘着剤層（Ａ）形成材料を共押出しして基材層／粘着剤層（Ａ）の積層体を形成させた後に、防汚層形成材料を該基材層の該粘着剤層（Ａ）の反対側の面上に塗布して防汚層を形成し、該粘着剤層（Ａ）の該基材層の反対側の面上に水蒸気バリア層を貼付し、該水蒸気バリア層の該粘着剤層（Ａ）の反対側の面上に粘着剤層（Ｂ）形成材料を塗布して粘着剤層（Ｂ）を形成する方法、
などが挙げられる。 The aquatic organism adhesion prevention adhesive tape of this invention can be manufactured by arbitrary appropriate methods. As such a method, for example,
(1) A pressure-sensitive adhesive layer (A) forming material is applied to one surface of the base material layer to form a pressure-sensitive adhesive layer (A), and the surface of the base material layer opposite to the pressure-sensitive adhesive layer (A) An antifouling layer-forming material is applied to form an antifouling layer, and a water vapor barrier layer is pasted on the surface of the pressure-sensitive adhesive layer (A) opposite to the base material layer. A method of forming a pressure-sensitive adhesive layer (B) by applying a pressure-sensitive adhesive layer (B) forming material on the surface opposite to the pressure-sensitive adhesive layer (A);
(2) A base material layer forming material and an adhesive layer (A) forming material are coextruded to form a base material layer / adhesive layer (A) laminate, and then the antifouling layer forming material is used as the base material layer. An antifouling layer is formed on the surface of the adhesive layer (A) opposite to the surface of the adhesive layer, and a water vapor barrier layer is applied to the surface of the adhesive layer (A) opposite to the substrate layer. A method of forming the pressure-sensitive adhesive layer (B) by applying a pressure-sensitive adhesive layer (B) forming material on the surface of the water vapor barrier layer opposite to the pressure-sensitive adhesive layer (A),
Etc.
　防汚層形成材料を基材層上に塗布する方法としては、例えば、スプレー、ハケ塗り、ローラー、カーテンフロー、ロール、ディップ、コーターなどが挙げられる。これらの方法で防汚層形成材料を基材層上に塗布して、例えば、室温から２５０℃までの温度（好ましくは、室温から１８０℃の温度）で乾燥させることにより、防汚層を形成することができる。特に、本発明の水生生物付着防止粘着テープにおいては、コンマコーターなどの精密コーターを採用して防汚層形成材料を基材層上に塗布することは、好ましい実施形態の一つである。 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 coater. 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. In particular, in the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention, it is one of preferred embodiments that a precision coater such as a comma coater is used to apply the antifouling layer forming material onto the base material layer.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
＜透湿度の測定＞
ＪＩＳ－Ｚ０２０８「防湿包装材量の透湿度試験方法」の諸条件に準じ、下記手法で評価した。
　透湿面積７０ｍｍΦ透湿カップに吸湿剤として無水塩化カルシウム約２０ｇを入れ、その上にサンプルを乗せ、封ろう剤で完全に密閉した。そのカップを温度４０℃、相対湿度９０％の恒温恒湿装置に入れ、２４時間の間隔で１４日間まで質量測定（０．１ｍｇ単位）を行い、透湿度を下記式から算出した。
　透湿度（ｇ／ｍ２・２４ｈ）＝（ｍ／ｓ）／ｔ
　　ｍ； 試験期間最後２回の秤量間隔の増加質量（ｇ）
　　ｓ； 透湿面積（ｍ２）
　　ｔ； 試験期間最後２回の秤量間隔の時間（ｈ）／２４（ｈ）
　下記の基準によって評価を行った。
◎：透湿度が１０ｇ／ｍ２・２４ｈ以下。
○：透湿度が１０ｇ／ｍ２・２４ｈを超えて５０ｇ／ｍ２・２４ｈ以下。
×：透湿度が５０ｇ／ｍ２・２４ｈを超える。 <Measurement of moisture permeability>
In accordance with various conditions of JIS-Z0208 “Method of testing moisture permeability of moisture-proof packaging material”, evaluation was performed by the following method.
About 20 g of anhydrous calcium chloride was put as a moisture absorbent in a moisture permeable area 70 mmΦ moisture permeable cup, and a sample was placed thereon and completely sealed with a sealing wax. The cup was placed in a constant temperature and humidity device at a temperature of 40 ° C. and a relative humidity of 90%, and mass measurement (in units of 0.1 mg) was performed at intervals of 24 hours for up to 14 days.
