Tape for preventing adhesion of aquatic organisms

Abstract

This tape for preventing adhesion of aquatic organisms comprises a base material and an adhesive layer provided on at least one surface of the base material. The base material contains an antifouling material.

Description

Tape for preventing aquatic organisms from fouling

[0001] The present invention relates to a tape for preventing the adhesion of aquatic organisms.

[0002] Marine organisms such as barnacles, oysters, mussels, hydra, serpula, sea squirts, bryozoans, sea lettuce, green laver, and attached diatoms can attach to and multiply on underwater structures such as ships and buoys in areas that come into contact with water. The attachment and proliferation of marine organisms can lead to reduced performance of equipment and machinery, such as increased fluid resistance and reduced thermal conductivity, and can also lead to the spread of attached marine organisms overseas. Furthermore, the removal of attached marine organisms requires a great deal of time and effort, resulting in economic losses and contributing to social problems.

[0003]

[0003] A common measure to prevent adhesion of marine organisms is to apply paint to underwater structures. Tapes have also been applied to underwater structures, and tapes for this purpose have been proposed. For example, Patent Document 1 discloses an invention relating to an adhesive tape for preventing adhesion of aquatic organisms, which tape includes an antifouling layer, a substrate layer, and an adhesive layer in this order, and the antifouling layer contains a certain amount of silicone resin.

[0004] Patent No. 5721108

[0005] In order to stably adhere an aquatic organism adhesion-preventing adhesive tape to an adherend for a long period of time and prevent peeling, for example, it is necessary to make the adhesive layer thick. However, with the aquatic organism adhesion-preventing adhesive tape described in Patent Document 1, if the adhesive layer is made thick, a problem occurs in that aquatic organisms adhere to the cross sections of the adhesive layer and then multiply therefrom, resulting in the tape being unable to prevent the adhesion of aquatic organisms to the adherend.

[0006] Therefore, an object of the present disclosure is to provide a tape for preventing the adhesion of aquatic organisms that can prevent marine organisms from adhering not only to the back surface of the tape but also to the cross sections of the tape.

[0007] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by including an antifouling material in the substrate constituting the tape for preventing the adhesion of aquatic organisms. That is, the present invention provides the following [1] to [9].

[0008] [1] An aquatic organism adhesion prevention tape comprising a substrate and a pressure-sensitive adhesive layer provided on at least one surface of the substrate, wherein the substrate comprises an antifouling material. [2] The aquatic organism adhesion prevention tape according to [1], wherein the substrate has a total light transmittance per μm of thickness of 99.97% or less. [3] The aquatic organism adhesion prevention tape according to [1] or [2], wherein the substrate has a contact angle with water of 100° or more. [4] The aquatic organism adhesion prevention tape according to any one of [1] to [3], wherein the substrate has a thickness of 50 to 1000 μm. [5] The aquatic organism adhesion prevention tape according to any one of [1] to [4], wherein the antifouling material is a methyl-para-tolyl sulfone halogen compound. [6] The aquatic organism adhesion prevention tape according to any one of [1] to [5], wherein the substrate comprises a thermoplastic elastomer. [7] The tape for preventing the adhesion of aquatic organisms according to any one of [1] to [6], wherein the thickness of the adhesive layer is 20 to 3000 μm. [8] The tape for preventing the adhesion of aquatic organisms according to any one of [1] to [7], wherein the adhesive strength of the tape for preventing the adhesion of aquatic organisms is 10 N / 25 mm or more. [9] The tape for preventing the adhesion of aquatic organisms according to any one of [1] to [8], wherein the adhesive layer is made of an acrylic adhesive.

[0009] According to the present invention, it is possible to provide a tape for preventing adhesion of aquatic organisms that can prevent adhesion of aquatic organisms not only to the back surface of the tape but also to the cross section of the tape.

[0010] 1 is a schematic diagram illustrating one embodiment of a pressure-sensitive adhesive tape of the present invention.

[0011] [Tape for preventing adhesion of aquatic organisms] The tape for preventing adhesion of aquatic organisms of the present invention comprises a substrate and a pressure-sensitive adhesive layer provided on at least one surface of the substrate. Each layer will be described in detail below.

