WO2013103085A1 - Adhesive tape for preventing aquatic biofouling - Google Patents

Adhesive tape for preventing aquatic biofouling Download PDF

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Publication number
WO2013103085A1
WO2013103085A1 PCT/JP2012/082751 JP2012082751W WO2013103085A1 WO 2013103085 A1 WO2013103085 A1 WO 2013103085A1 JP 2012082751 W JP2012082751 W JP 2012082751W WO 2013103085 A1 WO2013103085 A1 WO 2013103085A1
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layer
weight
manufactured
base material
thickness
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PCT/JP2012/082751
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French (fr)
Japanese (ja)
Inventor
鈴木 聡
内藤 友也
太樹 末吉
倉田 直記
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日東電工株式会社
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Publication of WO2013103085A1 publication Critical patent/WO2013103085A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B63SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63BSHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B59/00Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
    • B63B59/04Preventing hull fouling
    • B63B59/045Preventing hull fouling by wrapping the submerged hull or part of the hull with an impermeable sheet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29Laminated material
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/10Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16Additional 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
    • C09J2301/162Additional 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2421/00Presence of unspecified rubber
    • C09J2421/006Presence of unspecified rubber in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00Presence of polyurethane
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00Presence of polysiloxane
    • C09J2483/006Presence of polysiloxane in the substrate

Definitions

  • the present invention relates to an aquatic organism adhesion preventing adhesive tape.
  • the present invention is that underwater organisms adhere to underwater structures (such as ships, buoys, harbor facilities, offshore oilfield facilities, waterways for power plant cooling water, waterways for factory cooling water, water floating passages, etc.).
  • the present invention relates to an aquatic organism adhesion prevention adhesive tape for preventing breeding.
  • antifouling paint In order to prevent such damage, antifouling paint has been conventionally applied to underwater structures. Antifouling paints have long contained toxic antifouling agents such as organotin compounds and now cuprous oxide. The adhesion growth of marine organisms can be almost suppressed by the toxicity of antifouling paints, but toxic antifouling agents such as organotin compounds and cuprous oxide have a considerable adverse effect on the human body and the environment. It becomes. Further, when the antifouling paint is dried after being applied, about 30% by weight of the organic solvent (VOC) is volatilized, which adversely affects the work environment and the surrounding environment. In spray coating, in addition to discharging VOC into the atmosphere, it is said that 10% to 20% by weight of the paint is scattered around by the wind.
  • VOC organic solvent
  • antifouling paints so far have an adhesion inhibiting effect on marine organisms, they have a great adverse effect on the human body and the environment, and the current situation is that many problems have not been solved. .
  • an antifouling tape composed of two layers of silicone rubber and an adhesive
  • the silicone rubber layer responsible for the antifouling effect does not contain an antifouling agent such as oil, and is a silicone rubber itself.
  • the antifouling agent is not included, the adhesion of marine organisms can be suppressed by its water repellency in the short term, but the antifouling effect cannot be sustained in the long term.
  • an antifouling tape is composed of two layers of silicone rubber and an adhesive, there is a great concern about strength.
  • silicone rubber has a very low strength at break, and therefore, when such an antifouling tape is peeled off after use, it is difficult to peel off as a tape state, which is not practical.
  • Patent Document 4 a sheet-like tape has been proposed in which a silicone elastomer is provided on a base material via a primer and an adhesive layer is provided on the opposite side of the base material (see Patent Document 4).
  • Patent Document 4 since there is no description regarding the adhesive composition that can be used in water and no description regarding adhesive strength, Patent Document 4 is not realistic in considering application to an aquatic organism adhesion prevention adhesive tape.
  • Patent Document 4 does not have such description at all, and is not realistic in considering application to an aquatic organism adhesion prevention adhesive tape.
  • an antifouling layer is provided on the base material layer.
  • the base material layer and the antifouling layer are caused by the difference in required functions. Since the physical properties are different, there is a problem that the mutual adhesion cannot be sufficiently ensured and is easily peeled off. In particular, when such an antifouling tape is applied to an underwater structure, the ease of peeling between the base material layer and the antifouling layer becomes remarkable.
  • An object of the present invention is an adhesive tape that can effectively prevent adhesion of aquatic organisms, including an antifouling layer, a base material layer, and an adhesive layer in this order, and has excellent adhesion between the antifouling layer and the base material layer. It is another object of the present invention to provide an aquatic organism adhesion preventing adhesive tape.
  • the aquatic organism adhesion preventing adhesive tape of the present invention is An adhesive tape comprising an antifouling layer, a base material layer and an adhesive layer in this order, At least one selected from the antifouling layer and the base material layer includes at least one selected from a silane coupling agent, silicone powder, and silica particles.
  • the total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the antifouling layer and the base material layer is 0.01 wt% to 100 wt%. is there.
  • the base material layer contains an elastomer resin.
  • the elastomer resin is at least one selected from a polyurethane acrylic resin and a polyurethane resin.
  • the antifouling layer contains a silicone resin.
  • the adhesive tape includes the antifouling layer, the base material layer, and the adhesive layer in this order, and can effectively prevent attachment of aquatic organisms, and has excellent adhesion between the antifouling layer and the base material layer.
  • an aquatic organism adhesion preventing adhesive tape can be provided.
  • FIG. 1 It is a schematic sectional drawing of an example of the aquatic organism adhesion prevention adhesive tape of this invention. It is a photograph figure which shows the state of the adhesive test result of the adhesive tape (1) obtained in Example 1. FIG. It is a photograph figure which shows the state after the running water test of the adhesive tape (1) obtained in Example 1. FIG. It is a photograph figure which shows the state of the adhesive test result of the adhesive tape (C1) obtained by the comparative example 1. FIG. It is a photograph figure which shows the state after the flowing water test of the adhesive tape (C1) obtained by the comparative example 1.
  • the aquatic organism adhesion preventing adhesive tape of the present invention comprises an antifouling layer, a base material layer and an adhesive layer in this order.
  • the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has any appropriate other layer as long as the antifouling layer, the base material layer, and the pressure-sensitive adhesive layer are included in this order, as long as the effects of the present invention are not impaired. May be.
  • the thickness of the aquatic organism adhesion prevention adhesive tape of this invention is set to arbitrary appropriate thickness in the range which does not impair the effect of this invention by the thickness of each layer contained in it.
  • the thickness of the aquatic organism adhesion preventing adhesive tape of the present invention is preferably 50 ⁇ m to 500 ⁇ m.
  • FIG. 1 shows a schematic cross-sectional view of an example of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the aquatic organism adhesion prevention adhesive tape 100 of this invention contains the antifouling layer 2, the base material layer 3, and the adhesion layer 4 in this order.
  • a release film 1 may be provided on the surface of the antifouling layer 2 or the surface of the adhesive layer 4.
  • At least one selected from the antifouling layer and the base material layer includes at least one selected from a silane coupling agent, silicone powder, and silica particles. That is, (1) When the antifouling layer contains at least one selected from a silane coupling agent, silicone powder, and silica particles, and the substrate layer does not contain any of the silane coupling agent, silicone powder, and silica particles (2) The antifouling layer does not contain any of the silane coupling agent, silicone powder, and silica particles, and the base material layer is at least one selected from silane coupling agent, silicone powder, and silica particles. It may be a case containing seeds, or (3) both the antifouling layer and the base material layer may contain at least one selected from a silane coupling agent, silicone powder, and silica particles.
  • the antifouling layer and the base material layer contains at least one selected from a silane coupling agent, silicone powder, and silica particles
  • high adhesion between the antifouling layer and the base material layer is exhibited. can do. If the adhesion between the antifouling layer and the base material layer is low, the antifouling layer that exerts the antifouling effect peels off from the base material layer due to impact or physical damage during use, and the original antifouling effect is obtained. May not be sustainable.
  • the adhesion between the antifouling layer and the base material layer is particularly remarkable when the antifouling layer contains a silicone resin. This is due to the low surface energy that is a characteristic of silicone resins. In this invention, even if it is a case where an antifouling layer contains a silicone resin, the high adhesiveness of an antifouling layer and a base material layer can be expressed.
  • silane coupling agent Only one type of silane coupling agent may be used, or two or more types may be used.
  • silane coupling agent examples include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane, etc.
  • vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane
  • 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 3-glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, 3-glycidoxypropyl
  • Styryl group-containing silane coupling agent 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Methacrylic group-containing silane coupling agent such as silane; Acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Amino group-containing silane coupling agents such as phenyl-3-a
  • silane coupling agents include KBM5103, KBM1003, KBM903, KBM403, and KBM802 manufactured by Shin-Etsu Chemical Co., Ltd.
  • silicone powder Only one type of silicone powder may be used, or two or more types may be used.
  • the average particle size of the silicone powder is preferably 1 nm to 100 ⁇ m, more preferably 10 nm to 70 ⁇ m, still more preferably 100 nm to 50 ⁇ m, and particularly preferably 500 nm to 20 ⁇ m.
  • the average particle diameter of the silicone powder is within the above range, high adhesion between the antifouling layer and the base material layer can be expressed more effectively.
  • silicone powder examples include silicone rubber particles having a structure in which linear dimethylpolysiloxane is crosslinked, and a silicone resin that is a cured product of polyorganosilsesquioxane having a structure in which siloxane bonds are crosslinked in a three-dimensional network.
  • silicone resin examples include particles and silicone composite particles in which the surface of silicone rubber particles is coated with a silicone resin.
  • silicone powders include silicone composite powders (KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.) manufactured by Shin-Etsu Chemical Co., Ltd. Silicone rubber powder (KMP-597, KMP-598, KMP-594, X-52-875, etc.), silicone resin powder (KMP-590, KMP-701, X-52-854, X-52-1621, etc.) Can be mentioned.
  • silicone composite powders KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.
  • Silicone rubber powder KMP-597, KMP-598, KMP-594, X-52-875, etc.
  • silicone resin powder KMP-590, KMP-701, X-52-854, X-52-1621, etc.
  • the silica particles may be only one kind or two or more kinds.
  • the average particle diameter of the silica particles is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 70 ⁇ m, still more preferably 3 nm to 50 ⁇ m, and particularly preferably 5 nm to 30 ⁇ m.
  • the average particle diameter of the silica particles falls within the above range, high adhesion between the antifouling layer and the base material layer can be expressed more effectively.
  • silica particles examples include silicon dioxide (SiO 2 ) particles or particles composed of silicon dioxide (SiO 2 ), and examples include hydrophobic silica particles and hydrophilic silica particles.
  • examples of the silica particles include particles whose surface has been subjected to a hydrophobic treatment and particles whose surface has been subjected to a hydrophilic treatment.
  • silica particles include Aerosil series (produced by Nippon Aerosil Co., Ltd.). More specifically, in hydrophobicity, Aerosil R8200 (primary average particle size: 12 nm, hexamethyldisilazane treatment), Aerosil R104 (Primary average particle size: 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R972 (Primary average particle size: 16 nm, dimethyldichlorosilane treatment), Aerosil R974 (Primary average particle size: 12 nm, dimethyldichlorosilane treatment), Aerosil R812 (Primary average particle size: 7 nm, hexamethyldisilazane treatment), etc. Examples of hydrophilicity include Aerosil 200 (primary average particle size: 12 nm), Aerosil 300 (primary average particle size: 7 nm), and the like.
  • the total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the antifouling layer and the base material layer is preferably 0.01% by weight to 100% by weight, and more preferably 0.5% by weight. % To 30% by weight, more preferably 0.1% to 10% by weight, and particularly preferably 1% to 5% by weight.
  • the said content rate is settled in the said range, the high adhesiveness of a pollution protection layer and a base material layer can be expressed more effectively.
  • the said content rate is less than 0.01 weight%, there exists a possibility that sufficient adhesiveness cannot be expressed between a base material layer and an antifouling layer.
  • the upper limit of the content ratio of the silane coupling agent relative to the total of the antifouling layer and the base material layer is preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. is there.
  • the silane coupling agent with respect to the total of the antifouling layer and the base material layer is within the above range, the silane coupling agent becomes a crosslinking point and the layer containing the silane coupling agent becomes too hard. This can be suppressed.
  • a primer may be applied to the base material layer in advance.
  • any appropriate material can be adopted as long as the effects of the present invention are not impaired.
  • Such a material for the base material layer is preferably excellent in water resistance, strength, flexibility and tearability.
  • 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.
  • the base material layer preferably contains an elastomer resin.
  • the elastomer resin any appropriate elastomer resin can be adopted as long as the effects of the present invention are not impaired.
  • examples of such elastomer resins include vulcanized rubber and thermoplastic elastomer.
  • examples of the thermoplastic elastomer include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like.
  • the content ratio of the elastomer resin in the base material layer is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 99% by weight, particularly preferably. 80 to 98% by weight, most preferably 90 to 97% by weight.
  • the elastomer resin that can be contained in the base material layer may be only one kind or two or more kinds. Since the base material layer contains an elastomer resin, it can be easily applied to parts other than flat surfaces such as curved surfaces and acute angles with good workability, and appearance defects such as wrinkles and floats are unlikely to occur on the surface after application.
  • a bioadhesion-preventing adhesive tape can be provided.
  • the elastomer resin that can be included in the base material layer is preferably a urethane-based elastomer.
  • the urethane elastomer is preferably at least one selected from polyurethane acrylic resins and polyurethane resins.
  • the polyurethane resin include carbonate-based polyurethane, ester-based polyurethane, and ether-based polyurethane.
  • Polyurethane acrylic resin has an acrylic component and a urethane component. More specifically, the polyurethane acrylic resin is a composite polymer containing a (meth) acrylic polymer and a urethane polymer.
  • the weight ratio of the (meth) acrylic polymer to the urethane polymer in the polyurethane acrylic resin is within the above range, the increase in the viscosity of the precursor mixture can be suppressed and workability can be maintained well, and the polyurethane acrylic resin can be maintained. Can provide excellent flexibility and excellent strength.
  • the viscosity of the precursor mixture may be high and workability may be deteriorated. If it exceeds 80/20, flexibility and strength as a polyurethane acrylic resin may be obtained. May not be obtained.
  • (meth) acryl means acrylic and / or methacrylic.
  • the (meth) acrylic polymer in the polyurethane acrylic resin is preferably a polymer obtained using a monomer component containing a (meth) acrylic acid monomer and a monofunctional (meth) acrylic monomer.
  • the (meth) acrylic polymer in the polyurethane acrylic resin is a polymer obtained by using a monomer component including a monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of a homopolymer of 0 ° C. or higher. Is preferred.
  • the (meth) acrylic polymer in the polyurethane acrylic resin has a glass transition temperature (Tg) of the homopolymer in addition to the monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of the homopolymer of 0 ° C. or higher. ) Is more preferably a polymer obtained by using a monomer component containing a monofunctional (meth) acrylic monomer having a temperature of less than 0 ° C.
  • (Meth) acrylic acid monomer is a (meth) acrylic monomer having a carboxyl group.
  • examples of the (meth) acrylic acid monomer include acrylic acid, methacrylic acid, maleic acid, crotonic acid and the like.
  • a preferable example of the (meth) acrylic acid-based monomer is acrylic acid in that the effects of the present invention can be further exhibited.
  • the content ratio of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin is preferably 1% by weight to 15% by weight, and more preferably 2% by weight to 10% by weight.
  • the content ratio of the (meth) acrylic acid monomer in the monomer component that is the raw material of the polyurethane acrylic resin falls within the above range, the synthesis reaction of the polyurethane acrylic resin can be smoothly advanced, and it is sufficient for the polyurethane acrylic resin. High strength and water resistance.
  • the content of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin is less than 1% by weight, the polyurethane acrylic resin may take a long time for the synthesis reaction, and the polyurethane acrylic resin has sufficient strength. May not have.
  • the content ratio of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin exceeds 15% by weight, the water absorption of the polyurethane acrylic resin increases, which may cause a problem in water resistance. .
  • the (meth) acrylic acid monomer greatly affects the compatibility between the urethane component and the acrylic component in the polyurethane acrylic resin.
  • Examples of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher include acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and lauryl acrylate.
  • the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher may be only one type or two or more types.
  • the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher is preferably at least one selected from acryloylmorpholine, isobornyl acrylate, and dicyclopentanyl acrylate in that the effects of the present invention can be further exhibited. More preferably, isobornyl acrylate is used.
  • the content ratio of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is preferably 20% by weight to 99% by weight, More preferably, it is 30 to 98% by weight. It is sufficient for polyurethane acrylic resin because the content ratio of monofunctional (meth) acrylic monomer having Tg of 0 ° C. or more in the monomer component constituting (meth) acrylic polymer in polyurethane acrylic resin is within the above range. In addition to imparting high strength, it is possible to suppress an excessive increase in rigidity of the polyurethane acrylic resin.
  • the polyurethane acrylic resin is sufficient. May not have strength.
  • the content of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin exceeds 99% by weight, the rigidity of the polyurethane acrylic resin is increased. May rise and become brittle.
  • Examples of monofunctional (meth) acrylic monomers having a Tg of less than 0 ° C. include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofluorofuryl acrylate, Examples include phenoxyethyl acrylate, ethoxyethyl acrylate, and 3-methoxybutyl acrylate.
  • the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. may be only one type or two or more types.
  • the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. is preferably n-butyl acrylate, from the viewpoint that the effects of the present invention can be further exhibited.
  • the content ratio of the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is preferably 50% by weight or less, more preferably 45% by weight or less. It is sufficient for polyurethane acrylic resin because the content ratio of monofunctional (meth) acrylic monomer with Tg of less than 0 ° C in the monomer component constituting (meth) acrylic polymer in polyurethane acrylic resin is within the above range. Can provide a high strength. When the content of the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin exceeds 50% by weight, the polyurethane acrylic resin May not have sufficient strength.
  • (Meth) acrylic monomers such as (meth) acrylic acid monomers and monofunctional (meth) acrylic monomers contained in the raw material monomers for (meth) acrylic polymers in polyurethane acrylic resins are compatible with urethane, In consideration of the polymerizability at the time of photocuring such as radiation and the characteristics of the high molecular weight substance to be obtained, the type, combination, amount used and the like are appropriately determined.