Moisture permeability (g / m 2 · 24h) = (m / s) / t
m: Mass increase in the last two weighing intervals (g)
s; Moisture permeable area (m 2 )
t: Time of last two weighing intervals (h) / 24 (h)
Evaluation was performed according to the following criteria.
A: The moisture permeability is 10 g / m 2 · 24 h or less.
○: Moisture permeability exceeds 10 g / m 2 · 24 h and is 50 g / m 2 · 24 h or less.
X: Moisture permeability exceeds 50 g / m 2 · 24 h.
＜オズモシス試験＞
　試験対象の粘着テープを８ｃｍ×１２ｃｍにカットし、３ｃｍ×１０ｃｍサイズのＦＲＰ板（表面にゲルコート層を有する）を包み込むようにハンドローラーで貼り合わせた。さらに、水が浸入しないように、粘着テープの余分な部分を、粘着剤を用いて硬く閉じた。このようにして作製したサンプルを６０℃のイオン交換水に浸漬させ、１０日間静置し、オズモシスの発生の有無を確認した。下記の基準によって評価を行った。
◎：水疱の数が０～４個／ｃｍ２。
○：水疱の数が５～９個／ｃｍ２。
×：水疱の数が１０個／ｃｍ２以上。 <Osmosis test>
The test target adhesive tape was cut into 8 cm × 12 cm, and bonded with a hand roller so as to wrap a 3 cm × 10 cm FRP plate (having a gel coat layer on the surface). Furthermore, the excess part of the adhesive tape was tightly closed with an adhesive so that water did not enter. The sample thus prepared was immersed in ion exchange water at 60 ° C. and allowed to stand for 10 days, and the presence or absence of osmosis was confirmed. Evaluation was performed according to the following criteria.
A: The number of blisters is 0 to 4 / cm 2 .
○: The number of blisters is 5 to 9 / cm 2 .
X: The number of blisters is 10 / cm 2 or more.
＜密着性評価＞
　試験対象の粘着テープを幅２０ｍｍ、長さ１５０ｍｍに切断し、端部（短辺側）を持って、手で１０％伸ばしたときの防汚層の様子を目視で観察した。下記の基準によって評価を行った。
○：防汚層が基材層に密着していた。
×：防汚層が基材層から剥離していた。 <Adhesion evaluation>
The test target adhesive tape was cut into a width of 20 mm and a length of 150 mm, and the state of the antifouling layer was visually observed when the end (short side) was held and stretched by 10% by hand. Evaluation was performed according to the following criteria.
○: The antifouling layer was in close contact with the base material layer.
X: The antifouling layer was peeled off from the base material layer.
＜曲面追従性評価＞
　セパラブルフラスコ丸型１Ｌ（柴田科学株式会社製）の底面（曲率半径＝７０ｍｍ）に試験対象の粘着テープを貼り付け、５ｃｍ×５ｃｍの範囲の仕上がり具合について、下記の基準によって評価を行った。
○：シワなく施工できた。
△：シワが若干あるが施工できた。
×：施工が極端に困難であった。 <Curved surface follow-up evaluation>
An adhesive tape to be tested was attached to the bottom surface (curvature radius = 70 mm) of a separable flask 1L (manufactured by Shibata Kagaku Co., Ltd.), and the finished condition in the range of 5 cm × 5 cm was evaluated according to the following criteria.
○: Construction was possible without wrinkles.
(Triangle | delta): Although there was some wrinkles, it was able to construct.
X: Construction was extremely difficult.
＜弾性率＞
　基材層を幅１０ｍｍ、長さ１００ｍｍに切断し、チャック間距離が５０ｍｍとなるように設置して、引張試験機（商品名「Ａｕｔｏｇｒａｐｈ　ＡＧ－Ｘ　２００Ｎ」、（株）島津製作所製）によりＳ－Ｓ試験（温度：２３℃、湿度：６５％ＲＨ、引張速度：３００ｍｍ／ｍｉｎ）を行った。得られたＳ－Ｓ曲線の初期立ち上がりの傾きから弾性率を求めた。
　下記の基準によって評価を行った。
◎：弾性率が１００ＭＰａ以下。
○：弾性率が１００ＭＰａを超えて５００ＭＰａ以下。
×：弾性率が５００ＭＰａを超える。 <Elastic modulus>
The base material layer was cut to a width of 10 mm and a length of 100 mm, and installed so that the distance between chucks was 50 mm, and S was measured using a tensile tester (trade name “Autograph AG-X 200N”, manufactured by Shimadzu Corporation). -S test (temperature: 23 ° C., humidity: 65% RH, tensile speed: 300 mm / min) was performed. The elastic modulus was determined from the slope of the initial rise of the obtained SS curve.