[0012] (Substrate) The substrate constituting the tape for preventing the adhesion of aquatic organisms of the present invention contains an antifouling material. By including an antifouling material, it is possible to prevent aquatic organisms from adhering not only to the back surface of the tape but also to the cross section of the tape. Examples of the antifouling material include methyl para-tolyl sulfone compounds, with methyl para-tolyl sulfone halogen compounds being preferred. Examples of methyl para-tolyl sulfone halogen compounds include fluorides, chlorides, bromides, and iodides, as well as combinations thereof. Of these, iodides are more preferred, with diiodomethyl-p-tolyl sulfone being particularly preferred. The antifouling material may contain antifouling materials other than methyl para-tolyl sulfone halogen compounds. Other antifouling materials include, but are not limited to, antibacterial agents, pharmaceuticals such as meditomidine, anti-algae agents such as 3-(3,4-dichlorodiphenyl)-1,1-dimethylurea, diatom adhesion inhibitors such as metal salts of bis(2-pyridinethiol-1-oxide), and physical adhesion inhibitors such as wax, petrolactam, vegetable oils and fats, and fatty acids, as well as combinations thereof.

[0013] The content of the antifouling material in the substrate is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the resin constituting the substrate, which will be described later. When the content of the antifouling material is equal to or greater than the lower limit, adhesion of aquatic organisms is more effectively prevented. Furthermore, when the content of the antifouling material is equal to or less than the upper limit, mixing of the antifouling material with the resin constituting the substrate during tape production is easier, which tends to improve tape productivity. Furthermore, transparency of the tape is more easily ensured.

[0014] The substrate preferably contains a resin, and the above-mentioned antifouling material may be dispersed in the resin. The resin constituting the substrate is not particularly limited, and examples thereof include olefin-based resins, polyester-based resins such as polyethylene terephthalate (PET), acrylic resins, thermoplastic elastomers, etc. The resin constituting the substrate may be a thermoplastic resin, and the above-mentioned olefin-based resins, polyester-based resins, and acrylic resins may be thermoplastic resins. The resin constituting the substrate may be used alone or in combination of two or more types. The resin constituting the substrate may also constitute a resin film. That is, the substrate may be, for example, a resin film containing the above-mentioned resin.

[0015] Specific examples of olefin-based thermoplastic resins include polyethylene resins, polypropylene resins, and ethylene-vinyl acetate copolymers, among which polyethylene resins are preferred. Examples of polyethylene resins include polyethylene resins polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene catalyst, or a chromium oxide compound.

[0016] Furthermore, linear low-density polyethylene is preferred as the polyethylene resin. The linear low-density polyethylene is more preferably a linear low-density polyethylene obtained by copolymerizing ethylene (for example, 75% by mass or more, preferably 90% by mass or more, based on the total amount of monomers) with a small amount of an α-olefin as needed. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. Of these, α-olefins having 4 to 10 carbon atoms are preferred. The density of the polyethylene resin, for example, the linear low-density polyethylene described above, is 0.870 to 0.925 g / cm from the viewpoint of flexibility. ３ is preferably 0.890 to 0.925 g / cm ３ More preferably, 0.910 to 0.925 g / cm ３ As the polyethylene resin, a plurality of polyethylene resins may be used, and a polyethylene resin having a density outside the above range may be added.

[0017] Examples of the ethylene-vinyl acetate copolymer used as the olefin-based thermoplastic resin include an ethylene-vinyl acetate copolymer containing 50% by mass or more of ethylene. Examples of polypropylene resins include homopolypropylene and propylene-α-olefin copolymers containing 50% by mass or more of propylene. These may be used alone or in combination of two or more. Specific examples of the α-olefin constituting the propylene-α-olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. Of these, α-olefins having 6 to 12 carbon atoms are preferred.

[0018] Examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, etc. As the thermoplastic elastomer, one of these components may be used alone, or two or more of them may be used in combination.