  • the raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin may contain any appropriate other monomer as long as the effects of the present invention are not impaired.
  • examples of such other monomers include vinyl acetate, vinyl propionate, styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, derivatives thereof, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, N, N— Dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, 2-hydroxypropyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, imide acrylate, N-vinylpyrrolidone, oligoester acrylate, ⁇ -caprolactone Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxy
  • the raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin may contain other polyfunctional monomers as long as the effects of the present invention are not impaired.
  • polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth).
  • Acrylate pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate and the like.
  • trimethylolpropane tri (meth) acrylate is preferably used in that the effects of the present invention can be further exhibited.
  • the content is preferably 1 weight with respect to the (meth) acrylic monomer in the raw material monomer. % To 20% by weight. If the content ratio is 1% by weight or more, the cohesive force of the polyurethane acrylic resin can be maintained sufficiently high, and if the content ratio is 20% by weight or less, the elastic modulus of the polyurethane acrylic resin becomes too high. It is possible to follow the irregularities on the surface of the adherend satisfactorily.
  • the urethane polymer in the polyurethane acrylic resin is preferably obtained by reacting a diol with a diisocyanate.
  • a catalyst may be used for the reaction between the hydroxyl group of the diol and the isocyanate.
  • low molecular weight diol examples include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol.
  • Examples of the high molecular weight diol include polyether polyols obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, and the like; divalent alcohols described above, 1,4-butanediol, 1,6-hexanediol, and the like Examples include polyester polyols composed of polycondensates of alcohols with divalent basic acids such as adipic acid, azelaic acid, and sebacic acid; acrylic polyols; carbonate polyols; epoxy polyols; caprolactone polyols; Among these, as the high molecular weight diol, polyoxytetramethylene glycol (PTMG) and polyalkylene carbonate diol (PCD) are preferable because the effects of the present invention can be further exhibited.
  • PTMG polyoxytetramethylene glycol
  • PCD polyalkylene carbonate diol
  • acrylic polyol examples include a copolymer of a hydroxyl group-containing monomer and a (meth) acrylic monomer, in addition to a copolymer of a monomer having a hydroxyl group.
  • Examples of the epoxy polyol include amine-modified epoxy resins.
  • the urethane polymer in the polyurethane acrylic resin only one kind of the diol may be used in consideration of solubility in the (meth) acrylic monomer, reactivity with isocyanate, etc. Two or more kinds may be used.
  • it is effective to increase the amount of the urethane hard segment by the low molecular weight diol.
  • polyether polyols are generally inexpensive and have good water resistance. The polyester polyol can improve the strength of the polyurethane acrylic resin.
  • diisocyanate examples include aromatic, aliphatic, and alicyclic diisocyanates; dimers and trimers of these diisocyanates; polyphenylmethane diisocyanate; and the like. Only one diisocyanate may be used, or two or more diisocyanates may be used.
  • aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate (HXDI), isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanate methyl) Cyclohexane, methylcyclohexan
  • trimer of aromatic, aliphatic and alicyclic diisocyanates examples include isocyanurate type, burette type and allophanate type.
  • the diisocyanate is preferably hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4-diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI) in that the effects of the present invention can be further exhibited. ), Hydrogenated xylene diisocyanate (HXDI).
  • HDI hexamethylene diisocyanate
  • HTDI hydrogenated tolylene diisocyanate
  • HMDI hydrogenated 4,4-diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HXDI Hydrogenated xylene diisocyanate
  • the ratio of the diol component and diisocyanate component used to form the urethane polymer is preferably NCO / OH (equivalent ratio) of 1.1 to 2.0, more preferably 1.15 to 1.35. .
  • NCO / OH Equivalent ratio
  • the polyurethane acrylic resin can be provided with excellent strength, sufficient elongation, and sufficient flexibility.
  • NCO / OH (equivalent ratio) is less than 1.1, the strength of the polyurethane acrylic resin may be reduced. If NCO / OH (equivalent ratio) exceeds 2.0, the polyurethane acrylic resin may not be sufficiently stretched and flexible.
  • a hydroxyl group-containing (meth) acrylic monomer may be added to the urethane polymer.
  • a hydroxyl group-containing (meth) acrylic monomer By adding a hydroxyl group-containing (meth) acrylic monomer to the urethane polymer, a (meth) acryloyl group can be introduced at the molecular terminal of the urethane prepolymer, and the copolymerization with the (meth) acrylic monomer is possible.
  • compatibility between the urethane component and the acrylic component is increased, and SS characteristics such as breaking strength can be improved.
  • the amount of the hydroxyl group-containing (meth) acrylic monomer used is preferably 0.1% by weight to 10% by weight and more preferably 1% by weight with respect to the urethane polymer in that the effect of the present invention can be further exhibited. ⁇ 5% by weight.
  • hydroxyl group-containing (meth) acrylic monomer examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.
  • the polyurethane acrylic resin preferably has a heterogeneous network structure in which a (meth) acrylic polymer and a urethane polymer are bonded to each other by a graft structure or a crosslinked structure.
  • IPN structure interpenetrating polymer network layer in which (meth) acrylic polymer and urethane polymer each independently have a crosslinked structure, or one of (meth) acrylic polymer and urethane polymer has a crosslinked structure.
  • a semi-IPN structure in which one of these has a linear polymer chain and penetrates into the cross-linked structure, the stress at the time of expansion of the polyurethane acrylic resin may be difficult to develop.
  • the base material layer includes a (meth) acrylic monomer as a diluent and a diol and a diisocyanate in the (meth) acrylic monomer. Reaction is performed to form a urethane polymer, and a mixture containing (meth) acrylic monomer and urethane polymer as main components is applied onto a substrate (exfoliated if necessary), and photopolymerization is started.
  • a base material layer can be formed. Or it can also obtain in the form by which the base material layer was laminated
  • the base material layer is prepared by, for example, adding a diisocyanate or the like after dissolving a diol in a (meth) acrylic monomer.
  • the viscosity is adjusted by reacting with a diol, and this is applied to a support or the like, or, if necessary, applied to a release-treated surface of a support or the like, and then cured by using a low-pressure mercury lamp or the like.
  • the (meth) acrylic monomer may be added all at once during the urethane synthesis or may be added in several divided portions.
  • the diisocyanate is dissolved in the (meth) acrylic monomer
  • the diol may be reacted.
  • the molecular weight is not limited and a high molecular weight polyurethane can be produced, so that the molecular weight of the finally obtained urethane can be designed to an arbitrary size.
  • a release-treated sheet (separator, etc.) may be placed on the mixture coated on a support or the like to block oxygen, or in a container filled with an inert gas.
  • a base material may be added to lower the oxygen concentration.
  • the type of radiation and the type of lamp used for irradiation can be selected as appropriate.
  • lamps include low-pressure lamps such as fluorescent chemical lamps, black lights, and sterilization lamps; high-pressure lamps such as metal halide lamps and high-pressure mercury lamps.
  • Irradiation amounts such as ultraviolet rays can be arbitrarily set according to the characteristics of the base material layer.
  • the dose of ultraviolet rays is preferably 100mJ / cm 2 ⁇ 5000mJ / cm 2, more preferably 1000mJ / cm 2 ⁇ 4000mJ / cm 2, more preferably 2000mJ / cm 2 ⁇ 3000mJ / cm 2 .
  • the amount of ultraviolet irradiation within the above range, a sufficient polymerization rate can be obtained without deterioration.
  • the dose of ultraviolet ray is less than 100 mJ / cm 2, it might not provide a sufficient rate of polymerization, and is larger than 5000 mJ / cm 2, which may cause deterioration.
  • the temperature at the time of irradiation with ultraviolet rays or the like can be set to any appropriate temperature depending on the purpose. If the temperature at the time of irradiation with ultraviolet rays or the like is too high, a stop reaction due to polymerization heat tends to occur, which tends to cause deterioration of characteristics. For this reason, the temperature at the time of irradiating with ultraviolet rays or the like is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 30 ° C. or lower.
  • a mixture containing at least a urethane polymer preferably contains a photopolymerization initiator.
  • photopolymerization initiator examples include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether; substituted benzoin ethers such as anisole methyl ether; 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone.
  • Substituted alpha-ketols such as substituted acetophenone, 1-hydroxycyclohexyl, phenyl ketone, 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; 1-phenyl-1,1-propanedione-2 And photoactive oximes such as-(o-ethoxycarbonyl) -oxime.
  • the base material layer may contain any appropriate additive as long as the effects of the present invention are not impaired.
  • additives include olefin resins, silicone polymers, liquid acrylic copolymers, tackifiers, anti-aging agents, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, and antistatic agents. , Polyethyleneimine, fatty acid amide, fatty acid ester, phosphate ester, lubricant, surfactant, filler and pigment (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, carbon black, etc.).
  • the base material layer preferably contains an ultraviolet absorber.
  • the weather resistance of the aquatic organism adhesion prevention adhesive tape of this invention improves because a base material layer contains a ultraviolet absorber.
  • the base material layer does not contain an ultraviolet absorber, the base material is likely to be deteriorated by sunlight during outdoor use, and it may be difficult to maintain the initial base material strength.
  • the base material layer is frequently cut when the used aquatic organism adhesion preventing adhesive tape of the present invention is peeled off from the adherend, and the work efficiency may be significantly deteriorated. There is.
  • 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 has excellent adhesion between the antifouling layer and the base material layer, and is applied to sites other than flat surfaces such as curved surfaces and acute angle surfaces. Can be easily applied with good workability, and appearance defects such as wrinkles and floats are unlikely to occur on the surface after application.
  • any appropriate layer can be adopted as long as it can exhibit an antifouling effect.
  • the antifouling layer is preferably a layer that can exhibit an antifouling effect without using an antifouling paint.
  • any suitable resin having an antifouling effect is used as a material.
  • a resin Preferably, a silicone resin is mentioned.
  • the antifouling layer contains a silicone resin
  • any appropriate content can be adopted as the content of the silicone resin in the antifouling layer depending on the content of other components such as an antifouling agent.
  • the content of the silicone resin in the antifouling layer is preferably 30% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, and still more preferably 45% by weight to It is 96% by weight, particularly preferably 50% to 95% by weight.
  • the content ratio of the silicone resin in the antifouling layer is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the mechanical characteristics of the antifouling layer can be sufficiently expressed.
  • the content ratio of the silicone resin in the antifouling layer is less than 30% by weight, the mechanical properties of the antifouling layer may be deteriorated.
  • the content ratio of the silicone resin in the antifouling layer exceeds 98% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited.
  • any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used. Such a silicone resin may be a silicone resin that is liquid at normal temperature, or may be a silicone resin that is solid at normal temperature. Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin. Such a silicone resin may be a one-component silicone resin that is dried alone, or a two-component silicone resin that contains a curing agent. In the present invention, among these, a one-component room temperature curable (RTV) resin and a two-component room temperature curable (RTV) resin are preferable.
  • RTV room temperature curable
  • RTV room temperature curable
  • Examples of the one-component RTV resin include KE-3475, KE-45S, KE-445, KE-44, KE-441, KE-3497, and KE-4896 manufactured by Shin-Etsu Chemical Co., Ltd. .
  • Examples of the two-component RTV resin include KE106, KE-66, KE-1031, and KE-1800 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 may contain an antifouling agent. Only one type of antifouling agent may be used, or two or more types may be used.
  • the antifouling layer contains an antifouling agent, the antifouling agent migrates to the surface of the silicone resin as a matrix and covers the surface with an antifouling substance, thereby suppressing the adhesion of aquatic organisms to the silicone resin surface. Furthermore, since it is non-hydrolyzable, it can exhibit the effect of maintaining a high antifouling effect for a long period of time.
  • the content of the antifouling agent with respect to the silicone resin in the antifouling layer is preferably 2% by weight or more, more preferably 2% by weight to 200% by weight, and even more preferably 3% by weight. % To 150% by weight, particularly preferably 4% to 120% by weight, most preferably 5% to 100% by weight.
  • the content ratio of the antifouling agent to the silicone resin is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the appearance characteristics and mechanical characteristics of the antifouling layer can be sufficiently expressed.
  • the content ratio of the antifouling agent to the silicone resin is less than 2% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited.
  • the content of the antifouling agent relative to the silicone resin exceeds 200% by weight, the appearance of the final molded product or the film may be deteriorated, and the antifouling layer strength is lowered and the antifouling property cannot be maintained. There is a fear.
  • any appropriate antifouling agent can be adopted as long as the effects of the present invention are not impaired.
  • examples of such an antifouling agent include silicone oil, liquid paraffin, surfactant, wax, petrolatum, animal fats, fatty acids and the like.
  • the antifouling agent is preferably at least one selected from silicone oil, liquid paraffin, and surfactant.
  • the silicone oil is preferably one that does not have reactivity with the silicone resin or self-condensation.
  • any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired.
  • Such a silicone oil is preferably incompatible with the organopolysiloxane contained in the silicone resin to some extent, and is represented by, for example, the general formula (I) in that the antifouling effect can be maintained over a long period of time. Silicone oil is preferred.
  • 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 silicone oil represented by the general formula (I) has a number average molecular weight of preferably 180 to 20000, more preferably 1000 to 10,000.
  • the viscosity of the silicone oil represented by the general formula (I) is preferably 10 centistokes to 10000 centistokes, more preferably 100 centistokes to 5000 centistokes.
  • 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.
  • surfactant examples include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
  • antifouling agents diatomaceous adhesion inhibitors, agricultural chemicals, pharmaceuticals (such as medetomidine), enzyme activity inhibitors (such as alkylphenols and alkylresorcinol), and biological repellents may be used.
  • pharmaceuticals such as medetomidine
  • enzyme activity inhibitors such as alkylphenols and alkylresorcinol
  • biological repellents may be used.
  • the antifouling layer may contain any appropriate other additive as long as the effects of the present invention are not impaired.
  • the thickness of the antifouling layer may be any appropriate thickness depending on the application or use environment of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the thickness of the antifouling layer is preferably 5 ⁇ m to 500 ⁇ m. When the thickness of the antifouling layer is within the above range, the antifouling effect is effective for a sufficiently long time, and the handling property is excellent. When the thickness of the antifouling layer is less than 5 ⁇ m, the period during which the antifouling effect is effective is shortened and may not be practical. If the antifouling layer is thicker than 500 ⁇ m, the aquatic organism adhesion-preventing adhesive tape of the present invention becomes thick and increases in weight, resulting in poor handling, large irregularities at the joints of the tape, and dirt. There is a fear.
  • any appropriate adhesive layer can be adopted 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. Agents, silicone resin adhesives, and the like.
  • the material of the adhesive layer may be only one type or two or more types.
  • the thickness of the adhesive layer any appropriate thickness can be adopted depending on the application and use environment of the aquatic organism adhesion preventing adhesive tape of the present invention.
  • the thickness of the adhesive layer is preferably 10 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer is within the above range, the shape of the adherend can be sufficiently followed, the adhesion area can be sufficiently secured, and sufficient adhesive force can be expressed.
  • the thickness of the pressure-sensitive adhesive layer is less than 10 ⁇ m, it is impossible to sufficiently follow the shape of the adherend, the adhesion area is reduced, and there is a possibility that sufficient pressure-sensitive adhesive force cannot be expressed.
  • the upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 300 ⁇ m or less from the viewpoint of handleability.
  • the aquatic organism adhesion preventing adhesive tape of the present invention can be produced by any appropriate method.
  • a method of forming an antifouling layer by applying an antifouling layer forming material on the base material layer after pasting a separately prepared base material layer and an adhesive layer, and one of the base material layers.
  • a method of forming an adhesive layer by applying an adhesive layer forming material on the surface and forming an antifouling layer by applying an antifouling layer forming material to the other surface of the base material layer, the base layer forming material and the adhesive layer For example, a method of forming the antifouling layer by applying the antifouling layer forming material on the base material layer after co-extrusion of the forming material to form a base material layer / adhesive layer laminate.
  • Examples of the method for applying the antifouling layer forming material on the base material layer include spraying, brushing, roller, curtain flow, roll, dip and the like.
  • the antifouling layer-forming material is applied onto the base material layer by these methods, and the antifouling layer is formed, for example, by drying at a temperature from room temperature to 250 ° C. (preferably from room temperature to 180 ° C.). can do.
  • ⁇ Adhesion test> The pressure-sensitive adhesive tape to be evaluated was cut into a size of 2 cm ⁇ 6 cm, cut into the antifouling layer with a cutter, and stretched in the longitudinal direction to evaluate whether the antifouling layer was peeled off from the base material layer.
  • Example 1 (Adhesive layer) In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 2-ethylhexyl acrylate (2EHA, manufactured by Toagosei Co., Ltd.) as a (meth) acrylic monomer: 90 parts by weight, acrylic acid (AA ): 10 parts by weight, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator: 0.1 parts by weight are added and dispersed.
  • 2EHA 2-ethylhexyl acrylate
  • AA acrylic acid
  • Irgacure 651 2,2-dimethoxy-1,2-diphenylethane-1-one
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (1-B).
  • Adhesive tape The obtained adhesive layer (1-A) and substrate layer (1-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (1-B) of this tape with an applicator to form a syrup layer having a thickness of 150 ⁇ m. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (1).
  • the evaluation results are shown in Table 1. Moreover, the photograph figure which shows the state of the adhesive test result of an adhesive tape (1) was shown in FIG. 2, and the photograph figure which shows the state after the flowing water test of an adhesive tape (1) was shown in FIG.
  • Example 2 (Adhesive layer) In the same manner as in Example 1, an adhesive layer (2-A) having a thickness of 50 ⁇ m was obtained.
  • Base material layer In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 80 parts by weight, n -Butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 20 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) 68.4 parts by weight, dibutyltin dilaurate (DBTL): 2 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI,
  • urethane polymer- (meth) acrylic monomer mixture A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (2-B).