Evaluation was performed according to the following criteria.
A: Elastic modulus is 100 MPa or less.
○: The elastic modulus exceeds 100 MPa and is 500 MPa or less.
X: The elastic modulus exceeds 500 MPa.
＜１８０度ピール接着力の測定＞
　試験対象の粘着テープの粘着剤層の粘着剤をポリエステルフィルム（商品名「Ｓ－１０」、東レ（株）製、厚み３８μｍ）にハンドローラーを使用して転写し、基材付きの粘着シートを得た。これを８０ｍｍ×２０ｍｍの試験片サイズにカットした。被着体として３０ｍｍ×１００ｍｍ×厚さ２ｍｍのエポキシ樹脂にガラスクロスを入れて強化したプラスチックＦＲＰ板を使用した。被着体に試験片を２ｋｇローラーで１往復して貼り合わせ、２３℃で３０分放置後、初期の１８０度ピール接着力を測定した。引張速度は３００ｍｍ／ｍｉｎとした。 <Measurement of 180 degree peel adhesion>
Transfer the adhesive in the adhesive layer of the adhesive tape to be tested to a polyester film (trade name “S-10”, manufactured by Toray Industries, Inc., thickness 38 μm) using a hand roller, and attach the adhesive sheet with the substrate. Obtained. This was cut into a test piece size of 80 mm × 20 mm. As the adherend, a plastic FRP plate reinforced by putting a glass cloth in an epoxy resin of 30 mm × 100 mm × thickness 2 mm was used. The test piece was attached to the adherend by reciprocating once with a 2 kg roller, and allowed to stand at 23 ° C. for 30 minutes, and then the initial 180-degree peel adhesive strength was measured. The tensile speed was 300 mm / min.
〔実施例１〕
＜基材層（１）の準備＞
　カーボネート系ポリウレタンである商品名「ハイグレスＤＵＳ４５１－ＣＤＲ」（厚み＝１００μｍ）（シーダム（株）製）を基材層（１）とした。 [Example 1]
<Preparation of base material layer (1)>
The product name “Higres DUS451-CDR” (thickness = 100 μm) (manufactured by Seadam Co., Ltd.), which is a carbonate-based polyurethane, was used as the base material layer (1).
＜「防汚層（１）／基材層（１）」の積層体の製造＞
　シリコーン樹脂（付加型液状シリコーン樹脂（ＬＩＭＳ）、商品名「ＫＥ－１９５０－５０」、信越化学工業（株）製）：１００重量部、防汚剤としてシリコーンオイル（ＫＦ９６－１００ｃｓ、非反応性シリコーンオイル、信越化学工業（株）製）：９０重量部、紫外線吸収剤（商品名「ＴＩＮＵＶＩＮ５７１」、ＢＡＳＦ製）：２重量部、ナノシリカ（商品名「アエロジルＲＸ－３００」、日本アエロジル（株）製）：１重量部、流動パラフィン（キシダ化学（株）製）：５重量部を配合し、ホモミキサーを用いて撹拌して、均一な液状とし、脱泡して、防汚層材料液（１´）を得た。
　基材層（１）上に、防汚層材料液（１´）を、アプリケーターを用いて塗布し、１４０℃で２分間硬化させ、厚み１００μｍの防汚層（１）を基材層（１）上に形成させた。これにより、「防汚層（１）（厚み１００μｍ）／基材層（１）（厚み１００μｍ）」の積層体を得た。 <Manufacture of laminate of “antifouling layer (1) / base material layer (1)”>
Silicone resin (addition type liquid silicone resin (LIMS), trade name “KE-1950-50”, manufactured by Shin-Etsu Chemical Co., Ltd.): 100 parts by weight, silicone oil as antifouling agent (KF96-100cs, non-reactive silicone) Oil, manufactured by Shin-Etsu Chemical Co., Ltd.): 90 parts by weight, UV absorber (trade name “TINUVIN571”, manufactured by BASF): 2 parts by weight, nanosilica (trade name “Aerosil RX-300”, manufactured by Nippon Aerosil Co., Ltd.) ): 1 part by weight, liquid paraffin (manufactured by Kishida Chemical Co., Ltd.): 5 parts by weight, stirred using a homomixer to make a uniform liquid, defoamed, antifouling layer material liquid (1 ') Was obtained.