[0019] Examples of olefin-based thermoplastic elastomers include blend-type, dynamically crosslinked-type, and polymerized-type elastomers. More specifically, examples include thermoplastic elastomers that use a thermoplastic crystalline polyolefin such as polypropylene or polyethylene for the hard segment and fully vulcanized or partially vulcanized rubber for the soft segment. Examples of thermoplastic crystalline polyolefins include homopolymers of α-olefins having 1 to 4 carbon atoms or copolymers of two or more α-olefins, with polyethylene or polypropylene being preferred. Examples of soft segment components include butyl rubber, halobutyl rubber, EPDM, EPM, acrylonitrile / butadiene rubber, NBR, and natural rubber, with EPDM being preferred.

[0020] Further, the olefin-based thermoplastic elastomer may be a block copolymer type. Examples of the block copolymer type include those having a crystalline block and a soft segment block, and more specifically, a crystalline olefin block-ethylene-butylene copolymer-crystalline olefin block copolymer (CEBC). In the CEBC, the crystalline olefin block is preferably a crystalline ethylene block, and examples of commercially available CEBCs include "DYNARON 6200P" manufactured by JSR Corporation.

[0021] Examples of the styrene-based thermoplastic elastomer include block copolymers having a styrene polymer or copolymer block and a conjugated diene compound polymer or copolymer block. Examples of the conjugated diene compound include isoprene and butadiene. The styrene-based thermoplastic elastomer used in the present invention may or may not be hydrogenated. When hydrogenation is performed, the hydrogenation can be performed by a known method.

[0022] The styrene-based thermoplastic elastomer is usually a block copolymer, and examples thereof include styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene / butylene block copolymer (SEB), styrene-ethylene / propylene block copolymer (SEP), and styrene-ethylene / butylene-crystalline olefin block copolymer (SEBC).

[0023] As the styrene-based thermoplastic elastomer, commercially available products may be used, and specific examples include those manufactured by JSR Corporation under the product name "DYNARON 8600P" (styrene content: 15% by mass), "DYNARON 4600P" (styrene content: 20% by mass), and "DYNARON 1321P" (styrene content: 10% by mass), and those manufactured by Kuraray Co., Ltd. under the product name "HYBRAR 7311".

[0024] Among the resins mentioned above, the resin constituting the substrate preferably contains a thermoplastic elastomer, and more preferably a styrene-based thermoplastic elastomer, from the viewpoint of smoothing the surface of the substrate (the surface that will become the back surface of the tape) and making it easier to prevent the adhesion of aquatic organisms. The resin may constitute the main component of the substrate, and its content may be, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, based on the total amount of the substrate. It is preferable to select a resin that is compatible with the antifouling material from the viewpoint of surface energy (low is preferable) so that the antifouling material can be appropriately dispersed in the resin, and from the viewpoint of improving slipperiness when an oil component such as a plasticizer is included. For example, one preferred embodiment includes a methyl-para-tolyl sulfone halogen compound as the antifouling material and a styrene-based thermoplastic elastomer as the resin constituting the substrate. The oil component may be incorporated as an additive, as described below.

[0025] In addition to the above-mentioned antifouling material and resin, the base material may contain additives such as oil components such as plasticizers, pigments, dyes, ultraviolet absorbers, antioxidants, light stabilizers, flexibility imparting agents, flame retardants, and antistatic agents, as needed.

[0026] When the tape of the present invention is a single-sided adhesive tape as described below, the substrate may be release-treated with a release agent on the surface that will become the back surface of the tape. By performing the release treatment, the contact angle of the back surface, as described below, becomes equal to or greater than a certain level, making it easier to prevent the adhesion of aquatic organisms. When the back surface of the substrate is release-treated, the tape of the present invention may be configured to include an adhesive layer, a substrate, and a release agent layer in this order. When performing the release treatment, the resin contained in the substrate is not particularly limited, but polyester resins are preferred, and polyethylene terephthalate is more preferred. The release agent that can be used for the release treatment is not particularly limited, and for example, a silicone-based release agent, a long-chain alkyl-based release agent, etc. may be used. The thickness of the release agent layer is not particularly limited, but the amount of adhesion may be, for example, 0.1 g / m ２ 10g / m or more ２ or less, preferably 0.3 g / m ２ 5g / m or more ２ The amount may be adjusted to the following extent.