  • Adhesive tape The obtained adhesive layer (2-A) and substrate layer (2-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (2-B) of this tape with an applicator to form a syrup layer having a thickness of 150 ⁇ m. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (2).
  • Example 3 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (3-B).
  • Adhesive tape The obtained adhesive layer (3-A) and substrate layer (3-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (3-B) of this tape with an applicator to form a syrup layer having a thickness of 150 ⁇ m. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (3).
  • Example 4 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • silicone powder (KMP600, manufactured by Shin-Etsu Chemical Co., Ltd.): 5 parts by weight, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, light Diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a polymerization initiator: 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF) : 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 part by weight was added to obtain a syrup.
  • TMPTA trimethylolpropane triacrylate
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, manufactured by BASF
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (4-B).
  • Example 5 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (5-B).
  • Example 6 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • TMPTA trimethylolpropane triacrylate
  • diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, BASF
  • Product A syrup was obtained by adding 0.6 parts by weight.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (6-B).
  • Example 7 Adhesive layer
  • an adhesive layer (7-A) having a thickness of 50 ⁇ m was obtained.
  • a urethane resin substrate (XUS2098, manufactured by Seadam Co., Ltd.) was used to form a substrate layer (7-B) having a thickness of 150 ⁇ m.
  • Adhesive tape The obtained adhesive layer (7-A) and substrate layer (7-B) were bonded together with a hand roller to obtain a tape.
  • Example 8 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (DBTL): 0.
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • TMPTA trimethylolpropane triacrylate
  • diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, BASF
  • Product A syrup was obtained by adding 0.6 parts by weight.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (8-B).
  • Example 9 Adhesive layer
  • an adhesive layer (9-A) having a thickness of 50 ⁇ m was obtained.
  • Base material layer A urethane resin base material (DUS451, manufactured by Seadam Co., Ltd.) was used to form a base material layer (9-B) having a thickness of 150 ⁇ m.
  • Adhesive tape The obtained adhesive layer (9-A) and substrate layer (9-B) were bonded together with a hand roller to obtain a tape.
  • Example 10 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (ABS-A): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxyte
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • silica particles (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.): 2.5 parts by weight, trimethylolpropane triacrylate (TMPTA): 5 parts by weight Diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, BASF) Product: 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 part by weight was added to obtain a syrup.
  • TMPTA trimethylolpropane triacrylate
  • Diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight
  • UV absorber (trade name “TINUVIN123”, BASF)
  • antioxidant trade name “TINUVIN400”, manufactured by BASF): 0.6 part by
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (10-B).
  • Adhesive tape The obtained adhesive layer (10-A) and substrate layer (10-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (10-B) of this tape, a condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and silica particles A mixed solution obtained by mixing (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.) at a ratio of 100: 50: 1 was applied with an applicator to form a syrup layer having a thickness of 150 ⁇ m. This was cured at 150 ° C.
  • a condensation type silicone elastomer KE445, manufactured by Shin-Etsu Chemical Co., Ltd.
  • silicone oil KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.
  • silica particles A mixed solution obtained by mixing (Aeros
  • Example 11 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (11-B).
  • Adhesive tape The obtained adhesive layer (11-A) and substrate layer (11-B) were bonded together with a hand roller to obtain a tape.
  • a condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silane cup
  • Example 12 Adhesive layer
  • An adhesive layer (12-A) having a thickness of 50 ⁇ m was obtained.
  • (Base material layer) A urethane resin base material (DUS451, manufactured by Sea Dam Co., Ltd.) was used to form a base material layer (12-B) having a thickness of 150 ⁇ m.
  • (Adhesive tape) The obtained adhesive layer (12-A) and substrate layer (12-B) were bonded together with a hand roller to obtain a tape.
  • Example 13 Adhesive layer
  • an adhesive layer (13-A) having a thickness of 50 ⁇ m was obtained.
  • Base material layer A urethane resin base material (DUS451, manufactured by Seadam Co., Ltd.) was used to form a base material layer (13-B) having a thickness of 150 ⁇ m.
  • Adhesive tape The obtained adhesive layer (13-A) and substrate layer (13-B) were bonded together with a hand roller to obtain a tape.
  • Example 14 Adhesive layer
  • a (meth) acrylic monomer isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate
  • urethane polymer- (meth) acrylic monomer mixture 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 9.15 parts by weight was added and reacted at 65 ° C. for 1 hour, so that acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • TMPTA trimethylolpropane triacrylate
  • diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, BASF
  • Product A syrup was obtained by adding 0.6 parts by weight.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is bonded onto this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (14-B).
  • Adhesive tape The obtained adhesive layer (14-A) and substrate layer (14-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (14-B) of this tape, an addition type silicone elastomer (TSE3032, manufactured by Momentive Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silane coupling agent.
  • TSE3032 silicone elastomer
  • silicone oil KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.
  • silane coupling agent a silane coupling agent.
  • urethane polymer- (meth) acrylic monomer mixture A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • TMPTA trimethylolpropane triacrylate
  • diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, BASF
  • Product A syrup was obtained by adding 0.6 parts by weight.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (C1-B).
  • urethane polymer- (meth) acrylic monomer mixture A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • TMPTA trimethylolpropane triacrylate
  • diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, BASF
  • Product A syrup was obtained by adding 0.6 parts by weight.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (C2-B).
  • urethane polymer- (meth) acrylic monomer mixture A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
  • hydroxyethyl acrylate trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.
  • TMPTA trimethylolpropane triacrylate
  • diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide
  • UV absorber trade name “TINUVIN123”, manufactured by BASF
  • antioxidant trade name “TINUVIN400”, BASF
  • Product A syrup was obtained by adding 0.6 parts by weight.
  • the obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 ⁇ m) with an applicator to form a syrup layer having a thickness of 150 ⁇ m.
  • a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 ⁇ m) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (C3-B).
  • Adhesive layer In the same manner as in Example 1, an adhesive layer (C4-A) having a thickness of 50 ⁇ m was obtained.
  • Base material layer A urethane resin base material (XUS2098, manufactured by Sea Dam Co., Ltd.) was used to form a base material layer (C4-B) having a thickness of 150 ⁇ m.
  • Adhesive tape The obtained adhesive layer (C4-A) and substrate layer (C4-B) were bonded together with a hand roller to obtain a tape.
  • an addition type silicone elastomer (LR7665, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was applied on the base material layer (C4-B) of this tape with an applicator to form a syrup layer having a thickness of 150 ⁇ m. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C4).
  • Adhesive layer In the same manner as in Example 1, a 50 ⁇ m thick adhesive layer (C5-A) was obtained.
  • Base material layer A urethane resin base material (DUS451, manufactured by Sea Dam Co., Ltd.) was used to form a base material layer (C5-B) having a thickness of 150 ⁇ m.
  • Adhesive tape The obtained adhesive layer (C5-A) and substrate layer (C5-B) were bonded together with a hand roller to obtain a tape.
  • an addition-type silicone elastomer (TSE3032, manufactured by Momentive Co., Ltd.) was applied on the base material layer (C5-B) of this tape with an applicator to form a syrup layer having a thickness of 150 ⁇ m. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C5).
  • 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 capable of effectively preventing aquatic biofouling, the adhesive tape comprising an antifouling layer, a substrate layer, and an adhesive layer, in the stated order, wherein the adhesive tape for preventing aquatic biofouling has excellent close adhesion between the antifouling layer and the substrate layer. This adhesive tape for preventing aquatic biofouling comprises an antifouling layer, a substrate layer, and an adhesive layer, in the stated order, wherein the antifouling layer and/or the substrate layer comprise(s) a silane coupling agent and/or a silicone powder.

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)に水中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 is that underwater organisms adhere to underwater structures (such as ships, buoys, harbor facilities, offshore oilfield facilities, waterways for power plant cooling water, waterways for factory cooling water, water floating passages, etc.). The present invention relates to an aquatic organism adhesion prevention adhesive tape for preventing breeding.
 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、付着珪藻などの海洋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、付着した海洋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、付着した海洋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, where they come into contact with seawater, marine organisms such as barnacles, oysters, purple mussels, hydra, cell plastics, squirts, bryozoans, Aosa, Aonori, and attached diatoms grow and grow, increasing fluid resistance. It causes unfavorable conditions such as deterioration of equipment and machine performance such as deterioration of thermal conductivity and diffusion of attached marine organisms overseas. In addition, the work for removing the attached marine organisms requires a large amount of labor and enormous time, and suffers an economic loss.
 上記のような被害を防止するため、従来、防汚塗料が水中構造物に塗装されている。防汚塗料には、古くは有機スズ化合物や現在では亜酸化銅などの毒性防汚剤が含まれている。防汚塗料の毒性によって海洋生物の付着成長はほぼ抑制できるが、有機スズ化合物や亜酸化銅などの毒性防汚剤は人体や環境に少なからず悪影響を与えるため、長期的にみれば深刻な問題となる。また、防汚塗料を塗装後に乾燥させる際には、30重量%程度の有機溶剤(VOC)が揮発し、作業環境や周辺の環境に悪影響を与えている。スプレー式塗装では、VOCの大気中への排出の他に、塗料の10重量%~20重量%は風により周囲に飛散していると言われている。一方で、長年使用した防汚塗料を塗り替える際には、古くなった防汚塗料をサンドブラストや金属研磨機で剥離するが、その際に、有機スズ化合物や亜酸化銅などの毒性防汚剤を含んだ大量の塗膜片が周囲に飛散して作業者や環境に悪影響を与えると共に、剥離した防汚塗料は産業廃棄物として処理されるため、大きな問題となっている。 In order to prevent such damage, antifouling paint has been conventionally applied to underwater structures. Antifouling paints have long contained toxic antifouling agents such as organotin compounds and now cuprous oxide. The adhesion growth of marine organisms can be almost suppressed by the toxicity of antifouling paints, but toxic antifouling agents such as organotin compounds and cuprous oxide have a considerable adverse effect on the human body and the environment. It becomes. Further, when the antifouling paint is dried after being applied, about 30% by weight of the organic solvent (VOC) is volatilized, which adversely affects the work environment and the surrounding environment. In spray coating, in addition to discharging VOC into the atmosphere, it is said that 10% to 20% by weight of the paint is scattered around by the wind. On the other hand, when repainting antifouling paints that have been used for many years, old antifouling paints are peeled off with sandblasting or a metal polishing machine, but at that time, toxic antifouling agents such as organotin compounds and cuprous oxide are removed. A large amount of the coated film pieces are scattered around and adversely affect the operator and the environment, and the peeled antifouling paint is treated as industrial waste, which is a big problem.
 以上の様に、これまでの防汚塗料では、海洋生物に対する付着阻害効果はあるものの、人体や環境に対して大きな悪影響があり、多くの問題が解決されないまま現在に至っているのが現状である。 As described above, although antifouling paints so far have an adhesion inhibiting effect on marine organisms, they have a great adverse effect on the human body and the environment, and the current situation is that many problems have not been solved. .
 そこで、銅薄と粘着剤とをプライマーを介して貼り合わせた粘着テープが提案されている(特許文献1、2参照)。しかし、このような粘着テープにおいては、海洋生物の付着抑制を銅薄の銅成分によって実現させているため、環境への悪影響の可能性があるという問題がある。また、このような粘着テープは、FRP板に対するピール接着力が2.6kg/25mmまたは7.5kg/25mm(プライマー前処理後)と非常に大きく設計されており、使用後の粘着テープを貼り替える場合に粘着テープが人力で容易に剥がれるとは考えにくく、結局、削り取るなどの行為が必要なため、大きな労力が必要となる。また、銅は比重が8.94g/cmと重い物質であり、船舶などの移動構造物に使用することは、燃費を悪化させ経済的に好ましくない。 Then, the adhesive tape which bonded copper thin and the adhesive through the primer is proposed (refer patent documents 1 and 2). However, such an adhesive tape has a problem that there is a possibility of an adverse effect on the environment because adhesion of marine organisms is suppressed by a thin copper component. In addition, such an adhesive tape is designed to have a peel adhesive strength to the FRP plate of 2.6 kg / 25 mm or 7.5 kg / 25 mm (after primer pretreatment), and the adhesive tape after use is replaced. In this case, it is difficult to think that the adhesive tape is easily peeled off by human power, and after all, an action such as scraping is required, which requires a lot of labor. Moreover, copper is a heavy substance with a specific gravity of 8.94 g / cm 3, and its use in a moving structure such as a ship deteriorates fuel efficiency and is not economically preferable.
 また、シリコーンゴムと粘着剤の2層から成る防汚テープが提案されている(特許文献3参照)。しかし、防汚効果を担うシリコーンゴム層にはオイルなどの防汚剤が含まれておらず、シリコーンゴムそのものである。防汚剤が含まれていない場合は、短期的には海洋生物の付着はその撥水性によって抑制できるものの、長期間にはその防汚効果が持続できない。また、このような防汚テープは、シリコーンゴムと粘着剤の2層で構成されているため、強度的に非常に不安がある。一般的に、シリコーンゴムは破断点強度が極めて低いため、このような防汚テープを使用後に剥がす場合、テープ状態として剥がすことが困難であり現実的ではない。 Further, an antifouling tape composed of two layers of silicone rubber and an adhesive has been proposed (see Patent Document 3). However, the silicone rubber layer responsible for the antifouling effect does not contain an antifouling agent such as oil, and is a silicone rubber itself. When the antifouling agent is not included, the adhesion of marine organisms can be suppressed by its water repellency in the short term, but the antifouling effect cannot be sustained in the long term. In addition, since such an antifouling tape is composed of two layers of silicone rubber and an adhesive, there is a great concern about strength. In general, silicone rubber has a very low strength at break, and therefore, when such an antifouling tape is peeled off after use, it is difficult to peel off as a tape state, which is not practical.
 また、基材上に下塗り剤を介してシリコーンエラストマーを設け、基材の逆側には粘着層を設けたシート状テープが提案されている(特許文献4参照)。しかし、特許文献4には、水中で使用できる粘着剤組成に関する記述や接着力に関する記述などが全く無いため、水生生物付着防止粘着テープへの適用を考える上では現実性に乏しい。また、防汚テープを水中構造物に施工する際には、曲面や鋭角面に施工できるように柔軟性や伸び性の設計が必要であり、また、使用後に防汚テープを剥離する際には基材が途中で破壊しないような強度設計が必要であるが、特許文献4にはそのような記述が全く無いため、水生生物付着防止粘着テープへの適用を考える上では現実性に乏しい。 Further, a sheet-like tape has been proposed in which a silicone elastomer is provided on a base material via a primer and an adhesive layer is provided on the opposite side of the base material (see Patent Document 4). However, since there is no description regarding the adhesive composition that can be used in water and no description regarding adhesive strength, Patent Document 4 is not realistic in considering application to an aquatic organism adhesion prevention adhesive tape. In addition, when applying antifouling tape to underwater structures, it is necessary to design for flexibility and extensibility so that it can be applied to curved surfaces and acute angles, and when antifouling tape is peeled off after use Although strength design is required so that the base material does not break in the middle, Patent Document 4 does not have such description at all, and is not realistic in considering application to an aquatic organism adhesion prevention adhesive tape.
 さらに、特許文献4で提案されているような防汚テープにおいては、基材層上に防汚層を設けられているが、基材層と防汚層は要求される機能の相違に起因して物性が異なるため、互いの密着性が十分に確保できず、互いに剥がれやすいという問題がある。特に、このような防汚テープを水中構造物に施工する際には、基材層と防汚層との互いの剥がれやすさは顕著となる。 Further, in the antifouling tape as proposed in Patent Document 4, an antifouling layer is provided on the base material layer. However, the base material layer and the antifouling layer are caused by the difference in required functions. Since the physical properties are different, there is a problem that the mutual adhesion cannot be sufficiently ensured and is easily peeled off. In particular, when such an antifouling tape is applied to an underwater structure, the ease of peeling between the base material layer and the antifouling layer becomes remarkable.
特公昭63-62487号公報Japanese Examined Patent Publication No. 63-62487 特公平1-54397号公報Japanese Patent Publication No. 1-54397 特許第3000101号公報Japanese Patent No. 3000101 特開2002-69246号公報JP 2002-69246 A
 本発明の課題は、防汚層と基材層と粘着層をこの順に含む、水生生物の付着を効果的に防止できる粘着テープであって、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することにある。 An object of the present invention is an adhesive tape that can effectively prevent adhesion of aquatic organisms, including an antifouling layer, a base material layer, and an adhesive layer in this order, and has excellent adhesion between the antifouling layer and the base material layer. It is another object of the present invention to provide an aquatic organism adhesion preventing adhesive tape.
 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層をこの順に含む粘着テープであって、
 該防汚層および該基材層から選ばれる少なくとも1種が、シランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含む。
The aquatic organism adhesion preventing adhesive tape of the present invention is
An adhesive tape comprising an antifouling layer, a base material layer and an adhesive layer in this order,
At least one selected from the antifouling layer and the base material layer includes at least one selected from a silane coupling agent, silicone powder, and silica particles.
 好ましい実施形態においては、上記防汚層および上記基材層の合計に対する、上記シランカップリング剤、上記シリコーンパウダー、および前記シリカ粒子の合計の含有割合が、0.01重量%~100重量%である。 In a preferred embodiment, the total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the antifouling layer and the base material layer is 0.01 wt% to 100 wt%. is there.
 好ましい実施形態においては、上記基材層がエラストマー樹脂を含む。 In a preferred embodiment, the base material layer contains an elastomer resin.
 好ましい実施形態においては、上記エラストマー樹脂がポリウレタンアクリル樹脂およびポリウレタン樹脂から選ばれる少なくとも1種である。 In a preferred embodiment, the elastomer resin is at least one selected from a polyurethane acrylic resin and a polyurethane resin.
 好ましい実施形態においては、上記防汚層がシリコーン樹脂を含む。 In a preferred embodiment, the antifouling layer contains a silicone resin.