On the base material layer (1), the antifouling layer material liquid (1 ′) is applied using an applicator and cured at 140 ° C. for 2 minutes to form an antifouling layer (1) having a thickness of 100 μm as the base material layer (1). ) Formed on top. As a result, a laminate of “antifouling layer (1) (thickness 100 μm) / base material layer (1) (thickness 100 μm)” was obtained.
＜粘着剤層（１Ａ）の作成＞
　冷却管、窒素導入管、温度計、および攪拌機を備えた反応容器に、（メタ）アクリル系モノマーとして、２－エチルヘキシルアクリレート（２ＥＨＡ、東亜合成（株）製）を９４重量部、アクリル酸（ＡＡ）を６重量部、光重合開始剤として２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名「イルガキュア６５１」、ＢＡＳＦ製）０．１重量部を投入して分散させ、攪拌しながら窒素気流下にて上部よりＵＶ照射することにより、一部のモノマーをポリマーに転化させて塗工可能な粘度に調整し、（メタ）アクリル系モノマー混合物を得た。この（メタ）アクリル系モノマー混合物に、アクリル系オリゴマー（ジシクロペンタニルメタクリレート／メチルメタクリレート＝６０重量％／４０重量％）：５重量部、架橋剤として１、６－ヘキサンジオールジアクリレート（ＨＤＤＡ）：０．１６重量部を添加し、これをセパレーター（商品名「ＭＲＦ５０」、三菱樹脂（株）製、厚み５０μｍ）の表面にアプリケーターを用いて塗布し、カバーセパレーター（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）することにより、厚み５０μｍの粘着剤層（１Ａ）を得た。粘着剤層（１Ａ）の１８０度ピール接着力を測定した結果、４．８Ｎ／２０ｍｍであった。 <Creation of adhesive layer (1A)>
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirrer, 94 parts by weight of 2-ethylhexyl acrylate (2EHA, manufactured by Toa Gosei Co., Ltd.) as a (meth) acrylic monomer, acrylic acid (AA) ) And 6 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator, and dispersed therein. By UV irradiation from above in a nitrogen stream while stirring, a part of the monomer was converted into a polymer and adjusted to a coatable viscosity to obtain a (meth) acrylic monomer mixture. To this (meth) acrylic monomer mixture, acrylic oligomer (dicyclopentanyl methacrylate / methyl methacrylate = 60% by weight / 40% by weight): 5 parts by weight, 1,6-hexanediol diacrylate (HDDA) as a crosslinking agent : 0.16 part by weight was added, and this was applied to the surface of a separator (trade name “MRF50”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 50 μm) using an applicator, and a cover separator (trade name “MRF38”, Mitsubishi) Resin Co., Ltd. (thickness 38 μm) is bonded with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ) with an ultraviolet lamp (BL type). Thus, an adhesive layer (1A) having a thickness of 50 μm was obtained. It was 4.8 N / 20mm as a result of measuring the 180 degree | times peel adhesive force of an adhesive layer (1A).
＜水蒸気バリア層（１）の準備＞
　商品名「サランラップ（登録商標）」（旭化成ホームプロダクツ株式会社製、厚み＝１１μｍ）を水蒸気バリア層（１）とした。水蒸気バリア層（１）の透湿度は、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、１ｇ／ｍ２・２４時間であった。 <Preparation of water vapor barrier layer (1)>
The product name “Saran Wrap (registered trademark)” (manufactured by Asahi Kasei Home Products Co., Ltd., thickness = 11 μm) was used as the water vapor barrier layer (1). The moisture permeability of the water vapor barrier layer (1) was 1 g / m 2 · 24 hours when the thickness was converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
＜粘着剤層（１Ｂ）の作成＞
　冷却管、窒素導入管、温度計、および攪拌機を備えた反応容器に、（メタ）アクリル系モノマーとして、２－エチルヘキシルアクリレート（２ＥＨＡ、東亜合成（株）製）を９４重量部、アクリル酸（ＡＡ）を６重量部、光重合開始剤として２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名「イルガキュア６５１」、ＢＡＳＦ製）０．１重量部を投入して分散させ、攪拌しながら窒素気流下にて上部よりＵＶ照射することにより、一部のモノマーをポリマーに転化させて塗工可能な粘度に調整し、（メタ）アクリル系モノマー混合物を得た。この（メタ）アクリル系モノマー混合物に、アクリル系オリゴマー（ジシクロペンタニルメタクリレート／メチルメタクリレート＝６０重量％／４０重量％）：５重量部、架橋剤として１、６－ヘキサンジオールジアクリレート（ＨＤＤＡ）：０．１６重量部を添加し、これをセパレーター（商品名「ＭＲＦ５０」、三菱樹脂（株）製、厚み５０μｍ）の表面にアプリケーターを用いて塗布し、カバーセパレーター（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）することにより、厚み５０μｍの粘着剤層（１Ｂ）を得た。粘着剤層（１Ｂ）の１８０度ピール接着力を測定した結果、４．８Ｎ／２０ｍｍであった。 <Creation of adhesive layer (1B)>