[0027] <Total Light Transmittance per μm Thickness> The total light transmittance per μm thickness of the substrate (hereinafter also referred to as "total light transmittance (Y)") is preferably 99.97% or less, more preferably 99.96% or less, and even more preferably 99.95% or less. Generally, when an antifouling material is blended into the substrate, the total light transmittance (Y) of the substrate decreases depending on the blending amount. Therefore, when the total light transmittance (Y) is below the above upper limit, the substrate contains a certain amount of antifouling material, which makes it easier to prevent the adhesion of aquatic organisms. Furthermore, from the viewpoint of improving tape productivity by blending a certain amount of repellent below, and from the viewpoint of transparency, the total light transmittance (Y) is preferably 99.7% or more, more preferably 99.8% or more, and even more preferably 99.9% or more. The total light transmittance (Y) can be determined by the calculation method described in the Examples below.

[0028] <Total Light Transmittance> The total light transmittance of the substrate (hereinafter also referred to as "total light transmittance (X)") is preferably 99% or less, more preferably 97% or less, and even more preferably 95% or less. When the total light transmittance (X) is equal to or less than the above upper limit, adhesion of aquatic organisms is easily prevented. Furthermore, from the viewpoint of productivity and transparency of the tape, the total light transmittance (X) is preferably 40% or more, more preferably 50% or more, and even more preferably 65% ​​or more. The total light transmittance (X) is the total light transmittance when viewed from the entire substrate, and can be determined by the measurement method described in the Examples below.

[0029] <Contact angle> The substrate preferably has a contact angle with water of 100° or more, more preferably 103° or more, and even more preferably 106° or more. When the contact angle with water is equal to or greater than the above lower limit, the surface of the substrate (i.e., the surface that becomes the back surface of the tape) becomes smooth, making it easier to prevent the adhesion of aquatic organisms. The contact angle with water is not particularly limited, but in practice it is, for example, 180° or less, preferably 150° or less. The contact angle of the substrate can be adjusted by the type of resin constituting the substrate or by providing a release layer on the surface of the substrate. The contact angle with water can be determined by the measurement method described in the examples below.

[0030] <Thickness> The thickness of the substrate is preferably 50 to 1000 μm, more preferably 100 to 1000 μm, and even more preferably 200 to 600 μm. When the thickness of the substrate is equal to or greater than the above-mentioned lower limit, adhesion of aquatic organisms is easily prevented for a long period of time. Furthermore, when the thickness of the substrate is equal to or less than the above-mentioned upper limit, productivity and workability of the tape are easily improved.

[0031] (Adhesive Layer) The adhesive layer is preferably formed from an adhesive. The type of adhesive is not particularly limited, but examples include acrylic adhesives, rubber adhesives, urethane adhesives, and silicone adhesives. These may be used alone or in combination. Among these, the adhesive layer is preferably formed from an acrylic adhesive.

[0032] <Acrylic Pressure-Sensitive Adhesive> The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer obtained by polymerizing a polymerizable monomer containing a (meth)acrylic acid alkyl ester monomer (A). In this specification, the term "(meth)acrylic acid alkyl ester" refers to a concept including both an acrylic acid alkyl ester and a methacrylic acid alkyl ester, and the same applies to other similar terms. In addition, the term "polymerizable monomer" refers to a concept including not only a compound having no repeating unit, but also a compound copolymerizable with a (meth)acrylic acid alkyl ester monomer (A), such as the olefin polymer (C) described below, which may have a repeating unit itself.

[0033] <<(Meth)acrylic Acid Alkyl Ester Monomer (A)>> The (meth)acrylic acid alkyl ester monomer (A) is an ester of (meth)acrylic acid and an aliphatic alcohol, and is preferably an alkyl ester derived from an aliphatic alcohol in which the number of carbon atoms in the alkyl group of the aliphatic alcohol is preferably 2 to 14, more preferably 4 to 10. When the number of carbon atoms in the alkyl group is within this range, it is easy to increase the adhesive strength, and it is also easy to adjust the storage modulus at 23°C of the pressure-sensitive adhesive, which will be described later, within a predetermined range.