 本発明によれば、防汚層と基材層と粘着層をこの順に含む、水生生物の付着を効果的に防止できる粘着テープであって、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することができる。 According to the present invention, the adhesive tape includes the antifouling layer, the base material layer, and the adhesive layer in this order, and can effectively prevent attachment of aquatic organisms, and has excellent adhesion between the antifouling layer and the base material layer. In addition, an aquatic organism adhesion preventing adhesive tape can be provided.
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. 実施例1で得られた粘着テープ(1)の密着性試験結果の状態を示す写真図である。It is a photograph figure which shows the state of the adhesive test result of the adhesive tape (1) obtained in Example 1. FIG. 実施例1で得られた粘着テープ(1)の流水試験後の状態を示す写真図である。It is a photograph figure which shows the state after the running water test of the adhesive tape (1) obtained in Example 1. FIG. 比較例1で得られた粘着テープ(C1)の密着性試験結果の状態を示す写真図である。It is a photograph figure which shows the state of the adhesive test result of the adhesive tape (C1) obtained by the comparative example 1. FIG. 比較例1で得られた粘着テープ(C1)の流水試験後の状態を示す写真図である。It is a photograph figure which shows the state after the flowing water test of the adhesive tape (C1) obtained by the comparative example 1. FIG.
 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層をこの順に含む。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層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。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50μm~500μmである。 The aquatic organism adhesion preventing adhesive tape of the present invention comprises an antifouling layer, a base material layer and an adhesive layer in this order. The aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has any appropriate other layer as long as the antifouling layer, the base material layer, and the pressure-sensitive adhesive layer are included in this order, as long as the effects of the present invention are not impaired. May be. The thickness of the aquatic organism adhesion prevention adhesive tape of this invention is set to arbitrary appropriate thickness in the range which does not impair the effect of this invention by the thickness of each layer contained in it. The thickness of the aquatic organism adhesion preventing adhesive tape of the present invention is preferably 50 μm to 500 μm.
 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。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と粘着層4をこの順に含む。図1に示すように、防汚層2の表面や、粘着層4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. The aquatic organism adhesion prevention adhesive tape 100 of this invention contains the antifouling layer 2, the base material layer 3, and the adhesion layer 4 in this order. As shown in FIG. 1, a release film 1 may be provided on the surface of the antifouling layer 2 or the surface of the adhesive layer 4.
 防汚層および基材層から選ばれる少なくとも1種は、シランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含む。すなわち、(1)防汚層がシランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含み、基材層がシランカップリング剤、シリコーンパウダー、およびシリカ粒子のいずれも含まない場合であっても良いし、(2)防汚層がシランカップリング剤、シリコーンパウダー、シリカ粒子のいずれも含まず、基材層がシランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含む場合であっても良いし、(3)防汚層および基材層の両方がシランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含む場合であっても良い。 At least one selected from the antifouling layer and the base material layer includes at least one selected from a silane coupling agent, silicone powder, and silica particles. That is, (1) When the antifouling layer contains at least one selected from a silane coupling agent, silicone powder, and silica particles, and the substrate layer does not contain any of the silane coupling agent, silicone powder, and silica particles (2) The antifouling layer does not contain any of the silane coupling agent, silicone powder, and silica particles, and the base material layer is at least one selected from silane coupling agent, silicone powder, and silica particles. It may be a case containing seeds, or (3) both the antifouling layer and the base material layer may contain at least one selected from a silane coupling agent, silicone powder, and silica particles.
 防汚層および基材層から選ばれる少なくとも1種がシランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含むことにより、防汚層と基材層との高い密着性を発現することができる。防汚層と基材層との密着性が低いと、防汚効果を発揮する防汚層が、使用中の衝撃や物理的ダメージによって基材層から剥離してしまい、本来の防汚効果が持続できないおそれがある。 When at least one selected from the antifouling layer and the base material layer contains at least one selected from a silane coupling agent, silicone powder, and silica particles, high adhesion between the antifouling layer and the base material layer is exhibited. can do. If the adhesion between the antifouling layer and the base material layer is low, the antifouling layer that exerts the antifouling effect peels off from the base material layer due to impact or physical damage during use, and the original antifouling effect is obtained. May not be sustainable.
 防汚層と基材層の密着性は、防汚層がシリコーン樹脂を含む場合に特に顕著である。これは、シリコーン樹脂の特性である低表面エネルギーが原因である。本発明においては、防汚層がシリコーン樹脂を含む場合であっても、防汚層と基材層の高い密着性を発現することができる。 The adhesion between the antifouling layer and the base material layer is particularly remarkable when the antifouling layer contains a silicone resin. This is due to the low surface energy that is a characteristic of silicone resins. In this invention, even if it is a case where an antifouling layer contains a silicone resin, the high adhesiveness of an antifouling layer and a base material layer can be expressed.
 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。 Only one type of silane coupling agent may be used, or two or more types may be used.
 シランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニル基含有シランカップリング剤;2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン等のエポキシ基含有シランカップリング剤;p-スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤;3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン等のメタクリル基含有シランカップリング剤;3-アクリロキシプロピルトリメトキシシラン等のアクリル基含有シランカップリング剤;N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-(ビニルベンジル)-2-アミノエチル-3-アミノプロピルトリメトキシシランの塩酸塩等のアミノ基含有シランカップリング剤;3-ウレイドプロピルトリエトキシシラン等のウレイド基含有シランカップリング剤;3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン等のメルカプト基含有シランカップリング剤;ビス(トリエトキシシリルプロピル)テトラスルフィド等のスルフィド基含有シランカップリング剤;3-イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤;などが挙げられる。 Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane, etc. Styryl group-containing silane coupling agent: 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Methacrylic group-containing silane coupling agent such as silane; Acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N Amino group-containing silane coupling agents such as phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; 3-ureidopropyltriethoxysilane Silane coupling containing ureido groups such as A mercapto group-containing silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; a sulfide group-containing silane coupling agent such as bis (triethoxysilylpropyl) tetrasulfide; 3-isocyanatopropyltri And isocyanate group-containing silane coupling agents such as ethoxysilane.
 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。 Specific examples of commercially available silane coupling agents include KBM5103, KBM1003, KBM903, KBM403, and KBM802 manufactured by Shin-Etsu Chemical Co., Ltd.
 シリコーンパウダーは、1種のみであっても良いし、2種以上であっても良い。 Only one type of silicone powder may be used, or two or more types may be used.
 シリコーンパウダーの平均粒径は、好ましくは1nm~100μmであり、より好ましくは10nm~70μmであり、さらに好ましくは100nm~50μmであり、特に好ましくは500nm~20μmである。シリコーンパウダーの平均粒径が上記範囲内に収まることによって、防汚層と基材層との高い密着性をより効果的に発現することができる。 The average particle size of the silicone powder is preferably 1 nm to 100 μm, more preferably 10 nm to 70 μm, still more preferably 100 nm to 50 μm, and particularly preferably 500 nm to 20 μm. When the average particle diameter of the silicone powder is within the above range, high adhesion between the antifouling layer and the base material layer can be expressed more effectively.
 シリコーンパウダーとしては、例えば、直鎖状のジメチルポリシロキサンを架橋した構造を持つシリコーンゴム粒子や、シロキサン結合が三次元網目状に架橋した構造を持つポリオルガノシルセスキオキサン硬化物であるシリコーンレジン粒子や、シリコーンゴム粒子の表面をシリコーンレジンで被膜したシリコーン複合粒子などが挙げられる。 Examples of the silicone powder include silicone rubber particles having a structure in which linear dimethylpolysiloxane is crosslinked, and a silicone resin that is a cured product of polyorganosilsesquioxane having a structure in which siloxane bonds are crosslinked in a three-dimensional network. Examples include particles and silicone composite particles in which the surface of silicone rubber particles is coated with a silicone resin.
 市販されている具体的なシリコーンパウダーとしては、例えば、信越化学工業(株)製のシリコーン複合パウダー(KMP-600、KMP-601、KMP-602、KMP-605、X-52-7030など)、シリコーンゴムパウダー(KMP-597、KMP-598、KMP-594、X-52-875など)、シリコーンレジンパウダー(KMP-590、KMP-701、X-52-854、X-52-1621など)が挙げられる。 Specific examples of commercially available silicone powders include silicone composite powders (KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.) manufactured by Shin-Etsu Chemical Co., Ltd. Silicone rubber powder (KMP-597, KMP-598, KMP-594, X-52-875, etc.), silicone resin powder (KMP-590, KMP-701, X-52-854, X-52-1621, etc.) Can be mentioned.
 シリカ粒子は、1種のみであっても良いし、2種以上であっても良い。 The silica particles may be only one kind or two or more kinds.
 シリカ粒子の平均粒径は、好ましくは1nm~100μmであり、より好ましくは2nm~70μmであり、さらに好ましくは3nm~50μmであり、特に好ましくは5nm~30μmである。シリカ粒子の平均粒径が上記範囲内に収まることによって、防汚層と基材層との高い密着性をより効果的に発現することができる。 The average particle diameter of the silica particles is preferably 1 nm to 100 μm, more preferably 2 nm to 70 μm, still more preferably 3 nm to 50 μm, and particularly preferably 5 nm to 30 μm. When the average particle diameter of the silica particles falls within the above range, high adhesion between the antifouling layer and the base material layer can be expressed more effectively.
 シリカ粒子としては、例えば、二酸化ケイ素(SiO)の粒子もしくは二酸化ケイ素(SiO)によって構成された粒子が挙げられ、例えば、疎水性のシリカ粒子や親水性のシリカ粒子が挙げられる。シリカ粒子としては、例えば、表面が疎水処理された粒子や表面が親水処理された粒子も挙げられる。 Examples of the silica particles include silicon dioxide (SiO 2 ) particles or particles composed of silicon dioxide (SiO 2 ), and examples include hydrophobic silica particles and hydrophilic silica particles. Examples of the silica particles include particles whose surface has been subjected to a hydrophobic treatment and particles whose surface has been subjected to a hydrophilic treatment.
 市販されている具体的なシリカ粒子としては、例えば、アエロジルシリーズ(日本アエロジル(株)製)が用いられる。より具体的には、疎水性においては、アエロジルR8200(1次平均粒子径:12nm、ヘキサメチルジシラザン処理)、アエロジルR104(1次平均粒子径:12nm、オクタメチルシクロテトラシロキサン処理)、アエロジルR972(1次平均粒子径:16nm、ジメチルジクロロシラン処理)、アエロジルR974(1次平均粒子径:12nm、ジメチルジクロロシラン処理)、アエロジルR812(1次平均粒子径:7nm、ヘキサメチルジシラザン処理)などが挙げられ、親水性においては、アエロジル200(1次平均粒子径:12nm)、アエロジル300(1次平均粒子径:7nm)などが挙げられる。 Specific examples of commercially available silica particles include Aerosil series (produced by Nippon Aerosil Co., Ltd.). More specifically, in hydrophobicity, Aerosil R8200 (primary average particle size: 12 nm, hexamethyldisilazane treatment), Aerosil R104 (Primary average particle size: 12 nm, octamethylcyclotetrasiloxane treatment), Aerosil R972 (Primary average particle size: 16 nm, dimethyldichlorosilane treatment), Aerosil R974 (Primary average particle size: 12 nm, dimethyldichlorosilane treatment), Aerosil R812 (Primary average particle size: 7 nm, hexamethyldisilazane treatment), etc. Examples of hydrophilicity include Aerosil 200 (primary average particle size: 12 nm), Aerosil 300 (primary average particle size: 7 nm), and the like.
 防汚層および基材層の合計に対する、シランカップリング剤、シリコーンパウダー、およびシリカ粒子の合計の含有割合は、好ましくは0.01重量%~100重量%であり、より好ましくは0.5重量%~30重量%であり、さらに好ましくは0.1重量%~10重量%であり、特に好ましくは1重量%~5重量%である。上記含有割合が上記範囲内に収まることにより、防汚層と基材層との高い密着性をより効果的に発現することができる。上記含有割合が0.01重量%未満の場合、基材層と防汚層との間に十分な密着性が発現できないおそれがある。 The total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the antifouling layer and the base material layer is preferably 0.01% by weight to 100% by weight, and more preferably 0.5% by weight. % To 30% by weight, more preferably 0.1% to 10% by weight, and particularly preferably 1% to 5% by weight. When the said content rate is settled in the said range, the high adhesiveness of a pollution protection layer and a base material layer can be expressed more effectively. When the said content rate is less than 0.01 weight%, there exists a possibility that sufficient adhesiveness cannot be expressed between a base material layer and an antifouling layer.
 なお、防汚層および基材層の合計に対するシランカップリング剤の含有割合の上限は、好ましくは30重量%以下であり、さらに好ましくは10重量%以下であり、特に好ましくは5重量%以下である。防汚層および基材層の合計に対するシランカップリング剤の含有割合の上限が上記範囲内に収まることにより、シランカップリング剤が架橋点となって該シランカップリング剤を含む層が硬くなり過ぎることを抑制できる。 The upper limit of the content ratio of the silane coupling agent relative to the total of the antifouling layer and the base material layer is preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. is there. When the upper limit of the content ratio of the silane coupling agent with respect to the total of the antifouling layer and the base material layer is within the above range, the silane coupling agent becomes a crosslinking point and the layer containing the silane coupling agent becomes too hard. This can be suppressed.
 基材層には、防汚層との密着性をさらに向上させるために、プライマーをあらかじめ塗工しておいても良い。 In order to further improve the adhesion to the antifouling layer, a primer may be applied to the base material layer in advance.
 基材層の材料としては、本発明の効果を損なわない範囲で、任意の適切な材料を採用し得る。このような基材層の材料としては、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 material of the base material layer, any appropriate material can be adopted as long as the effects of the present invention are not impaired. Such a material for the base material layer 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.
 基材層は、好ましくは、エラストマー樹脂を含む。エラストマー樹脂としては、本発明の効果を損なわない範囲で任意の適切なエラストマー樹脂を採用し得る。このようなエラストマー樹脂としては、例えば、加硫ゴム、熱可塑性エラストマーなどが挙げられる。熱可塑性エラストマーとしては、例えば、スチレン系エラストマー、オレフィン系エラストマー、塩ビ系エラストマー、ウレタン系エラストマー、エステル系エラストマー、アミド系エラストマーなどが挙げられる。基材層中のエラストマー樹脂の含有割合は、好ましくは50重量%以上であり、より好ましくは60重量%~100重量%であり、さらに好ましくは70重量%~99重量%であり、特に好ましくは80重量%~98重量%であり、最も好ましくは90重量%~97重量%である。 The base material layer preferably contains an elastomer resin. As the elastomer resin, any appropriate elastomer resin can be adopted as long as the effects of the present invention are not impaired. Examples of such elastomer resins include vulcanized rubber and thermoplastic elastomer. Examples of the thermoplastic elastomer include styrene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like. The content ratio of the elastomer resin in the base material layer is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 99% by weight, particularly preferably. 80 to 98% by weight, most preferably 90 to 97% by weight.
 基材層中に含まれ得るエラストマー樹脂は、1種のみであっても良いし、2種以上であっても良い。基材層がエラストマー樹脂を含むことにより、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でき、貼着後の表面にしわや浮きなどの外観不良が生じ難い、水生生物付着防止粘着テープを提供することができる。 The elastomer resin that can be contained in the base material layer may be only one kind or two or more kinds. Since the base material layer contains an elastomer resin, it can be easily applied to parts other than flat surfaces such as curved surfaces and acute angles with good workability, and appearance defects such as wrinkles and floats are unlikely to occur on the surface after application. A bioadhesion-preventing adhesive tape can be provided.
 本発明において、基材層に含まれ得るエラストマー樹脂としては、好ましくは、ウレタン系エラストマーである。ウレタン系エラストマーとしては、好ましくは、ポリウレタンアクリル樹脂およびポリウレタン樹脂から選ばれる少なくとも1種である。ポリウレタン樹脂としては、例えば、カーボネート系ポリウレタン、エステル系ポリウレタン、エーテル系ポリウレタンなどが挙げられる。エラストマー樹脂としてウレタン系エラストマーを採用することにより、曲面や鋭角面など、平面以外の部位にも一層容易に作業性良く貼着でき、貼着後の表面にしわや浮きなどの外観不良が一層生じ難い、水生生物付着防止粘着テープを提供することができる。 In the present invention, the elastomer resin that can be included in the base material layer is preferably a urethane-based elastomer. The urethane elastomer is preferably at least one selected from polyurethane acrylic resins and polyurethane resins. Examples of the polyurethane resin include carbonate-based polyurethane, ester-based polyurethane, and ether-based polyurethane. By using urethane elastomer as the elastomer resin, it can be easily applied to areas other than flat surfaces, such as curved surfaces and acute angles, with better workability, resulting in further appearance defects such as wrinkles and floats on the surface after application. It is difficult to provide an adhesive tape for preventing adhesion of aquatic organisms.
 ポリウレタンアクリル樹脂は、アクリル成分とウレタン成分を有する。ポリウレタンアクリル樹脂は、より具体的には、(メタ)アクリル系ポリマーとウレタンポリマーを含有する複合ポリマーである。ポリウレタンアクリル樹脂中における(メタ)アクリル系ポリマーとウレタンポリマーとの重量比率は、好ましくは、(メタ)アクリル系ポリマー/ウレタンポリマー=1/99~80/20である。ポリウレタンアクリル樹脂中における(メタ)アクリル系ポリマーとウレタンポリマーとの重量比率が上記範囲内に収まることにより、前駆体混合物の粘度の上昇を抑制できて作業性を良好に維持できるとともに、ポリウレタンアクリル樹脂に優れた柔軟性や優れた強度を付与できる。(メタ)アクリル系ポリマー/ウレタンポリマーが1/99未満では、前駆体混合物の粘度が高くなり、作業性が悪化するおそれがあり、80/20を超えると、ポリウレタンアクリル樹脂としての柔軟性や強度が得られないおそれがある。 Polyurethane acrylic resin has an acrylic component and a urethane component. More specifically, the polyurethane acrylic resin is a composite polymer containing a (meth) acrylic polymer and a urethane polymer. The weight ratio of (meth) acrylic polymer to urethane polymer in the polyurethane acrylic resin is preferably (meth) acrylic polymer / urethane polymer = 1/99 to 80/20. When the weight ratio of the (meth) acrylic polymer to the urethane polymer in the polyurethane acrylic resin is within the above range, the increase in the viscosity of the precursor mixture can be suppressed and workability can be maintained well, and the polyurethane acrylic resin can be maintained. Can provide excellent flexibility and excellent strength. If the (meth) acrylic polymer / urethane polymer is less than 1/99, the viscosity of the precursor mixture may be high and workability may be deteriorated. If it exceeds 80/20, flexibility and strength as a polyurethane acrylic resin may be obtained. May not be obtained.