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirrer, 94 parts by weight of 2-ethylhexyl acrylate (2EHA, manufactured by Toa Gosei Co., Ltd.) as a (meth) acrylic monomer, acrylic acid (AA) ) And 6 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator, and dispersed therein. By UV irradiation from above in a nitrogen stream while stirring, a part of the monomer was converted into a polymer and adjusted to a coatable viscosity to obtain a (meth) acrylic monomer mixture. To this (meth) acrylic monomer mixture, acrylic oligomer (dicyclopentanyl methacrylate / methyl methacrylate = 60% by weight / 40% by weight): 5 parts by weight, 1,6-hexanediol diacrylate (HDDA) as a crosslinking agent : 0.16 part by weight was added, and this was applied to the surface of a separator (trade name “MRF50”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 50 μm) using an applicator, and a cover separator (trade name “MRF38”, Mitsubishi) Resin Co., Ltd. (thickness 38 μm) is bonded with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ) with an ultraviolet lamp (BL type). Thus, an adhesive layer (1B) having a thickness of 50 μm was obtained. It was 4.8 N / 20mm as a result of measuring 180 degree | times peel adhesive force of an adhesive layer (1B).
＜粘着テープの作成＞
　得られた「防汚層（１）（厚み１００μｍ）／基材層（１）（厚み１００μｍ）」の積層体の基材層（１）側に、粘着剤層（１Ａ）（厚み５０μｍ）、水蒸気バリア層（１）（厚み５０μｍ）、粘着剤層（１Ｂ）（厚み５０μｍ）をこの順に、ハンドローラーを用いて貼り合わせ、「防汚層（１）（厚み１００μｍ）／基材層（１）（厚み１００μｍ）／粘着剤層（１Ａ）（厚み５０μｍ）／水蒸気バリア層（１）（厚み５０μｍ）／粘着剤層（１Ｂ）（厚み５０μｍ）」からなる粘着テープ（１）を得た。
　各種評価結果を表１に示した。 <Creation of adhesive tape>
On the base material layer (1) side of the obtained laminate of “antifouling layer (1) (thickness 100 μm) / base material layer (1) (thickness 100 μm)”, an adhesive layer (1A) (thickness 50 μm), The water vapor barrier layer (1) (thickness 50 μm) and the pressure-sensitive adhesive layer (1B) (thickness 50 μm) were bonded together in this order using a hand roller, and “antifouling layer (1) (thickness 100 μm) / base material layer (1 ) (Thickness 100 μm) / adhesive layer (1A) (thickness 50 μm) / water vapor barrier layer (1) (thickness 50 μm) / adhesive layer (1B) (thickness 50 μm) ”was obtained.
Various evaluation results are shown in Table 1.
〔実施例２〕
　水蒸気バリア層（１）を、ポリエチレンフィルム（商品名「ＡＮＥ－５５」、愛知プラスチックス工業（株）製、厚み＝５５μｍ）である水蒸気バリア層（２）に代えた以外は、実施例１と同様に行い、粘着テープ（２）を得た。水蒸気バリア層（２）の透湿度は、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、６ｇ／ｍ２・２４時間であった。
　各種評価結果を表１に示した。 [Example 2]
Example 1 except that the water vapor barrier layer (1) was replaced with a water vapor barrier layer (2) which is a polyethylene film (trade name “ANE-55”, manufactured by Aichi Plastics Industry Co., Ltd., thickness = 55 μm). It carried out similarly and obtained the adhesive tape (2). The moisture permeability of the water vapor barrier layer (2) was 6 g / m 2 · 24 hours when the thickness was converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
Various evaluation results are shown in Table 1.