[0034] Specific examples of the (meth)acrylic acid alkyl ester monomer (A) include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (meth)acrylate. Among these, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-octyl (meth)acrylate are preferred, and n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or a combination thereof is more preferred. Of these, it is even more preferred to use at least one of n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. By using these, the adhesiveness of the pressure-sensitive adhesive can be appropriately controlled, improving workability when applying the tape. Furthermore, the (meth)acrylic acid alkyl ester-based monomer (A) is preferably an acrylic acid alkyl ester. The (meth)acrylic acid alkyl ester-based monomer (A) may be used alone or in combination of two or more types.

[0035] The structural unit derived from the (meth)acrylic acid alkyl ester monomer (A) constitutes the main component of the pressure-sensitive adhesive layer, and its content is generally 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total amount of the pressure-sensitive adhesive layer. Increasing the content of the structural unit derived from the (meth)acrylic acid alkyl ester monomer (A) makes it easier to impart the desired adhesive strength to the pressure-sensitive adhesive layer. Furthermore, the content of the structural unit derived from the (meth)acrylic acid alkyl ester monomer (A) is, for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less, in order to contain a certain amount or more of other components. The content of the structural unit derived from the (meth)acrylic acid alkyl ester monomer (A) in the pressure-sensitive adhesive layer is substantially the same as the content of the (meth)acrylic acid alkyl ester monomer (A) in the pressure-sensitive adhesive composition described below, and can therefore be expressed interchangeably. The same applies to components other than component (A), such as components (B) and (C) described below.

[0036] <<Polar Group-Containing Vinyl Monomer (B)>> The polymerizable monomer preferably contains a polar group-containing vinyl monomer (B) in addition to the (meth)acrylic acid alkyl ester-based monomer (A). The polar group-containing vinyl monomer (B) has a polar group and a vinyl group. Use of the polar group-containing vinyl monomer (B) makes it easier to improve adhesive strength to an adherend. Examples of the polar group-containing vinyl monomer (B) include carboxylic acid vinyl esters such as vinyl acetate, carboxylic acids containing a vinyl group such as (meth)acrylic acid and itaconic acid, and anhydrides thereof, vinyl monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone-modified (meth)acrylate, polyoxyethylene (meth)acrylate, and polyoxypropylene (meth)acrylate, and nitrogen-containing vinyl monomers such as (meth)acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyllaurolactam, (meth)acryloylmorpholine, (meth)acrylamide, dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and dimethylaminomethyl (meth)acrylate. Among these, (meth)acrylic acid, itaconic acid, and other vinyl group-containing carboxylic acids and their anhydrides are preferred, (meth)acrylic acid is more preferred, and among these, acrylic acid is even more preferred from the viewpoint of making it easier to maintain a certain level of adhesive strength retention. These polar group-containing vinyl monomers (B) may be used alone or in combination of two or more.

[0037] When a polar group-containing vinyl monomer (B) is used, the content of the structural units derived from the polar group-containing vinyl monomer (B) in the pressure-sensitive adhesive layer is preferably 1 part by mass or more and 15 parts by mass or less, more preferably 2 parts by mass or more and 12 parts by mass or less, and even more preferably 3 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the structural units derived from the (meth)acrylic acid alkyl ester monomer (A). By setting the content of the polar group-containing vinyl monomer (B) within this range, the adhesive strength of the tape can be easily improved.

[0038] <<Olefin Polymer (C)>> The polymerizable monomer preferably further contains an olefin polymer (C) having a polymerizable bond at one end. Use of such an olefin polymer (C) facilitates improving the adhesive strength of the tape. The polymerizable bond refers to an unsaturated carbon-carbon bond that can be polymerized with the polymerizable monomer, such as an unsaturated double bond, preferably a (meth)acryloyl group. Examples of the olefin polymer (C) include polyolefins having a (meth)acryloyl group at one end. The polyolefin is a polymer of an aliphatic hydrocarbon compound having a double bond, such as ethylene, propylene, butane, butadiene, or isoprene, or a hydrogenated product thereof.

[0039] Examples of polyolefins having a (meth)acryloyl group at one end include polyethylene having a (meth)acryloyl group at one end, which is prepared by reacting polyethylene having an epoxy group at one end with (meth)acrylic acid. Also included are polybutadiene having a (meth)acryloyl group at one end or hydrogenated products thereof, and examples of commercially available products include "L-1253" manufactured by Kuraray Co., Ltd.