 なお、本発明において「(メタ)アクリル」とは、アクリルおよび/またはメタクリルを意味する。 In the present invention, “(meth) acryl” means acrylic and / or methacrylic.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーは、(メタ)アクリル酸系モノマーと単官能(メタ)アクリル系モノマーを含むモノマー成分を用いて得られるポリマーであることが好ましい。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーは、特に、ホモポリマーのガラス転移温度(Tg)が0℃以上の単官能(メタ)アクリル系モノマーを含むモノマー成分を用いて得られるポリマーであることが好ましい。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーは、上記ホモポリマーのガラス転移温度(Tg)が0℃以上の単官能(メタ)アクリル系モノマーに加えて、さらに、ホモポリマーのガラス転移温度(Tg)が0℃未満の単官能(メタ)アクリル系モノマーを含むモノマー成分を用いて得られるポリマーであることがより好ましい。 The (meth) acrylic polymer in the polyurethane acrylic resin is preferably a polymer obtained using a monomer component containing a (meth) acrylic acid monomer and a monofunctional (meth) acrylic monomer. The (meth) acrylic polymer in the polyurethane acrylic resin is a polymer obtained by using a monomer component including a monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of a homopolymer of 0 ° C. or higher. Is preferred. The (meth) acrylic polymer in the polyurethane acrylic resin has a glass transition temperature (Tg) of the homopolymer in addition to the monofunctional (meth) acrylic monomer having a glass transition temperature (Tg) of the homopolymer of 0 ° C. or higher. ) Is more preferably a polymer obtained by using a monomer component containing a monofunctional (meth) acrylic monomer having a temperature of less than 0 ° C.
 (メタ)アクリル酸系モノマーとは、カルボキシル基を有する(メタ)アクリル系モノマーである。(メタ)アクリル酸系モノマーとしては、例えば、アクリル酸、メタクリル酸、マレイン酸、クロトン酸等が挙げられる。本発明の効果を一層発現できる点で、(メタ)アクリル酸系モノマーとしては、好ましくは、アクリル酸が挙げられる。 (Meth) acrylic acid monomer is a (meth) acrylic monomer having a carboxyl group. Examples of the (meth) acrylic acid monomer include acrylic acid, methacrylic acid, maleic acid, crotonic acid and the like. A preferable example of the (meth) acrylic acid-based monomer is acrylic acid in that the effects of the present invention can be further exhibited.
 ポリウレタンアクリル樹脂の原料となるモノマー成分中の(メタ)アクリル酸系モノマーの含有割合は、好ましくは1重量%~15重量%であり、より好ましくは2重量%~10重量%である。ポリウレタンアクリル樹脂の原料となるモノマー成分中の(メタ)アクリル酸系モノマーの含有割合が上記範囲内に収まることにより、ポリウレタンアクリル樹脂の合成反応を円滑に進ませることができ、ポリウレタンアクリル樹脂に十分な強度と耐水性を付与できる。ポリウレタンアクリル樹脂の原料となるモノマー成分中の(メタ)アクリル酸系モノマーの含有割合が1重量%未満では、ポリウレタンアクリル樹脂の合成反応に長時間を要するおそれや、ポリウレタンアクリル樹脂が十分な強度を有しないおそれがある。ポリウレタンアクリル樹脂の原料となるモノマー成分中の(メタ)アクリル酸系モノマーの含有割合が15重量%を超える場合には、ポリウレタンアクリル樹脂の吸水率が大きくなり、耐水性に問題が生じるおそれがある。(メタ)アクリル酸系モノマーは、ポリウレタンアクリル樹脂中のウレタン成分とアクリル成分との相溶性に大きく影響するものである。 The content ratio of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin is preferably 1% by weight to 15% by weight, and more preferably 2% by weight to 10% by weight. When the content ratio of the (meth) acrylic acid monomer in the monomer component that is the raw material of the polyurethane acrylic resin falls within the above range, the synthesis reaction of the polyurethane acrylic resin can be smoothly advanced, and it is sufficient for the polyurethane acrylic resin. High strength and water resistance. If the content of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin is less than 1% by weight, the polyurethane acrylic resin may take a long time for the synthesis reaction, and the polyurethane acrylic resin has sufficient strength. May not have. When the content ratio of the (meth) acrylic acid monomer in the monomer component used as the raw material for the polyurethane acrylic resin exceeds 15% by weight, the water absorption of the polyurethane acrylic resin increases, which may cause a problem in water resistance. . The (meth) acrylic acid monomer greatly affects the compatibility between the urethane component and the acrylic component in the polyurethane acrylic resin.
 Tgが0℃以上の単官能(メタ)アクリル系モノマーとしては、例えば、アクリロイルモルホリン、イソボルニルアクリレート、ジシクロペンタニルアクリレート、t-ブチルアクリレート、シクロヘキシルアクリレート、ラウリルアクリレート等が挙げられる。Tgが0℃以上の単官能(メタ)アクリル系モノマーは、1種のみであっても良いし、2種以上であっても良い。 Examples of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher include acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and lauryl acrylate. The monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher may be only one type or two or more types.
 Tgが0℃以上の単官能(メタ)アクリル系モノマーとしては、本発明の効果を一層発現できる点で、好ましくは、アクリロイルモルホリン、イソボルニルアクリレート、ジシクロペンタニルアクリレートから選ばれる少なくとも1種であり、より好ましくは、イソボルニルアクリレートが挙げられる。 The monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or higher is preferably at least one selected from acryloylmorpholine, isobornyl acrylate, and dicyclopentanyl acrylate in that the effects of the present invention can be further exhibited. More preferably, isobornyl acrylate is used.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃以上の単官能(メタ)アクリル系モノマーの含有割合は、好ましくは20重量%~99重量%であり、より好ましくは30重量%~98重量%である。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃以上の単官能(メタ)アクリル系モノマーの含有割合が上記範囲内に収まることにより、ポリウレタンアクリル樹脂に十分な強度を付与できるとともに、ポリウレタンアクリル樹脂の剛性の上がり過ぎを抑制できる。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃以上の単官能(メタ)アクリル系モノマーの含有割合が、20重量%未満では、ポリウレタンアクリル樹脂が十分な強度を有しないおそれがある。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃以上の単官能(メタ)アクリル系モノマーの含有割合が、99重量%を超えると、ポリウレタンアクリル樹脂の剛性が上がりすぎて脆くなるおそれがある。 The content ratio of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is preferably 20% by weight to 99% by weight, More preferably, it is 30 to 98% by weight. It is sufficient for polyurethane acrylic resin because the content ratio of monofunctional (meth) acrylic monomer having Tg of 0 ° C. or more in the monomer component constituting (meth) acrylic polymer in polyurethane acrylic resin is within the above range. In addition to imparting high strength, it is possible to suppress an excessive increase in rigidity of the polyurethane acrylic resin. When the content ratio of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is less than 20% by weight, the polyurethane acrylic resin is sufficient. May not have strength. When the content of the monofunctional (meth) acrylic monomer having a Tg of 0 ° C. or more in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin exceeds 99% by weight, the rigidity of the polyurethane acrylic resin is increased. May rise and become brittle.
 Tgが0℃未満の単官能(メタ)アクリル系モノマーとしては、例えば、アクリル酸n-ブチル、アクリル酸2-エチルヘキシル、アクリル酸イソオクチル、アクリル酸イソブチル、2-メトキシエチルアクリレート、テトラヒドロフルオロフリルアクリレート、フェノキシエチルアクリレート、エトキシエチルアクリレート、3-メトキシブチルアクリレート等が挙げられる。Tgが0℃未満の単官能(メタ)アクリル系モノマーは、1種のみであっても良いし、2種以上であっても良い。 Examples of monofunctional (meth) acrylic monomers having a Tg of less than 0 ° C. include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofluorofuryl acrylate, Examples include phenoxyethyl acrylate, ethoxyethyl acrylate, and 3-methoxybutyl acrylate. The monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. may be only one type or two or more types.
 Tgが0℃未満の単官能(メタ)アクリル系モノマーとしては、本発明の効果を一層発現できる点で、好ましくは、アクリル酸n-ブチルが挙げられる。 The monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. is preferably n-butyl acrylate, from the viewpoint that the effects of the present invention can be further exhibited.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃未満の単官能(メタ)アクリル系モノマーの含有割合は、好ましくは50重量%以下であり、より好ましくは45重量%以下である。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃未満の単官能(メタ)アクリル系モノマーの含有割合が上記範囲内に収まることにより、ポリウレタンアクリル樹脂に十分な強度を付与できる。ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーを構成するモノマー成分中の、Tgが0℃未満の単官能(メタ)アクリル系モノマーの含有割合が、50重量%を超える場合には、ポリウレタンアクリル樹脂が十分な強度を有しないおそれがある。 The content ratio of the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin is preferably 50% by weight or less, more preferably 45% by weight or less. It is sufficient for polyurethane acrylic resin because the content ratio of monofunctional (meth) acrylic monomer with Tg of less than 0 ° C in the monomer component constituting (meth) acrylic polymer in polyurethane acrylic resin is within the above range. Can provide a high strength. When the content of the monofunctional (meth) acrylic monomer having a Tg of less than 0 ° C. in the monomer component constituting the (meth) acrylic polymer in the polyurethane acrylic resin exceeds 50% by weight, the polyurethane acrylic resin May not have sufficient strength.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーの原料モノマーに含まれる、(メタ)アクリル酸系モノマーや単官能(メタ)アクリル系モノマーなどの(メタ)アクリル系モノマーは、ウレタンとの相溶性、放射線等の光硬化時の重合性や、得られる高分子量体の特性を考慮して、種類、組合せ、使用量等が適宜決定される。 (Meth) acrylic monomers such as (meth) acrylic acid monomers and monofunctional (meth) acrylic monomers contained in the raw material monomers for (meth) acrylic polymers in polyurethane acrylic resins are compatible with urethane, In consideration of the polymerizability at the time of photocuring such as radiation and the characteristics of the high molecular weight substance to be obtained, the type, combination, amount used and the like are appropriately determined.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーの原料モノマーには、本発明の効果を損なわない範囲で、任意の適切な他のモノマーが含まれていても良い。このような他のモノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、スチレン、アクリルアミド、メタクリルアミド、マレイン酸のモノまたはジエステル、その誘導体、N-メチロールアクリルアミド、グリシジルアクリレート、グリシジルメタクリレート、N,N-ジメチルアミノエチルアクリレート、N,N-ジメチルアミノプロピルメタクリルアミド、2-ヒドロキシプロピルアクリレート、N,N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド、イミドアクリレート、N-ビニルピロリドン、オリゴエステルアクリレート、ε-カプロラクトンアクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、メトキシ化シクロドデカトリエンアクリレート、メトキシエチルアクリレート等が挙げられる。他のモノマーは、1種のみであっても良いし、2種以上であっても良い。他のモノマーの種類や使用量は、目的に応じて、適宜選択し得る。 The raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin may contain any appropriate other monomer as long as the effects of the present invention are not impaired. Examples of such other monomers include vinyl acetate, vinyl propionate, styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, derivatives thereof, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, N, N— Dimethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylamide, 2-hydroxypropyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, imide acrylate, N-vinylpyrrolidone, oligoester acrylate, ε-caprolactone Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxylated cyclododecatriene acrylate, methoxy Chill acrylate, and the like. One other monomer may be used, or two or more other monomers may be used. The type and amount of other monomers can be appropriately selected according to the purpose.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーの原料モノマーには、本発明の効果を損なわない範囲で、他の多官能モノマーが含まれていても良い。このような多官能モノマーとしては、例えば、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート等が挙げられる。本発明の効果を一層発現できる点で、このような多官能モノマーとしては、好ましくは、トリメチロールプロパントリ(メタ)アクリレートが挙げられる。 The raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin may contain other polyfunctional monomers as long as the effects of the present invention are not impaired. Examples of such polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate and the like. As such a polyfunctional monomer, trimethylolpropane tri (meth) acrylate is preferably used in that the effects of the present invention can be further exhibited.
 ポリウレタンアクリル樹脂中の(メタ)アクリル系ポリマーの原料モノマーに他の多官能モノマーが含まれている場合、その含有割合は、原料モノマー中の(メタ)アクリル系モノマーに対して、好ましくは1重量%~20重量%である。上記含有割合が1重量%以上であれば、ポリウレタンアクリル樹脂の凝集力を十分に高く維持することができ、上記含有割合が20重量%以下であれば、ポリウレタンアクリル樹脂の弾性率が高くなりすぎることがなく、被着体表面の凹凸に良好に追従することができる。 When other polyfunctional monomers are contained in the raw material monomer of the (meth) acrylic polymer in the polyurethane acrylic resin, the content is preferably 1 weight with respect to the (meth) acrylic monomer in the raw material monomer. % To 20% by weight. If the content ratio is 1% by weight or more, the cohesive force of the polyurethane acrylic resin can be maintained sufficiently high, and if the content ratio is 20% by weight or less, the elastic modulus of the polyurethane acrylic resin becomes too high. It is possible to follow the irregularities on the surface of the adherend satisfactorily.
 ポリウレタンアクリル樹脂中のウレタンポリマーは、好ましくは、ジオールとジイソシアネートとを反応させて得られる。ジオールの水酸基とイソシアネートとの反応には、触媒を用いても良い。 The urethane polymer in the polyurethane acrylic resin is preferably obtained by reacting a diol with a diisocyanate. A catalyst may be used for the reaction between the hydroxyl group of the diol and the isocyanate.
 低分子量のジオールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール等の2価のアルコールが挙げられる。 Examples of the low molecular weight diol include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol.
 高分子量のジオールとしては、例えば、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を付加重合して得られるポリエーテルポリオール;上述の2価のアルコール、1,4-ブタンジオール、1,6-ヘキサンジオール等のアルコールとアジピン酸、アゼライン酸、セバチン酸等の2価の塩基酸との重縮合物からなるポリエステルポリオール;アクリルポリオール;カーボネートポリオール;エポキシポリオール;カプロラクトンポリオール;等が挙げられる。本発明の効果を一層発現できる点で、高分子量のジオールとしては、これらの中でも、好ましくは、ポリオキシテトラメチレングリコール(PTMG)、ポリアルキレンカーボネートジオール(PCD)が挙げられる。 Examples of the high molecular weight diol include polyether polyols obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, and the like; divalent alcohols described above, 1,4-butanediol, 1,6-hexanediol, and the like Examples include polyester polyols composed of polycondensates of alcohols with divalent basic acids such as adipic acid, azelaic acid, and sebacic acid; acrylic polyols; carbonate polyols; epoxy polyols; caprolactone polyols; Among these, as the high molecular weight diol, polyoxytetramethylene glycol (PTMG) and polyalkylene carbonate diol (PCD) are preferable because the effects of the present invention can be further exhibited.
 アクリルポリオールとしては、水酸基を有するモノマーの共重合体の他、水酸基含有物と(メタ)アクリル系モノマーとの共重合体等が挙げられる。 Examples of the acrylic polyol include a copolymer of a hydroxyl group-containing monomer and a (meth) acrylic monomer, in addition to a copolymer of a monomer having a hydroxyl group.
 エポキシポリオールとしては、アミン変性エポキシ樹脂等が挙げられる。 Examples of the epoxy polyol include amine-modified epoxy resins.
 ポリウレタンアクリル樹脂中のウレタンポリマーを製造する際には、上記ジオールを、(メタ)アクリル系モノマーへの溶解性、イソシアネートとの反応性等を考慮して、1種のみを用いても良いし、2種以上を用いても良い。ポリウレタンアクリル樹脂の強度を向上させる場合には、低分子量ジオールによるウレタンハードセグメント量を増加させると効果的である。ポリウレタンアクリル樹脂の伸びを重視する場合には、分子量の大きなジオールを単独で使用すると効果的である。ポリエーテルポリオールは、一般的に、安価で耐水性が良好である。ポリエステルポリオールは、ポリウレタンアクリル樹脂の強度を向上させることができる。 When producing the urethane polymer in the polyurethane acrylic resin, only one kind of the diol may be used in consideration of solubility in the (meth) acrylic monomer, reactivity with isocyanate, etc. Two or more kinds may be used. In order to improve the strength of the polyurethane acrylic resin, it is effective to increase the amount of the urethane hard segment by the low molecular weight diol. When importance is attached to the elongation of the polyurethane acrylic resin, it is effective to use a diol having a large molecular weight alone. Polyether polyols are generally inexpensive and have good water resistance. The polyester polyol can improve the strength of the polyurethane acrylic resin.
 ジイソシアネートとしては、芳香族、脂肪族、脂環族のジイソシアネート;これらのジイソシアネートの二量体、三量体;ポリフェニルメタンジイソシアネート;などが挙げられる。ジイソシアネートは、1種のみであっても良いし、2種以上であっても良い。 Examples of the diisocyanate include aromatic, aliphatic, and alicyclic diisocyanates; dimers and trimers of these diisocyanates; polyphenylmethane diisocyanate; and the like. Only one diisocyanate may be used, or two or more diisocyanates may be used.