〔実施例３〕
　水蒸気バリア層（１）を、ＳＥＢＳ（商品名「Ｇ１６５２」、クレイトンポリマージャパン（株）製、厚み＝５０μｍ）である水蒸気バリア層（３）に代えた以外は、実施例１と同様に行い、粘着テープ（３）を得た。水蒸気バリア層（３）の透湿度は、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、３３ｇ／ｍ２・２４時間であった。
　各種評価結果を表１に示した。 Example 3
Except for replacing the water vapor barrier layer (1) with the water vapor barrier layer (3) which is SEBS (trade name “G1652”, manufactured by Kraton Polymer Japan, Inc., thickness = 50 μm), the same procedure as in Example 1 was performed. An adhesive tape (3) was obtained. The moisture permeability of the water vapor barrier layer (3) was 33 g / m 2 · 24 hours when the thickness was converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
Various evaluation results are shown in Table 1.
〔実施例４〕
　水蒸気バリア層（１）を、ＰＶＣフィルム（一般軟質ＰＶＣ、サンビック株式会社製、厚み＝１３０μｍ）である水蒸気バリア層（４）に代えた以外は、実施例１と同様に行い、粘着テープ（４）を得た。水蒸気バリア層（４）の透湿度は、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、１８ｇ／ｍ２・２４時間であった。
　各種評価結果を表１に示した。 Example 4
Except having replaced the water vapor | steam barrier layer (1) with the water vapor | steam barrier layer (4) which is a PVC film (General soft PVC, the Sanvik Co., Ltd. make, thickness = 130 micrometers), it carries out similarly to Example 1 and performs adhesive tape (4 ) The moisture permeability of the water vapor barrier layer (4) was 18 g / m 2 · 24 hours when the thickness was converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
Various evaluation results are shown in Table 1.
〔実施例５〕
　水蒸気バリア層（１）を、ＰＥＴフィルム（商品名「ルミラーＳ－１０」、東レ製、厚み＝３８μｍ）である水蒸気バリア層（５）に代えた以外は、実施例１と同様に行い、粘着テープ（５）を得た。水蒸気バリア層（５）の透湿度は、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、３６ｇ／ｍ２・２４時間であった。
　各種評価結果を表１に示した。 Example 5
The same procedure as in Example 1 was conducted except that the water vapor barrier layer (1) was replaced with a water vapor barrier layer (5) which was a PET film (trade name “Lumirror S-10”, manufactured by Toray, thickness = 38 μm). Tape (5) was obtained. The moisture permeability of the water vapor barrier layer (5) was 36 g / m 2 · 24 hours when the thickness was converted to 25 μm in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH.
Various evaluation results are shown in Table 1.
〔比較例１〕
＜粘着剤層（Ｃ１）の作成＞
　冷却管、窒素導入管、温度計、および攪拌機を備えた反応容器に、（メタ）アクリル系モノマーとして、２－エチルヘキシルアクリレート（２ＥＨＡ、東亜合成（株）製）を９４重量部、アクリル酸（ＡＡ）を６重量部、光重合開始剤として２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名「イルガキュア６５１」、ＢＡＳＦ製）０．１重量部を投入して分散させ、攪拌しながら窒素気流下にて上部よりＵＶ照射することにより、一部のモノマーをポリマーに転化させて塗工可能な粘度に調整し、（メタ）アクリル系モノマー混合物を得た。この（メタ）アクリル系モノマー混合物に、アクリル系オリゴマー（ジシクロペンタニルメタクリレート／メチルメタクリレート＝６０重量％／４０重量％）：５重量部、架橋剤として１、６－ヘキサンジオールジアクリレート（ＨＤＤＡ）：０．１６重量部を添加し、これをセパレーター（商品名「ＭＲＦ５０」、三菱樹脂（株）製、厚み５０μｍ）の表面にアプリケーターを用いて塗布し、カバーセパレーター（商品名「ＭＲＦ３８」、三菱樹脂（株）製、厚み３８μｍ）をハンドローラーにて貼り合わせ、さらに紫外線ランプ（ＢＬタイプ）により紫外線を照射（紫外線照度：３．４ｍＷ／ｃｍ２、積算照射量：２０００ｍＪ／ｃｍ２）することにより、厚み５０μｍの粘着剤層（Ｃ１）を得た。粘着剤層（Ｃ１）の１８０度ピール接着力を測定した結果、４．８Ｎ／２０ｍｍであった。 [Comparative Example 1]
<Creation of pressure-sensitive adhesive layer (C1)>
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirrer, 94 parts by weight of 2-ethylhexyl acrylate (2EHA, manufactured by Toa Gosei Co., Ltd.) as a (meth) acrylic monomer, acrylic acid (AA) ) And 6 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator, and dispersed therein. By UV irradiation from above in a nitrogen stream while stirring, a part of the monomer was converted into a polymer and adjusted to a coatable viscosity to obtain a (meth) acrylic monomer mixture. To this (meth) acrylic monomer mixture, acrylic oligomer (dicyclopentanyl methacrylate / methyl methacrylate = 60% by weight / 40% by weight): 5 parts by weight, 1,6-hexanediol diacrylate (HDDA) as a crosslinking agent : 0.16 part by weight was added, and this was applied to the surface of a separator (trade name “MRF50”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 50 μm) using an applicator, and a cover separator (trade name “MRF38”, Mitsubishi) Resin Co., Ltd. (thickness 38 μm) is bonded with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW / cm 2 , integrated irradiation amount: 2000 mJ / cm 2 ) with an ultraviolet lamp (BL type). Thus, an adhesive layer (C1) having a thickness of 50 μm was obtained. It was 4.8 N / 20mm as a result of measuring the 180 degree | times peel adhesive force of an adhesive layer (C1).