[0040] The olefin polymer (C) preferably has a number average molecular weight of 500 to 20,000, more preferably 1,000 to 10,000. The number average molecular weight may be measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene. The content of the structural units derived from the olefin polymer (C) in the pressure-sensitive adhesive layer is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less, and even more preferably 3 parts by mass or more and 12 parts by mass or less, per 100 parts by mass of the structural units derived from the (meth)acrylic acid alkyl ester monomer (A).

[0041] <<Crosslinking Agent (D)>> The polymerizable monomer preferably further contains a crosslinking agent. Examples of the crosslinking agent include polyfunctional monomers having two or more vinyl groups, and preferably polyfunctional (meth)acrylates having two or more (meth)acryloyl groups. The use of polyfunctional monomers makes it easier to adjust the adhesive strength of the pressure-sensitive adhesive layer to an appropriate range. Examples of polyfunctional (meth)acrylates include, but are not limited to, hexanediol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, proxilated trimethylolpropane triacrylate, proxilated glyceryl triacrylate, neopentyl glycol adipate diacrylate, and the like, as well as polymers such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and liquid hydrogenated 1,2-polybutadiene di(meth)acrylate. Among these polyfunctional (meth)acrylates, polymers are preferred, and liquid hydrogenated 1,2-polybutadiene diacrylate is more preferred. Commercially available liquid hydrogenated 1,2-polybutadiene diacrylates include "TEAI-1000" manufactured by Nippon Soda Co., Ltd. The content of the structural units derived from the crosslinking agent in the pressure-sensitive adhesive layer is preferably 0.01 parts by mass or more and 4 parts by mass or less, more preferably 0.1 parts by mass or more and 2 parts by mass or less, and even more preferably 0.2 parts by mass or more and 1.5 parts by mass or less, relative to 100 parts by mass of the structural units derived from the (meth)acrylic acid alkyl ester monomer (A).

[0042] <<Polymerization Initiator>> The acrylic pressure-sensitive adhesive preferably contains a polymerization initiator. Examples of the polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether, acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-methylanthraquinone, 2-amylanthraquinone, Examples of suitable polymerization initiators include anthraquinone compounds such as 2-t-butylanthraquinone and 1-chloroanthraquinone, xanthone compounds such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone, ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone compounds such as 4-(1-t-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone, and acylphosphine oxide compounds. The content of the polymerization initiator in the acrylic pressure-sensitive adhesive is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass, and even more preferably 0.15 to 0.7 parts by mass, relative to 100 parts by mass of the structural units derived from the (meth)acrylic acid alkyl ester monomer (A).

[0043] <<Tackifier Resin>> The acrylic pressure-sensitive adhesive may contain a tackifier resin to improve adhesive strength. Preferred tackifier resins are those with low polymerization inhibition properties, such as hydrogenated terpene resins, hydrogenated rosins, disproportionated rosin resins, and petroleum resins. Among these, hydrogenated resins are preferred, as tackifier resins containing many double bonds inhibit polymerization reactions, and hydrogenated petroleum resins are particularly preferred. The softening point of the tackifier resin may be approximately 95°C or higher to improve the cohesive strength and adhesive strength of the pressure-sensitive adhesive, but preferably includes a tackifier resin with a softening point of 120°C or higher. Furthermore, to improve adhesiveness to an adherend, for example, a tackifier resin with a softening point of 95°C or higher but lower than 120°C and a tackifier resin with a softening point of 120°C or higher but lower than 150°C may be used in combination. The softening point may be measured by the ring and ball method specified in JIS K2207.

[0044] The content of the tackifier resin in the acrylic pressure-sensitive adhesive is preferably 3 parts by mass or more and 40 parts by mass or less, more preferably 4 parts by mass or more and 30 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the structural units derived from the (meth)acrylic acid alkyl ester-based monomer (A).