 芳香族、脂肪族、脂環族のジイソシアネートとしては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート(HXDI)、イソホロンジイソシアネート、水添ジフェニルメタンジイソシアネート、1,5-ナフチレンジイソシアネート、1,3-フェニレンジイソシアネート、1,4-フェニレンジイソシアネート、ブタン-1,4-ジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、シクロヘキサン-1,4-ジイソシアネート、ジシクロヘキシルメタン-4,4-ジイソシアネート、1,3-ビス(イソシアネートメチル)シクロヘキサン、メチルシクロヘキサンジイソシアネート、m-テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate (HXDI), isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanate methyl) Cyclohexane, methylcyclohexane diisocyanate, m- tetramethylxylylene diisocyanate, and the like.
 芳香族、脂肪族、脂環族のジイソシアネートの三量体としては、例えば、イソシアヌレート型、ビューレット型、アロファネート型等が挙げられる。 Examples of the trimer of aromatic, aliphatic and alicyclic diisocyanates include isocyanurate type, burette type and allophanate type.
 本発明の効果を一層発現できる点で、ジイソシアネートとしては、好ましくは、ヘキサメチレンジイソシアネート(HDI)、水添トリレンジイソシアネート(HTDI)、水添4,4-ジフェニルメタンジイソシアネート(HMDI)、イソホロンジイソシアネート(IPDI)、水添キシレンジイソシアネート(HXDI)が挙げられる。 The diisocyanate is preferably hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4-diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI) in that the effects of the present invention can be further exhibited. ), Hydrogenated xylene diisocyanate (HXDI).
 ウレタンポリマーを形成するためのジオール成分とジイソシアネート成分の使用割合は、NCO/OH(当量比)が、好ましくは1.1~2.0であり、より好ましくは1.15~1.35である。NCO/OH(当量比)が上記範囲内に収まることにより、ポリウレタンアクリル樹脂に優れた強度、十分な伸び、十分な柔軟性を付与できる。NCO/OH(当量比)が1.1未満の場合、ポリウレタンアクリル樹脂の強度が低下するおそれがある。NCO/OH(当量比)が2.0を超えると、ポリウレタンアクリル樹脂の伸びと柔軟性を十分に確保することができないおそれがある。 The ratio of the diol component and diisocyanate component used to form the urethane polymer is preferably NCO / OH (equivalent ratio) of 1.1 to 2.0, more preferably 1.15 to 1.35. . When NCO / OH (equivalent ratio) falls within the above range, the polyurethane acrylic resin can be provided with excellent strength, sufficient elongation, and sufficient flexibility. When NCO / OH (equivalent ratio) is less than 1.1, the strength of the polyurethane acrylic resin may be reduced. If NCO / OH (equivalent ratio) exceeds 2.0, the polyurethane acrylic resin may not be sufficiently stretched and flexible.
 ウレタンポリマーに対して水酸基含有(メタ)アクリル系モノマーを添加しても良い。ウレタンポリマーに対して水酸基含有(メタ)アクリル系モノマーを添加することにより、ウレタンプレポリマーの分子末端に(メタ)アクリロイル基を導入することができ、(メタ)アクリル系モノマーとの共重合性が付与され、ウレタン成分とアクリル成分との相溶性が高まり、破断強度などのS-S特性の向上を図ることができる。本発明の効果を一層発現できる点で、水酸基含有(メタ)アクリル系モノマーの使用量は、ウレタンポリマーに対して、好ましくは0.1重量%~10重量%であり、より好ましくは1重量%~5重量%である。 A hydroxyl group-containing (meth) acrylic monomer may be added to the urethane polymer. By adding a hydroxyl group-containing (meth) acrylic monomer to the urethane polymer, a (meth) acryloyl group can be introduced at the molecular terminal of the urethane prepolymer, and the copolymerization with the (meth) acrylic monomer is possible. As a result, compatibility between the urethane component and the acrylic component is increased, and SS characteristics such as breaking strength can be improved. The amount of the hydroxyl group-containing (meth) acrylic monomer used is preferably 0.1% by weight to 10% by weight and more preferably 1% by weight with respect to the urethane polymer in that the effect of the present invention can be further exhibited. ~ 5% by weight.
 水酸基含有(メタ)アクリル系モノマーとしては、例えば、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート、ヒドロキシへキシル(メタ)アクリレート等が挙げられる。 Examples of the hydroxyl group-containing (meth) acrylic monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and the like.
 ポリウレタンアクリル樹脂は、好ましくは、(メタ)アクリル系ポリマーとウレタンポリマーとがグラフト構造や架橋構造により相互に結合したヘテロジニアスネットワーク構造を有する。(メタ)アクリル系ポリマーとウレタンポリマーとが、それぞれ独自に架橋構造をとるIPN構造(相互侵入高分子網目層)や、(メタ)アクリル系ポリマーとウレタンポリマーの一方が架橋構造を有し、他の一方がリニア構造の高分子鎖を有していて該架橋構造の中に侵入しているようなsemi-IPN構造の場合は、ポリウレタンアクリル樹脂の伸張時の応力が発現しにくい場合がある。 The polyurethane acrylic resin preferably has a heterogeneous network structure in which a (meth) acrylic polymer and a urethane polymer are bonded to each other by a graft structure or a crosslinked structure. IPN structure (interpenetrating polymer network layer) in which (meth) acrylic polymer and urethane polymer each independently have a crosslinked structure, or one of (meth) acrylic polymer and urethane polymer has a crosslinked structure. In the case of a semi-IPN structure in which one of these has a linear polymer chain and penetrates into the cross-linked structure, the stress at the time of expansion of the polyurethane acrylic resin may be difficult to develop.
 基材層に含まれ得るエラストマー樹脂がポリウレタンアクリル樹脂である場合、該基材層は、例えば、(メタ)アクリル系モノマーを希釈剤として、この(メタ)アクリル系モノマー中でジオールとジイソシアネートとの反応を行ってウレタンポリマーを形成し、(メタ)アクリル系モノマーとウレタンポリマーとを主成分として含む混合物を基材(必要に応じて剥離処理されている)等の上に塗布し、光重合開始剤の種類等に応じて、α線、β線、γ線、中性子線、電子線等の電離性放射線や紫外線等の放射線、可視光等を照射して硬化させ、その後、基材等を剥離除去することにより、基材層を形成することができる。あるいは、基材等を剥離除去せずに、基材等の上に基材層が積層された形態で得ることもできる。 When the elastomer resin that can be included in the base material layer is a polyurethane acrylic resin, for example, the base material layer includes a (meth) acrylic monomer as a diluent and a diol and a diisocyanate in the (meth) acrylic monomer. Reaction is performed to form a urethane polymer, and a mixture containing (meth) acrylic monomer and urethane polymer as main components is applied onto a substrate (exfoliated if necessary), and photopolymerization is started. Depending on the type of agent, etc., it is cured by irradiation with ionizing radiation such as α-rays, β-rays, γ-rays, neutrons, electron beams, ultraviolet rays, visible light, etc., and then the substrate is peeled off. By removing, a base material layer can be formed. Or it can also obtain in the form by which the base material layer was laminated | stacked on the base material etc., without peeling and removing a base material etc.
 基材層に含まれ得るエラストマー樹脂がポリウレタンアクリル樹脂である場合、該基材層は、より具体的には、例えば、ジオールを(メタ)アクリル系モノマーに溶解させた後、ジイソシアネート等を添加してジオールと反応させて粘度調整を行い、これを支持体等に、あるいは、必要に応じて支持体等の剥離処理面に塗工した後、低圧水銀ランプ等を用いて硬化させることによって得ることができる。この方法では、(メタ)アクリル系モノマーをウレタン合成中に一度に添加してもよいし、何回かに分割して添加してもよい。また、ジイソシアネートを(メタ)アクリル系モノマーに溶解させた後、ジオールを反応させてもよい。この方法によれば、分子量が限定されるということはなく、高分子量のポリウレタンを生成することもできるので、最終的に得られるウレタンの分子量を任意の大きさに設計することができる。酸素による重合阻害を避けるために、支持体等上に塗布した混合物の上に、剥離処理したシート(セパレーター等)をのせて酸素を遮断してもよいし、不活性ガスを充填した容器内に基材を入れて、酸素濃度を下げてもよい。 When the elastomer resin that can be contained in the base material layer is a polyurethane acrylic resin, more specifically, the base material layer is prepared by, for example, adding a diisocyanate or the like after dissolving a diol in a (meth) acrylic monomer. The viscosity is adjusted by reacting with a diol, and this is applied to a support or the like, or, if necessary, applied to a release-treated surface of a support or the like, and then cured by using a low-pressure mercury lamp or the like. Can do. In this method, the (meth) acrylic monomer may be added all at once during the urethane synthesis or may be added in several divided portions. Further, after the diisocyanate is dissolved in the (meth) acrylic monomer, the diol may be reacted. According to this method, the molecular weight is not limited and a high molecular weight polyurethane can be produced, so that the molecular weight of the finally obtained urethane can be designed to an arbitrary size. In order to avoid polymerization inhibition due to oxygen, a release-treated sheet (separator, etc.) may be placed on the mixture coated on a support or the like to block oxygen, or in a container filled with an inert gas. A base material may be added to lower the oxygen concentration.
 放射線等の種類や照射に使用されるランプの種類等は適宜選択することができる。このようなランプとしては、例えば、蛍光ケミカルランプ、ブラックライト、殺菌ランプ等の低圧ランプ;メタルハライドランプ、高圧水銀ランプ等の高圧ランプ;等が挙げられる。 ¡The type of radiation and the type of lamp used for irradiation can be selected as appropriate. Examples of such lamps include low-pressure lamps such as fluorescent chemical lamps, black lights, and sterilization lamps; high-pressure lamps such as metal halide lamps and high-pressure mercury lamps.
 紫外線などの照射量は、基材層の特性に応じて、任意に設定することができる。一般的には、紫外線の照射量は、好ましくは100mJ/cm~5000mJ/cmであり、より好ましくは1000mJ/cm~4000mJ/cmであり、さらに好ましくは2000mJ/cm~3000mJ/cmである。紫外線の照射量を上記範囲内に収めることにより、劣化させることなく十分な重合率が得られる。紫外線の照射量が100mJ/cmより少ないと、十分な重合率が得られないおそれがあり、5000mJ/cmより大きいと、劣化の原因となるおそれがある。紫外線等を照射する際の温度は、目的に応じて、任意の適切な温度に設定することができる。紫外線等を照射する際の温度が高すぎると、重合熱による停止反応が起こり易くなり、特性低下の原因となりやすい。このため、紫外線等を照射する際の温度は、好ましくは70℃以下であり、より好ましくは50℃以下であり、さらに好ましくは30℃以下である。 Irradiation amounts such as ultraviolet rays can be arbitrarily set according to the characteristics of the base material layer. Generally, the dose of ultraviolet rays is preferably 100mJ / cm 2 ~ 5000mJ / cm 2, more preferably 1000mJ / cm 2 ~ 4000mJ / cm 2, more preferably 2000mJ / cm 2 ~ 3000mJ / cm 2 . By keeping the amount of ultraviolet irradiation within the above range, a sufficient polymerization rate can be obtained without deterioration. When the dose of ultraviolet ray is less than 100 mJ / cm 2, it might not provide a sufficient rate of polymerization, and is larger than 5000 mJ / cm 2, which may cause deterioration. The temperature at the time of irradiation with ultraviolet rays or the like can be set to any appropriate temperature depending on the purpose. If the temperature at the time of irradiation with ultraviolet rays or the like is too high, a stop reaction due to polymerization heat tends to occur, which tends to cause deterioration of characteristics. For this reason, the temperature at the time of irradiating with ultraviolet rays or the like is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 30 ° C. or lower.
 ポリウレタンアクリル樹脂を調製するにあたり、少なくともウレタンポリマーを含む混合物(例えば、(メタ)アクリル系モノマーとウレタンポリマーとを主成分とする混合物)には、好ましくは光重合開始剤が含まれる。 In preparing a polyurethane acrylic resin, a mixture containing at least a urethane polymer (for example, a mixture containing (meth) acrylic monomer and urethane polymer as main components) preferably contains a photopolymerization initiator.
 光重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインエーテル;アニソールメチルエーテル等の置換ベンゾインエーテル;2,2-ジエトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン等の置換アセトフェノン、1-ヒドロキシシクロヘキシル フェニル ケトン、2-メチル-2-ヒドロキシプロピオフェノン等の置換アルファーケトール;2-ナフタレンスルフォニルクロライド等の芳香族スルフォニルクロライド;1-フェニル-1,1-プロパンジオン-2-(o-エトキシカルボニル)-オキシム等の光活性オキシム;などが挙げられる。 Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether; substituted benzoin ethers such as anisole methyl ether; 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone. Substituted alpha-ketols such as substituted acetophenone, 1-hydroxycyclohexyl, phenyl ketone, 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; 1-phenyl-1,1-propanedione-2 And photoactive oximes such as-(o-ethoxycarbonyl) -oxime.
 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、紫外線吸収剤を含むことが好ましい。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。基材層が紫外線吸収剤を含んでいない場合、野外での使用において太陽光によって基材が劣化しやすくなり、当初の基材強度を維持することが難しくなるおそれがある。そして、基材が劣化してしまうと、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、基材層が頻繁に切断してしまい、作業効率が著しく悪くなるおそれがある。 The base material layer preferably contains an ultraviolet absorber. The weather resistance of the aquatic organism adhesion prevention adhesive tape of this invention improves because a base material layer contains a ultraviolet absorber. When the base material layer does not contain an ultraviolet absorber, the base material is likely to be deteriorated by sunlight during outdoor use, and it may be difficult to maintain the initial base material strength. When the base material deteriorates, the base material layer is frequently cut when the used aquatic organism adhesion preventing adhesive tape of the present invention is peeled off from the adherend, and the work efficiency may be significantly deteriorated. There is.
 基材層の厚みは、目的に応じて、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収めることにより、本発明の水生生物付着防止粘着テープは、防汚層と基材層との密着性に優れ、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でき、貼着後の表面にしわや浮きなどの外観不良が生じ難い。 Any appropriate thickness can be adopted as the thickness of the base material layer according to the purpose. The thickness of the base material layer is preferably 1 μm to 1000 μm, more preferably 10 μm to 800 μm, and still more preferably 20 μm to 500 μm. By keeping the thickness of the base material layer within the above range, the aquatic organism adhesion-preventing pressure-sensitive adhesive tape of the present invention has excellent adhesion between the antifouling layer and the base material layer, and is applied to sites other than flat surfaces such as curved surfaces and acute angle surfaces. Can be easily applied with good workability, and appearance defects such as wrinkles and floats are unlikely to occur on the surface after application.
 防汚層としては、防汚効果を発現できる層であれば、任意の適切な層を採用し得る。 As the antifouling layer, any appropriate layer can be adopted as long as it can exhibit an antifouling effect.
 防汚層としては、好ましくは、防汚塗料を用いることなく防汚効果を発現できる層であり、例えば、防汚効果を有する任意の適切な樹脂を材料とする。このような樹脂としては、好ましくは、シリコーン樹脂が挙げられる。 The antifouling layer is preferably a layer that can exhibit an antifouling effect without using an antifouling paint. For example, any suitable resin having an antifouling effect is used as a material. As such a resin, Preferably, a silicone resin is mentioned.
 防汚層がシリコーン樹脂を含む場合、防汚層中のシリコーン樹脂の含有割合は、防汚剤などの他の成分の含有割合によって、任意の適切な含有割合を採用し得る。防汚層がシリコーン樹脂を含む場合、防汚層中のシリコーン樹脂の含有割合は、好ましくは30重量%~98重量%、より好ましくは40重量%~97重量%、さらに好ましくは45重量%~96重量%、特に好ましくは50重量%~95重量%である。防汚層中のシリコーン樹脂の含有割合が上記範囲内に収まることにより、防汚層の防汚効果が十分に発現できるとともに、防汚層の機械的特性が十分に発現できる。防汚層中のシリコーン樹脂の含有割合が30重量%未満の場合、防汚層の機械的特性が低下するおそれがある。防汚層中のシリコーン樹脂の含有割合が98重量%を超える場合、防汚層の防汚効果が十分に発現できないおそれがある。 When the antifouling layer contains a silicone resin, any appropriate content can be adopted as the content of the silicone resin in the antifouling layer depending on the content of other components such as an antifouling agent. When the antifouling layer contains a silicone resin, the content of the silicone resin in the antifouling layer is preferably 30% by weight to 98% by weight, more preferably 40% by weight to 97% by weight, and still more preferably 45% by weight to It is 96% by weight, particularly preferably 50% to 95% by weight. When the content ratio of the silicone resin in the antifouling layer is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the mechanical characteristics of the antifouling layer can be sufficiently expressed. When the content ratio of the silicone resin in the antifouling layer is less than 30% by weight, the mechanical properties of the antifouling layer may be deteriorated. When the content ratio of the silicone resin in the antifouling layer exceeds 98% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited.
 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。本発明においては、これらの中でも、1液型の室温硬化性(RTV)樹脂、2液型の室温硬化性(RTV)樹脂が好ましい。1液型のRTV樹脂としては、例えば、信越化学工業(株)製のKE-3475、KE-45S、KE-445、KE-44、KE-441、KE-3497、KE-4896などが挙げられる。2液型のRTV樹脂としては、例えば、信越化学工業(株)製のKE106、KE-66、KE-1031、KE-1800などが挙げられる。 As the silicone resin, any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. Only one type of silicone resin may be used, or two or more types may be used. Such a silicone resin may be a silicone resin that is liquid at normal temperature, or may be a silicone resin that is solid at normal temperature. Such a silicone resin may be a condensation type silicone resin or an addition type silicone resin. Such a silicone resin may be a one-component silicone resin that is dried alone, or a two-component silicone resin that contains a curing agent. In the present invention, among these, a one-component room temperature curable (RTV) resin and a two-component room temperature curable (RTV) resin are preferable. Examples of the one-component RTV resin include KE-3475, KE-45S, KE-445, KE-44, KE-441, KE-3497, and KE-4896 manufactured by Shin-Etsu Chemical Co., Ltd. . Examples of the two-component RTV resin include KE106, KE-66, KE-1031, and KE-1800 manufactured by Shin-Etsu Chemical Co., Ltd.