＜粘着テープの作成＞
　実施例１で得られた「防汚層（１）（厚み１００μｍ）／基材層（１）（厚み１００μｍ）」の積層体の基材層（１）側に、粘着剤層（Ｃ１）（厚み５０μｍ）を、ハンドローラーを用いて貼り合わせ、「防汚層（１）（厚み１００μｍ）／基材層（１）（厚み１００μｍ）／粘着剤層（Ｃ１）（厚み５０μｍ）」からなる粘着テープ（Ｃ１）を得た。
　各種評価結果を表１に示した。 <Creation of adhesive tape>
On the base material layer (1) side of the laminate of “antifouling layer (1) (thickness 100 μm) / base material layer (1) (thickness 100 μm)” obtained in Example 1, the pressure-sensitive adhesive layer (C1) ( Adhesion consisting of “antifouling layer (1) (thickness 100 μm) / base material layer (1) (thickness 100 μm) / adhesive layer (C1) (thickness 50 μm)” A tape (C1) was obtained.
Various evaluation results are shown in Table 1.
〔比較例２〕
　実施例４で用いた水蒸気バリア層（４）上に、実施例１で用いた防汚層材料液（１´）を、アプリケーターを用いて塗布し、１４０℃で２分間硬化させ、厚み１００μｍの防汚層（１）を水蒸気バリア層（４）上に形成させた。次いで、水蒸気バリア層（４）の防汚層（１）の反対側に、実施例１で用いた粘着剤層（１Ｂ）（厚み５０μｍ）を、ハンドローラーを用いて貼り合わせ、「防汚層（１）（厚み１００μｍ）／水蒸気バリア層（４）（厚み５０μｍ）／粘着剤層（１Ｂ）（厚み５０μｍ）」からなる粘着テープ（Ｃ２）を得た。
　各種評価結果を表１に示した。 [Comparative Example 2]
On the water vapor barrier layer (4) used in Example 4, the antifouling layer material liquid (1 ′) used in Example 1 was applied using an applicator, cured at 140 ° C. for 2 minutes, and a thickness of 100 μm. An antifouling layer (1) was formed on the water vapor barrier layer (4). Next, the pressure-sensitive adhesive layer (1B) (thickness 50 μm) used in Example 1 was bonded to the opposite side of the water vapor barrier layer (4) to the antifouling layer (1) using a hand roller. An adhesive tape (C2) consisting of (1) (thickness 100 μm) / water vapor barrier layer (4) (thickness 50 μm) / adhesive layer (1B) (thickness 50 μm) ”was obtained.
Various evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の水生生物付着防止粘着テープは、水中生物が付着して繁殖することを防止できるため、水中構造物（船舶、ブイ、港湾設備、海上油田設備、発電所冷却水用の水路、工場冷却水用の水路、水上浮遊通路など）に好適に利用できる。 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.
　　１　　　　　　剥離フィルム
　　２　　　　　　防汚層
　　３　　　　　　基材層
　　４　　　　　　粘着剤層（Ａ）
　　５　　　　　　水蒸気バリア層
　　６　　　　　　粘着剤層（Ｂ）
１００　　　　　　水生生物付着防止粘着テープ DESCRIPTION OF SYMBOLS 1 Release film 2 Antifouling layer 3 Base material layer 4 Adhesive layer (A)
5 Water vapor barrier layer 6 Adhesive layer (B)
100 Aquatic organism adhesion prevention adhesive tape

Claims (9)

  1. 　防汚層と粘着剤層（Ａ）と水蒸気バリア層と粘着剤層（Ｂ）をこの順に含む、水生生物付着防止粘着テープ。 An aquatic organism adhesion preventing adhesive tape comprising an antifouling layer, an adhesive layer (A), a water vapor barrier layer and an adhesive layer (B) in this order.