[0045] <<Microparticles>> The acrylic pressure-sensitive adhesive may contain microparticles. By including microparticles, adhesive strength can be further improved. Examples of the microparticles include inorganic hollow particles such as glass balloons, shirasu balloons, and fly ash balloons; organic hollow particles made of polymethyl methacrylate, acrylonitrile-vinylidene chloride copolymer, polystyrene, and phenolic resin; inorganic microparticles such as glass beads, silica beads, and synthetic mica; and organic microparticles such as polyethyl acrylate, polyurethane, polyethylene, and polypropylene. The content of the microparticles in the acrylic pressure-sensitive adhesive is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the structural units derived from the (meth)acrylic acid alkyl ester monomer (A).

[0046] <<Other Components>> The acrylic pressure-sensitive adhesive used in the pressure-sensitive adhesive layer may contain, in addition to the components described above, various additives conventionally used in pressure-sensitive adhesives, such as plasticizers, softeners, pigments, dyes, dispersants, thickeners, and flame retardants.

[0047] <Rubber-Based Pressure-Sensitive Adhesives> Rubber-based pressure-sensitive adhesives contain a rubber component and a tackifying resin, and it is preferable to use a styrene-isoprene block copolymer as the rubber component. The styrene-isoprene block copolymer preferably has a diblock ratio of 25 to 70% by mass, more preferably 30 to 65% by mass, and even more preferably 45 to 60% by weight. Here, "diblock" refers to a diblock composed of styrene and isoprene. By setting the diblock ratio within the above range, it becomes easier to increase adhesive strength. In addition to diblock copolymers, styrene-isoprene block copolymers also include those having three or more blocks, such as triblocks composed of styrene, isoprene, and styrene blocks.

[0048] The amount of styrene in the styrene-isoprene block copolymer is not particularly limited, but is preferably 14 to 24% by mass, more preferably 15 to 18% by mass. If the styrene amount is 14% by mass or more, the resulting adhesive tends to have high cohesive strength. Furthermore, if the styrene amount is 24% by mass or less, the cohesive strength becomes moderate and adhesive strength is easily exerted. The molecular weight of the styrene-isoprene block copolymer is not particularly limited, but is preferably 100,000 to 400,000 in mass average molecular weight, more preferably 150,000 to 250,000. The mass average molecular weight referred to here refers to the molecular weight measured as polystyrene equivalent by GPC (gel permeation chromatography) method.

[0049] Various tackifying resins can be used for rubber-based pressure-sensitive adhesives, but petroleum-based resins, terpene resins, and coumarone resins are preferred. Tackifying resins may be used alone or in combination of two or more, but it is preferable to use a petroleum-based resin in combination with at least one selected from terpene resins and coumarone resins. Such a combination of tackifying resins facilitates improved adhesive strength. The rubber-based pressure-sensitive adhesive may contain fine particles, sacrificial anticorrosive metals, conductive materials, softeners, antioxidants, fillers, etc., as needed.

[0050] <Urethane-Based Pressure-Sensitive Adhesives> The urethane-based pressure-sensitive adhesive is not particularly limited, and examples thereof include urethane resins obtained by reacting at least a polyol with a polyisocyanate compound. Examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. Examples of the polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate. These urethane-based pressure-sensitive adhesives may be used alone or in combination of two or more. Furthermore, examples of the urethane-based pressure-sensitive adhesive include urethane resins obtained by reacting a polyurethane polyol with a polyfunctional isocyanate curing agent. Examples of polyurethane polyols include those obtained by reacting the above-mentioned polyols with a polyisocyanate compound, or those obtained by reacting a polyol, a polyisocyanate compound, and a chain extender such as a diamine. The polyfunctional isocyanate curing agent may be any compound having two or more isocyanate groups, and the above-mentioned isocyanate compounds can be used. The urethane-based adhesive may contain the above-mentioned fine particles in addition to the urethane resin, and may also contain a tackifying resin, a sacrificial anticorrosive metal, a conductive material, a softener, an antioxidant, a filler, etc., as necessary.