 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、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、防汚剤を含んでいても良い。防汚剤は、1種のみであっても良いし、2種以上であっても良い。防汚層が防汚剤を含む場合、該防汚剤は、マトリックスであるシリコーン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、さらに非加水分解性であることから、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。 The antifouling layer may contain an antifouling agent. Only one type of antifouling agent may be used, or two or more types may be used. When the antifouling layer contains an antifouling agent, the antifouling agent migrates to the surface of the silicone resin as a matrix and covers the surface with an antifouling substance, thereby suppressing the adhesion of aquatic organisms to the silicone resin surface. Furthermore, since it is non-hydrolyzable, it can exhibit the effect of maintaining a high antifouling effect for a long period of time.
 防汚層が防汚剤を含む場合、防汚層中、シリコーン樹脂に対する防汚剤の含有割合は、好ましくは2重量%以上、より好ましくは2重量%~200重量%、さらに好ましくは3重量%~150重量%、特に好ましくは4重量%~120重量%、最も好ましくは5重量%~100重量%である。シリコーン樹脂に対する防汚剤の含有割合が上記範囲内に収まることにより、防汚層の防汚効果が十分に発現できるとともに、防汚層の外観特性や機械的特性が十分に発現できる。シリコーン樹脂に対する防汚剤の含有割合が2重量%未満の場合、防汚層の防汚効果が十分に発現できないおそれがある。シリコーン樹脂に対する防汚剤の含有割合が200重量%を超える場合、最終成形品や被膜の外観が不良となるおそれがあり、また、防汚層の強度が低下して防汚性を持続できなくなるおそれがある。 When the antifouling layer contains an antifouling agent, the content of the antifouling agent with respect to the silicone resin in the antifouling layer is preferably 2% by weight or more, more preferably 2% by weight to 200% by weight, and even more preferably 3% by weight. % To 150% by weight, particularly preferably 4% to 120% by weight, most preferably 5% to 100% by weight. When the content ratio of the antifouling agent to the silicone resin is within the above range, the antifouling effect of the antifouling layer can be sufficiently exhibited, and the appearance characteristics and mechanical characteristics of the antifouling layer can be sufficiently expressed. When the content ratio of the antifouling agent to the silicone resin is less than 2% by weight, the antifouling effect of the antifouling layer may not be sufficiently exhibited. When the content of the antifouling agent relative to the silicone resin exceeds 200% by weight, the appearance of the final molded product or the film may be deteriorated, and the antifouling layer strength is lowered and the antifouling property cannot be maintained. There is a fear.
 防汚剤としては、本発明の効果を損なわない範囲で、任意の適切な防汚剤を採用し得る。このような防汚剤としては、例えば、シリコーンオイル、流動パラフィン、界面活性剤、ワックス、ペトロラタム、動物脂類、脂肪酸などが挙げられる。本発明においては、防汚剤としては、好ましくは、シリコーンオイル、流動パラフィン、界面活性剤から選ばれる少なくとも1種である。 As the antifouling agent, any appropriate antifouling agent can be adopted as long as the effects of the present invention are not impaired. Examples of such an antifouling agent include silicone oil, liquid paraffin, surfactant, wax, petrolatum, animal fats, fatty acids and the like. In the present invention, the antifouling agent is preferably at least one selected from silicone oil, liquid paraffin, and surfactant.
 シリコーンオイルとしては、シリコーン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、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。このようなシリコーンオイルとしては、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。 The silicone oil is preferably one that does not have reactivity with the silicone resin or self-condensation. As such a silicone oil, any appropriate silicone oil can be adopted as long as the effects of the present invention are not impaired. Such a silicone oil is preferably incompatible with the organopolysiloxane contained in the silicone resin to some extent, and is represented by, for example, the general formula (I) in that the antifouling effect can be maintained over a long period of time. Silicone oil is preferred.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
 一般式(I)中、R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、R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。 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.
 一般式(I)中のR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R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。 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、より好ましくは1000~10000である。 The silicone oil represented by the general formula (I) has a number average molecular weight of preferably 180 to 20000, more preferably 1000 to 10,000.
 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、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R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、RおよびR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.
 界面活性剤としては、例えば、アニオン系界面活性剤、カチオン系界面活性剤、ノニ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 cationic surfactant, and a nonionic surfactant.
 防汚剤として、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)、生物忌避剤を用いても良い。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 antifouling agents, diatomaceous adhesion inhibitors, agricultural chemicals, pharmaceuticals (such as medetomidine), enzyme activity inhibitors (such as alkylphenols and alkylresorcinol), and biological repellents may be used. By using these antifouling agents, the adhesion preventing effect of aquatic organisms such as diatoms and barnacles is further improved.
 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。 The antifouling layer may contain any appropriate other additive as long as the effects of the present invention are not impaired.
 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。防汚層の厚みが上記範囲内に収まることにより、防汚効果が十分に長く有効に働くとともに、ハンドリング性に優れ、テープのつなぎ目部分の凹凸が小さく、汚れが付きにくい。防汚層の厚みが5μmより薄いと、防汚効果が有効に働く期間が短くなり、実用的ではなくなるおそれがある。防汚層の厚みが500μmより厚いと、本発明の水生生物付着防止粘着テープが分厚くなって重量が大きくなるため、ハンドリング性が悪くなり、テープのつなぎ目部分の凹凸が大きくなり、汚れが付きやすいおそれがある。 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. When the thickness of the antifouling layer is within the above range, the antifouling effect is effective for a sufficiently long time, and the handling property is excellent. When the thickness of the antifouling layer is less than 5 μm, the period during which the antifouling effect is effective is shortened and may not be practical. If the antifouling layer is thicker than 500 μm, the aquatic organism adhesion-preventing adhesive tape of the present invention becomes thick and increases in weight, resulting in poor handling, large irregularities at the joints of the tape, and dirt. There is a fear.
 粘着層としては、本発明の効果を損なわない範囲で、任意の適切な粘着層を採用し得る。このような粘着層の材料としては、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。粘着層の材料は、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 adhesive layer, any appropriate adhesive layer can be adopted as long as the effects of the present invention are not impaired. Examples of the material for such an adhesive layer include acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (vinyl acetate polymers, etc.) adhesives, and curable acrylic resin adhesives. Agents, silicone resin adhesives, and the like. The material of the adhesive layer may be only one type or two or more types.
 粘着層の厚みは、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。粘着層の厚みは、好ましくは10μm以上である。粘着層の厚みが上記範囲内に収まることにより、被着体の形状に十分に追従でき、接着面積を十分に確保でき、十分な粘着力が発現できる。粘着層の厚みが10μmより薄いと、被着体の形状に十分に追従できなくなり、接着面積が減少してしまい、十分な粘着力が発現できないおそれがある。粘着層の厚みの上限は、取扱性の観点から、好ましくは300μm以下である。 As the thickness of the adhesive layer, any appropriate thickness can be adopted depending on the application and use environment of the aquatic organism adhesion preventing adhesive tape of the present invention. The thickness of the adhesive layer is preferably 10 μm or more. When the thickness of the pressure-sensitive adhesive layer is within the above range, the shape of the adherend can be sufficiently followed, the adhesion area can be sufficiently secured, and sufficient adhesive force can be expressed. When the thickness of the pressure-sensitive adhesive layer is less than 10 μm, it is impossible to sufficiently follow the shape of the adherend, the adhesion area is reduced, and there is a possibility that sufficient pressure-sensitive adhesive force cannot be expressed. The upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 300 μm or less from the viewpoint of handleability.
 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、別途準備した基材層と粘着層を貼付した後に防汚層形成材料を基材層上に塗布して防汚層を形成する方法、基材層の一方の面に粘着層形成材料を塗布して粘着層を形成し、基材層のもう一方の面に防汚層形成材料を塗布して防汚層を形成する方法、基材層形成材料と粘着層形成材料を共押出しして基材層/粘着層の積層体を形成させた後に防汚層形成材料を基材層上に塗布して防汚層を形成する方法、などが挙げられる。 The aquatic organism adhesion preventing adhesive tape of the present invention can be produced by any appropriate method. Examples of such a method include, for example, a method of forming an antifouling layer by applying an antifouling layer forming material on the base material layer after pasting a separately prepared base material layer and an adhesive layer, and one of the base material layers. A method of forming an adhesive layer by applying an adhesive layer forming material on the surface and forming an antifouling layer by applying an antifouling layer forming material to the other surface of the base material layer, the base layer forming material and the adhesive layer For example, a method of forming the antifouling layer by applying the antifouling layer forming material on the base material layer after co-extrusion of the forming material to form a base material layer / adhesive layer laminate.
 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。 Examples of the method for applying the antifouling layer forming material on the base material layer include spraying, brushing, roller, curtain flow, roll, dip and the like. The antifouling layer-forming material is applied onto the base material layer by these methods, and the antifouling layer is formed, for example, by drying at a temperature from room temperature to 250 ° C. (preferably from room temperature to 180 ° C.). can do.
 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.
<密着性試験>
 評価対象の粘着テープを2cm×6cmのサイズにカットし、防汚層にカッターで切り込みを入れ、長尺方向に延伸させ、防汚層が基材層から剥がれるか否かを評価した。
<Adhesion test>
The pressure-sensitive adhesive tape to be evaluated was cut into a size of 2 cm × 6 cm, cut into the antifouling layer with a cutter, and stretched in the longitudinal direction to evaluate whether the antifouling layer was peeled off from the base material layer.
<流水試験>
 流水試験機((株)豊中製作所製)を用い、2cm×6cmのサイズにカットした評価対象の粘着テープを回転円板に設置し、水中において、10ノット(knot)相当で1週間回転させ、流水によって防汚層が基材層から剥がれるか否かを評価した。
<Running water test>
Using a running water tester (manufactured by Toyonaka Seisakusho Co., Ltd.), the adhesive tape to be evaluated, cut to a size of 2 cm × 6 cm, was placed on a rotating disk, and rotated in water for one week at an equivalent of 10 knots. It was evaluated whether the antifouling layer was peeled off from the base material layer by running water.
〔実施例1〕
(粘着層)
 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):90重量部、アクリル酸(AA):10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、架橋剤として1,6-ヘキサンジオールジアクリレート(HDDA):0.08重量部を添加し、これをセパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み50μm)の表面にアプリケーターにて塗布し、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/cm、積算照射量:2000mJ/cm)することにより、厚み50μmの粘着層(1-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、3-アクリロキシプロピルトリメトキシシラン(KBM-5103、信越化学工業(株)製):1重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(1-B)を得た。
(粘着テープ)
 得られた粘着層(1-A)と基材層(1-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(1-B)上に、シリコーンエラストマー(バイオクリンDK、中国塗料(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(1)を作成した。
 粘着テープ(1)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
 また、粘着テープ(1)の密着性試験結果の状態を示す写真図を図2に示し、粘着テープ(1)の流水試験後の状態を示す写真図を図3に示した。
[Example 1]
(Adhesive layer)
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 2-ethylhexyl acrylate (2EHA, manufactured by Toagosei Co., Ltd.) as a (meth) acrylic monomer: 90 parts by weight, acrylic acid (AA ): 10 parts by weight, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by BASF) as a photopolymerization initiator: 0.1 parts by weight are added and dispersed. Then, UV irradiation was performed from above in a nitrogen stream while stirring to convert a part of the monomer into a polymer to adjust the viscosity so that it could be applied to obtain a (meth) acrylic monomer mixture. To this (meth) acrylic monomer mixture, 1,6-hexanediol diacrylate (HDDA): 0.08 part by weight is added as a crosslinking agent, and this is added to a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.). , 50 μm thick) with an applicator, and a cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., 38 μm thick) is bonded with a hand roller, and ultraviolet rays are emitted from an ultraviolet lamp (BL type). Irradiation (ultraviolet light illuminance: 3.4 mW / cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) gave an adhesive layer (1-A) having a thickness of 50 μm.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight, trimethylolpropane triacrylate ( TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator: 0.25 parts by weight, UV absorber (product) The name “TINUVIN123” (manufactured by BASF): 1.25 parts by weight and antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight were added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (1-B).
(Adhesive tape)
The obtained adhesive layer (1-A) and substrate layer (1-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (1-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (1).
The structure of the adhesive tape (1) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state of the adhesive test result of an adhesive tape (1) was shown in FIG. 2, and the photograph figure which shows the state after the flowing water test of an adhesive tape (1) was shown in FIG.
〔実施例2〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(2-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):80重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):20重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):2重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、3-アクリロキシプロピルトリメトキシシラン(KBM-5103、信越化学工業(株)製):1重量部、アクリル酸(AA):1重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(2-B)を得た。
(粘着テープ)
 得られた粘着層(2-A)と基材層(2-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(2-B)上に、シリコーンエラストマー(バイオクリンDK、中国塗料(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(2)を作成した。
 粘着テープ(2)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
[Example 2]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (2-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 80 parts by weight, n -Butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 20 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) 68.4 parts by weight, dibutyltin dilaurate (DBTL): 2 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25.5 parts while stirring. A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight, acrylic acid (AA): 1 part by weight, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as photopolymerization initiator: 0 .25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight A syrup was obtained.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (2-B).
(Adhesive tape)
The obtained adhesive layer (2-A) and substrate layer (2-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (2-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (2).
The structure of the adhesive tape (2) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例3〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(3-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、3-アクリロキシプロピルトリメトキシシラン(KBM-5103、信越化学工業(株)製):5重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(3-B)を得た。
(粘着テープ)
 得られた粘着層(3-A)と基材層(3-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(3-B)上に、シリコーンエラストマー(バイオクリンDK、中国塗料(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(3)を作成した。
 粘着テープ(3)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 3
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (3-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 5 parts by weight, trimethylolpropane triacrylate ( TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator: 0.25 parts by weight, UV absorber (product) The name “TINUVIN123” (manufactured by BASF): 1.25 parts by weight and antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight were added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (3-B).
(Adhesive tape)
The obtained adhesive layer (3-A) and substrate layer (3-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (3-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (3).
The configuration of the adhesive tape (3) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例4〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(4-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、シリコーンパウダー(KMP600、信越化学工業(株)製):5重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(4-B)を得た。
(粘着テープ)
 得られた粘着層(4-A)と基材層(4-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(4-B)上に、縮合型シリコーンエラストマー(KE445、信越化学(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)を100:50で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(4)を作成した。
 粘着テープ(4)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 4
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (4-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, silicone powder (KMP600, manufactured by Shin-Etsu Chemical Co., Ltd.): 5 parts by weight, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, light Diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a polymerization initiator: 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF) : 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 part by weight was added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (4-B).
(Adhesive tape)
The obtained adhesive layer (4-A) and base material layer (4-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (4-B) of this tape, a condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) were added 100: 50. The mixed solution mixed in was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (4).
The configuration of the adhesive tape (4) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例5〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(5-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、3-アクリロキシプロピルトリメトキシシラン(KBM-5103、信越化学工業(株)製):5重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(5-B)を得た。
(粘着テープ)
 得られた粘着層(5-A)と基材層(5-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(5-B)上に、付加型シリコーンエラストマー(LR7665、旭化成ワッカーシリコーン(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)を100:50で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(5)を作成した。
 粘着テープ(5)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 5
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (5-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 5 parts by weight, trimethylolpropane triacrylate ( TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator: 0.25 parts by weight, UV absorber (product) The name “TINUVIN123” (manufactured by BASF): 1.25 parts by weight and antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight were added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (5-B).
(Adhesive tape)
The obtained adhesive layer (5-A) and base material layer (5-B) were bonded together with a hand roller to obtain a tape. Further, on the base material layer (5-B) of this tape, an addition-type silicone elastomer (LR7665, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) are 100: The mixed solution mixed at 50 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (5).
The configuration of the adhesive tape (5) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例6〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(6-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(6-B)を得た。
(粘着テープ)
 得られた粘着層(6-A)と基材層(6-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(6-B)上に、縮合型シリコーンエラストマー(KE445、信越化学工業(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシリカ粒子(アエロジルR974、日本アエロジル(株)製)を100:50:1で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(6)を作成した。
 粘着テープ(6)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 6
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (6-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, BASF) Product): A syrup was obtained by adding 0.6 parts by weight.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (6-B).
(Adhesive tape)
The obtained adhesive layer (6-A) and substrate layer (6-B) were bonded together with a hand roller to obtain a tape. And on the base material layer (6-B) of this tape, condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and silica particles A mixed solution obtained by mixing (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.) at a ratio of 100: 50: 1 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (6).
The configuration of the adhesive tape (6) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例7〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(7-A)を得た。
(基材層)
 ウレタン樹脂基材(XUS2098、シーダム(株)製)を用い、厚み150μmの基材層(7-B)とした。
(粘着テープ)
 得られた粘着層(7-A)と基材層(7-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(7-B)上に、縮合型シリコーンエラストマー(KE445、信越化学工業(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシリカ粒子(アエロジルR974、日本アエロジル(株)製)を100:50:1で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(7)を作成した。
 粘着テープ(7)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 7
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (7-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin substrate (XUS2098, manufactured by Seadam Co., Ltd.) was used to form a substrate layer (7-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (7-A) and substrate layer (7-B) were bonded together with a hand roller to obtain a tape. And on the base material layer (7-B) of this tape, a condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and silica particles A mixed solution obtained by mixing (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.) at a ratio of 100: 50: 1 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (7).
The configuration of the adhesive tape (7) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例8〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(8-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(8-B)を得た。
(粘着テープ)
 得られた粘着層(8-A)と基材層(8-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(8-B)上に、付加型シリコーンエラストマー(LR7665、旭化成ワッカーシリコーン(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシリコーンパウダー(KMP600、信越化学工業(株)製)を100:50:10で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(8)を作成した。
 粘着テープ(8)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 8
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (8-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, BASF) Product): A syrup was obtained by adding 0.6 parts by weight.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (8-B).