  2. 　前記水蒸気バリア層の透湿度が、温度４０℃、湿度９０％ＲＨの雰囲気下において、厚みを２５μｍに換算したときに、８００ｇ／ｍ２・２４時間未満である、請求項１に記載の水生生物付着防止粘着テープ。 The aquatic organism according to claim 1, wherein the moisture permeability of the water vapor barrier layer is less than 800 g / m 2 · 24 hours when the thickness is converted to 25 µm in an atmosphere of a temperature of 40 ° C and a humidity of 90% RH. Adhesion prevention adhesive tape.
  3. 　前記透湿度が５０ｇ／ｍ２・２４時間以下である、請求項２に記載の水生生物付着防止粘着テープ。 The aquatic organism adhesion prevention adhesive tape of Claim 2 whose said water vapor transmission rate is 50 g / m < 2 > * 24 hours or less.
  4. 　前記透湿度が１０ｇ／ｍ２・２４時間以下である、請求項２に記載の水生生物付着防止粘着テープ。 The aquatic organism adhesion prevention adhesive tape according to claim 2 , wherein the moisture permeability is 10 g / m 2 · 24 hours or less.
  5. 　前記水蒸気バリア層の材料が有機高分子材料である、請求項１に記載の水生生物付着防止粘着テープ。 The aquatic organism adhesion preventing adhesive tape according to claim 1, wherein the material of the water vapor barrier layer is an organic polymer material.
  6. 　前記水蒸気バリア層の厚みが０．０１μｍ～１０００μｍである、請求項１に記載の水生生物付着防止粘着テープ。 2. The aquatic organism adhesion preventing adhesive tape according to claim 1, wherein the water vapor barrier layer has a thickness of 0.01 μm to 1000 μm.
  7. 　前記厚みが０．１μｍ～５００μｍである、請求項６に記載の水生生物付着防止粘着テープ。 The aquatic organism adhesion preventing adhesive tape according to claim 6, wherein the thickness is 0.1 μm to 500 μm.
  8. 　弾性率が３００ＭＰａ以下である、請求項１に記載の水生生物付着防止粘着テープ。 The aquatic organism adhesion preventing adhesive tape according to claim 1, wherein the elastic modulus is 300 MPa or less.
  9. 　前記防汚層と前記粘着剤層（Ａ）との間に基材層を有する、請求項１に記載の水生生物付着防止粘着テープ。
          The aquatic organism adhesion prevention adhesive tape of Claim 1 which has a base material layer between the said antifouling layer and the said adhesive layer (A).
PCT/JP2015/083148 2014-12-04 2015-11-26 Adhesive tape for preventing attachment of aquatic organisms WO2016088631A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11339301B2 (en) 2015-01-26 2022-05-24 Avery Dennison Corporation Self adhesive fouling release coating composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000167955A (en) * 1998-12-04 2000-06-20 Nippon Carbide Ind Co Inc Water super-repellent adhesive film
JP2001220524A (en) * 2000-02-08 2001-08-14 Mizusawa Kikai Shoji:Kk Underwater coating composition, method for forming underwater coating film, and underwater coating member
WO2015182611A1 (en) * 2014-05-30 2015-12-03 日東電工株式会社 Adhesive tape preventing adhesion by aquatic organisms
WO2015182610A1 (en) * 2014-05-30 2015-12-03 日東電工株式会社 Adhesive tape for preventing adhesion by aquatic organisms

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000167955A (en) * 1998-12-04 2000-06-20 Nippon Carbide Ind Co Inc Water super-repellent adhesive film
JP2001220524A (en) * 2000-02-08 2001-08-14 Mizusawa Kikai Shoji:Kk Underwater coating composition, method for forming underwater coating film, and underwater coating member
WO2015182611A1 (en) * 2014-05-30 2015-12-03 日東電工株式会社 Adhesive tape preventing adhesion by aquatic organisms
WO2015182610A1 (en) * 2014-05-30 2015-12-03 日東電工株式会社 Adhesive tape for preventing adhesion by aquatic organisms

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11339301B2 (en) 2015-01-26 2022-05-24 Avery Dennison Corporation Self adhesive fouling release coating composition

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