(Adhesive tape)
The obtained adhesive layer (8-A) and substrate layer (8-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (8-B) of this tape, addition type silicone elastomer (LR7665, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and silicone powder (KMP600, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed at 100: 50: 10 with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (8).
The structure of the adhesive tape (8) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例9〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(9-A)を得た。
(基材層)
 ウレタン樹脂基材(DUS451、シーダム(株)製)を用い、厚み150μmの基材層(9-B)とした。
(粘着テープ)
 得られた粘着層(9-A)と基材層(9-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(9-B)上に、付加型シリコーンエラストマー(LR3033/70、旭化成ワッカーシリコーン(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシリカ粒子(アエロジルR974、日本アエロジル(株)製)を100:50:1で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(9)を作成した。
 粘着テープ(9)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 9
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (9-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin base material (DUS451, manufactured by Seadam Co., Ltd.) was used to form a base material layer (9-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (9-A) and substrate layer (9-B) were bonded together with a hand roller to obtain a tape. And on the base material layer (9-B) of this tape, an addition type silicone elastomer (LR3033 / 70, manufactured by Asahi Kasei Wacker Silicone) and silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) A mixed solution in which silica particles (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.) were mixed at a ratio of 100: 50: 1 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (9).
The configuration of the adhesive tape (9) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例10〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(10-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、シリカ粒子(アエロジルR974、日本アエロジル(株)製):2.5重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(10-B)を得た。
(粘着テープ)
 得られた粘着層(10-A)と基材層(10-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(10-B)上に、縮合型シリコーンエラストマー(KE445、信越化学工業(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシリカ粒子(アエロジルR974、日本アエロジル(株)製)を100:50:1で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(10)を作成した。
 粘着テープ(10)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 10
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (10-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
In the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, silica particles (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.): 2.5 parts by weight, trimethylolpropane triacrylate (TMPTA): 5 parts by weight Diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, BASF) Product: 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 part by weight was added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (10-B).
(Adhesive tape)
The obtained adhesive layer (10-A) and substrate layer (10-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (10-B) of this tape, a condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and silica particles A mixed solution obtained by mixing (Aerosil R974, manufactured by Nippon Aerosil Co., Ltd.) at a ratio of 100: 50: 1 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (10).
The structure of the adhesive tape (10) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例11〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(11-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、3-アクリロキシプロピルトリメトキシシラン(KBM-5103、信越化学工業(株)製):5重量部、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(11-B)を得た。
(粘着テープ)
 得られた粘着層(11-A)と基材層(11-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(11-B)上に、縮合型シリコーンエラストマー(KE445、信越化学工業(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシランカップリング剤(KBM403、信越化学工業(株)製)を100:50:5で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(11)を作成した。
 粘着テープ(11)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 11
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (11-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the obtained acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.): 5 parts by weight, trimethylolpropane triacrylate ( TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator: 0.25 parts by weight, UV absorber (product) The name “TINUVIN123” (manufactured by BASF): 1.25 parts by weight and antioxidant (trade name “TINUVIN400”, manufactured by BASF): 0.6 parts by weight were added to obtain a syrup.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (11-B).
(Adhesive tape)
The obtained adhesive layer (11-A) and substrate layer (11-B) were bonded together with a hand roller to obtain a tape. On the base material layer (11-B) of this tape, a condensation type silicone elastomer (KE445, manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silane cup A mixed solution in which a ring agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed at 100: 50: 5 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (11).
The structure of the adhesive tape (11) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例12〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(12-A)を得た。
(基材層)
 ウレタン樹脂基材(DUS451、シーダム(株)製)を用い、厚み150μmの基材層(12-B)とした。
(粘着テープ)
 得られた粘着層(12-A)と基材層(12-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(12-B)上に、付加型シリコーンエラストマー(LR7665、旭化成ワッカーシリコーン(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシランカップリング剤(KBM5103、信越化学工業(株)製)を100:50:5で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(12)を作成した。
 粘着テープ(12)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 12
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (12-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin base material (DUS451, manufactured by Sea Dam Co., Ltd.) was used to form a base material layer (12-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (12-A) and substrate layer (12-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (12-B) of this tape, an addition type silicone elastomer (LR7665, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silane cup A mixed solution in which a ring agent (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed at 100: 50: 5 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (12).
The configuration of the adhesive tape (12) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例13〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(13-A)を得た。
(基材層)
 ウレタン樹脂基材(DUS451、シーダム(株)製)を用い、厚み150μmの基材層(13-B)とした。
(粘着テープ)
 得られた粘着層(13-A)と基材層(13-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(9-B)上に、付加型シリコーンエラストマー(TSE3032、モメンティブ(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシランカップリング剤(KBM5103、信越化学工業(株)製)を100:50:5で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(13)を作成した。
 粘着テープ(13)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 13
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (13-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin base material (DUS451, manufactured by Seadam Co., Ltd.) was used to form a base material layer (13-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (13-A) and substrate layer (13-B) were bonded together with a hand roller to obtain a tape. On the base material layer (9-B) of this tape, an addition type silicone elastomer (TSE3032, manufactured by Momentive Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silane coupling agent A mixed solution in which KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed at 100: 50: 5 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (13).
The structure of the adhesive tape (13) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔実施例14〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(14-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):71重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):10重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):0.01重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):9.15重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上にカバーセパレータ(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/cm、積算照射量:2000mJ/cm)し、基材層(14-B)を得た。
(粘着テープ)
 得られた粘着層(14-A)と基材層(14-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(14-B)上に、付加型シリコーンエラストマー(TSE3032、モメンティブ(株)製)とシリコーンオイル(KF96-100cs、信越化学工業(株)製)とシランカップリング剤(KBM5103、信越化学工業(株)製)を100:50:5で混合した混合液をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(14)を作成した。
 粘着テープ(14)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
Example 14
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (14-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 71 parts by weight, n -Butyl acrylate (BA, manufactured by Toagosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 10 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) Manufactured): 68.4 parts by weight, dibutyltin dilaurate (DBTL): 0.01 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25. 5 parts by weight were dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 9.15 parts by weight was added and reacted at 65 ° C. for 1 hour, so that acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, BASF) Product): A syrup was obtained by adding 0.6 parts by weight.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is bonded onto this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (14-B).
(Adhesive tape)
The obtained adhesive layer (14-A) and substrate layer (14-B) were bonded together with a hand roller to obtain a tape. Then, on the base material layer (14-B) of this tape, an addition type silicone elastomer (TSE3032, manufactured by Momentive Co., Ltd.), silicone oil (KF96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and a silane coupling agent. A mixed solution in which KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed at 100: 50: 5 was applied with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (14).
The configuration of the adhesive tape (14) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔比較例1〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(C1-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):80重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):20重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):2重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(C1-B)を得た。
(粘着テープ)
 得られた粘着層(C1-A)と基材層(C1-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(C1-B)上に、シリコーンエラストマー(バイオクリンDK、中国塗料(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(C1)を作成した。
 粘着テープ(C1)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
 また、粘着テープ(C1)の密着性試験結果の状態を示す写真図を図4に示し、粘着テープ(C1)の流水試験後の状態を示す写真図を図5に示した。
[Comparative Example 1]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (C1-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 80 parts by weight, n -Butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 20 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) 68.4 parts by weight, dibutyltin dilaurate (DBTL): 2 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25.5 parts while stirring. A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, BASF) Product): A syrup was obtained by adding 0.6 parts by weight.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (C1-B).
(Adhesive tape)
The obtained adhesive layer (C1-A) and substrate layer (C1-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (C1-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C1).
The configuration of the adhesive tape (C1) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
Moreover, the photograph figure which shows the state of the adhesive test result of an adhesive tape (C1) was shown in FIG. 4, and the photograph figure which shows the state after the flowing water test of an adhesive tape (C1) was shown in FIG.
〔比較例2〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(C2-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):80重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):20重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):2重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(C2-B)を得た。
(粘着テープ)
 得られた粘着層(C2-A)と基材層(C2-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(C2-B)上に、シリコーンエラストマー(バイオクリンDK、中国塗料(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(C2)を作成した。
 粘着テープ(C2)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
[Comparative Example 2]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (C2-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 80 parts by weight, n -Butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 20 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) 68.4 parts by weight, dibutyltin dilaurate (DBTL): 2 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25.5 parts while stirring. A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, BASF) Product): A syrup was obtained by adding 0.6 parts by weight.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (C2-B).
(Adhesive tape)
The obtained adhesive layer (C2-A) and substrate layer (C2-B) were bonded together with a hand roller to obtain a tape. Then, a silicone elastomer (Bioclin DK, manufactured by China Paint Co., Ltd.) was applied on the base material layer (C2-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C2).
The structure of the adhesive tape (C2) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔比較例3〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(C3-A)を得た。
(基材層)
 冷却管、温度計、および攪拌装置を備えた反応容器に、(メタ)アクリル系モノマーとして、イソボルニルアクリレート(商品名「IBXA」、大阪有機化学工業(株)製):80重量部、n-ブチルアクリレート(BA、東亜合成(株)製):19重量部、アクリル酸(AA):20重量部、ポリオールとして数平均分子量650のポリ(オキシテトラメチレン)グリコール(PTMG650、三菱化学(株)製):68.4重量部、触媒としてジラウリン酸ジブチルスズ(DBTL):2重量部を投入し、攪拌しながら、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン(株)製):25.5重量部を滴下し、65℃で5時間反応させ、ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(商品名「アクリックス HEA」、東亜合成(株)製):6.1重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物を得た。
 得られたアクリロイル基末端ウレタンポリマー-(メタ)アクリル系モノマー混合物に、トリメチロールプロパントリアクリレート(TMPTA):5重量部、光重合開始剤としてジフェニル(2,4,6,-トリメトキシベンゾイル)ホスフィンオキシド(商品名「ルシリンTPO」、BASF製):0.25重量部、紫外線吸収剤(商品名「TINUVIN123」、BASF製):1.25重量部、酸化防止剤(商品名「TINUVIN400」、BASF製):0.6重量部を添加することにより、シロップを得た。
 セパレーター(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)の表面に、得られたシロップをアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。このシロップ層上に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/cm、積算照射量:2000mJ/cm)し、基材層(C3-B)を得た。
(粘着テープ)
 得られた粘着層(C3-A)と基材層(C3-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(C3-B)上に、付加型シリコーンエラストマー(LR7665、旭化成ワッカーシリコーン(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(C3)を作成した。
 粘着テープ(C3)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
[Comparative Example 3]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (C3-A) having a thickness of 50 μm was obtained.
(Base material layer)
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, as a (meth) acrylic monomer, isobornyl acrylate (trade name “IBXA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 80 parts by weight, n -Butyl acrylate (BA, manufactured by Toa Gosei Co., Ltd.): 19 parts by weight, acrylic acid (AA): 20 parts by weight, poly (oxytetramethylene) glycol having a number average molecular weight of 650 as a polyol (PTMG650, Mitsubishi Chemical Corporation) 68.4 parts by weight, dibutyltin dilaurate (DBTL): 2 parts by weight as a catalyst, and hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): 25.5 parts while stirring. A portion was dropped and reacted at 65 ° C. for 5 hours to obtain a urethane polymer- (meth) acrylic monomer mixture. Thereafter, hydroxyethyl acrylate (trade name “Acrix HEA”, manufactured by Toa Gosei Co., Ltd.): 6.1 parts by weight were added and reacted at 65 ° C. for 1 hour, whereby acryloyl group-terminated urethane polymer- (meth) An acrylic monomer mixture was obtained.
To the resulting acryloyl group-terminated urethane polymer- (meth) acrylic monomer mixture, trimethylolpropane triacrylate (TMPTA): 5 parts by weight, diphenyl (2,4,6, -trimethoxybenzoyl) phosphine as a photopolymerization initiator Oxide (trade name “Lucirin TPO”, manufactured by BASF): 0.25 parts by weight, UV absorber (trade name “TINUVIN123”, manufactured by BASF): 1.25 parts by weight, antioxidant (trade name “TINUVIN400”, BASF) Product): A syrup was obtained by adding 0.6 parts by weight.
The obtained syrup was coated on the surface of a separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc., thickness 38 μm) with an applicator to form a syrup layer having a thickness of 150 μm. A cover separator (trade name “MRF38”, manufactured by Mitsubishi Plastics Co., Ltd., thickness 38 μm) is pasted on this syrup layer with a hand roller, and further irradiated with ultraviolet rays (ultraviolet illuminance: 3.4 mW) by an ultraviolet lamp (BL type). / Cm 2 , cumulative irradiation amount: 2000 mJ / cm 2 ) to obtain a base material layer (C3-B).
(Adhesive tape)
The obtained adhesive layer (C3-A) and substrate layer (C3-B) were bonded together with a hand roller to obtain a tape. Then, an addition type silicone elastomer (LR7665, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was applied on the base material layer (C3-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C3).
The structure of the adhesive tape (C3) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔比較例4〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(C4-A)を得た。
(基材層)
 ウレタン樹脂基材(XUS2098、シーダム(株)製)を用い、厚み150μmの基材層(C4-B)とした。
(粘着テープ)
 得られた粘着層(C4-A)と基材層(C4-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(C4-B)上に、付加型シリコーンエラストマー(LR7665、旭化成ワッカーシリコーン(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(C4)を作成した。
 粘着テープ(C4)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
[Comparative Example 4]
(Adhesive layer)
In the same manner as in Example 1, an adhesive layer (C4-A) having a thickness of 50 μm was obtained.
(Base material layer)
A urethane resin base material (XUS2098, manufactured by Sea Dam Co., Ltd.) was used to form a base material layer (C4-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (C4-A) and substrate layer (C4-B) were bonded together with a hand roller to obtain a tape. Then, an addition type silicone elastomer (LR7665, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was applied on the base material layer (C4-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C4).
The configuration of the adhesive tape (C4) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
〔比較例5〕
(粘着層)
 実施例1と同様に行い、厚み50μmの粘着層(C5-A)を得た。
(基材層)
 ウレタン樹脂基材(DUS451、シーダム(株)製)を用い、厚み150μmの基材層(C5-B)とした。
(粘着テープ)
 得られた粘着層(C5-A)と基材層(C5-B)をハンドローラーにて貼り合わせ、テープを得た。そして、このテープの基材層(C5-B)上に、付加型シリコーンエラストマー(TSE3032、モメンティブ(株)製)をアプリケーターにて塗工し、厚み150μmのシロップ層を形成した。これを150℃で10分間硬化させ、粘着テープ(C5)を作成した。
 粘着テープ(C5)の構成は、防汚層(厚み=150μm)/基材層(厚み=150μm)/粘着層(厚み=50μm)であった。
 評価結果を表1に示した。
[Comparative Example 5]
(Adhesive layer)
In the same manner as in Example 1, a 50 μm thick adhesive layer (C5-A) was obtained.
(Base material layer)
A urethane resin base material (DUS451, manufactured by Sea Dam Co., Ltd.) was used to form a base material layer (C5-B) having a thickness of 150 μm.
(Adhesive tape)
The obtained adhesive layer (C5-A) and substrate layer (C5-B) were bonded together with a hand roller to obtain a tape. Then, an addition-type silicone elastomer (TSE3032, manufactured by Momentive Co., Ltd.) was applied on the base material layer (C5-B) of this tape with an applicator to form a syrup layer having a thickness of 150 μm. This was cured at 150 ° C. for 10 minutes to prepare an adhesive tape (C5).
The configuration of the adhesive tape (C5) was antifouling layer (thickness = 150 μm) / base material layer (thickness = 150 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.
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      粘着層
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 100 Aquatic organism adhesion prevention adhesive tape

Claims (5)

  1.  防汚層と基材層と粘着層をこの順に含む粘着テープであって、
     該防汚層および該基材層から選ばれる少なくとも1種が、シランカップリング剤、シリコーンパウダー、およびシリカ粒子から選ばれる少なくとも1種を含む、
     水生生物付着防止粘着テープ。
    An adhesive tape comprising an antifouling layer, a base material layer and an adhesive layer in this order,
    At least one selected from the antifouling layer and the base material layer includes at least one selected from a silane coupling agent, a silicone powder, and silica particles;
    Aquatic organism adhesion prevention adhesive tape.
  2.  前記防汚層および前記基材層の合計に対する、前記シランカップリング剤、前記シリコーンパウダー、および前記シリカ粒子の合計の含有割合が、0.01重量%~100重量%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 total content of the silane coupling agent, the silicone powder, and the silica particles with respect to the total of the antifouling layer and the base material layer is 0.01 wt% to 100 wt%. The aquatic organism adhesion prevention adhesive tape of description.
  3.  前記基材層がエラストマー樹脂を含む、請求項1または2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 or 2, wherein the base material layer contains an elastomer resin.
  4.  前記エラストマー樹脂がポリウレタンアクリル樹脂およびポリウレタン樹脂から選ばれる少なくとも1種である、請求項3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 3, wherein the elastomer resin is at least one selected from a polyurethane acrylic resin and a polyurethane resin.
  5.  前記防汚層がシリコーン樹脂を含む、請求項1から4までのいずれかに記載の水生生物付着防止粘着テープ。
     
     
     
    The aquatic organism adhesion prevention adhesive tape in any one of Claim 1 to 4 in which the said antifouling layer contains a silicone resin.


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EP3885134A4 (en) * 2018-11-19 2022-08-17 Chugoku Marine Paints, Ltd. Antifouling coating film with cover film, method for producing same, antifouling tape, and method for producing structure which has antifouling coating film and is in contact with water

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JP6369935B2 (en) * 2014-07-25 2018-08-08 日東電工株式会社 Silicone resin composition, antifouling film, and aquatic organism adhesion preventing adhesive film

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JP2000167955A (en) * 1998-12-04 2000-06-20 Nippon Carbide Ind Co Inc Water super-repellent adhesive film
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EP3885134A4 (en) * 2018-11-19 2022-08-17 Chugoku Marine Paints, Ltd. Antifouling coating film with cover film, method for producing same, antifouling tape, and method for producing structure which has antifouling coating film and is in contact with water

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