[0051] <Silicone-based adhesive> Examples of silicone-based adhesives include addition reaction type, peroxide curing type, and condensation reaction type silicone-based adhesives. Among them, addition reaction type silicone-based adhesives are preferably used from the viewpoint of being able to cure at low temperature in a short time. Note that addition reaction type silicone-based adhesives cure when the adhesive layer is formed. When an addition reaction type silicone-based adhesive is used as the silicone-based adhesive, the silicone-based adhesive may contain a catalyst such as a platinum catalyst. Furthermore, the silicone-based adhesive may contain the above-mentioned fine particles, and may also contain a crosslinking agent and various additives for controlling adhesive strength.

[0052] <Thickness> The thickness of the pressure-sensitive adhesive layer is preferably 20 to 3000 μm, more preferably 50 to 2000 μm, even more preferably 100 to 1000 μm, and even more preferably 200 to 800 μm. By making the thickness of the pressure-sensitive adhesive layer at or above the above-mentioned lower limit, the adhesive strength is increased, making it easier to prevent marine organisms from attaching to the adherend over a long period of time. Furthermore, by making the thickness of the pressure-sensitive adhesive layer at or below the above-mentioned upper limit, a sufficient effect of preventing the attachment of marine organisms can be obtained.

[0053] <Method for Producing Acrylic Pressure-Sensitive Adhesive and Pressure-Sensitive Adhesive Layer> The acrylic pressure-sensitive adhesive can be obtained by irradiating a pressure-sensitive adhesive composition containing the above-described polymerizable monomer and, optionally, a polymerization initiator, with light to polymerize the polymerizable monomer. The pressure-sensitive adhesive composition may also contain, optionally, the above-described tackifier resin and at least one other component. More specifically, the polymerizable monomer, the optional polymerization initiator, the tackifier resin, and other components are first mixed in a reaction vessel such as a glass vessel to obtain a pressure-sensitive adhesive composition. Next, to remove dissolved oxygen from the pressure-sensitive adhesive composition, an inert gas such as nitrogen gas is generally supplied to purge the oxygen. The pressure-sensitive adhesive composition is then applied to a release sheet or substrate, and then irradiated with light to polymerize the polymerizable monomer, thereby obtaining a pressure-sensitive adhesive layer. In this case, a substrate or release sheet may be further placed on top of the applied pressure-sensitive adhesive composition before irradiating with light. The steps from applying or impregnating the pressure-sensitive adhesive composition to irradiating with light are preferably carried out under an inert gas atmosphere or in a state where oxygen is blocked by a film or the like. In the present production method, in order to increase the viscosity of the pressure-sensitive adhesive composition obtained by mixing the components, it may be pre-polymerized before being applied to a release sheet, a support, etc. Furthermore, although the above explanation has exemplified a photocurable embodiment in which the polymerizable monomer is polymerized by irradiation with light, the polymerizable monomer may also be polymerized by a method other than light irradiation.

[0054] (Adhesive Strength) The adhesive strength of the tape for preventing the adhesion of aquatic organisms of the present invention at 23°C is preferably 5 N / 25 mm or more, more preferably 10 N / 25 mm or more, even more preferably 21 N / 25 mm or more, and even more preferably 31 N / 25 mm or more. When the adhesive strength at 23°C is equal to or greater than the above-mentioned lower limit, the adhesive strength of the adhesive tape is increased and the tape adheres stably to the adherend even underwater for a long period of time, thereby further facilitating prevention of adhesion of aquatic organisms. The higher the adhesive strength at 23°C, the better, but in practical terms, it is 200 N / 25 mm or less, preferably 150 N / 25 mm or less. The adhesive strength of the tape for preventing the adhesion of aquatic organisms can be measured by laminating a 25 mm wide tape to an SUS plate with a 2 kg roller, and then peeling the tape from the SUS plate at a peel angle of 90° and a speed of 300 mm / min under conditions of 23°C and 50% RH.

[0055] (Structure of the tape) As described above, the tape for preventing the adhesion of aquatic organisms of the present invention has a pressure-sensitive adhesive layer provided on at least one surface of a substrate, but as shown in Figure 1, the tape 10 is preferably a single-sided pressure-sensitive adhesive tape having a substrate 12 and a pressure-sensitive adhesive layer 11 provided on one surface of the substrate 12. This allows the pressure-sensitive adhesive layer 11 to be protected by the substrate 12. The tape is used by adhering the surface 11A of the pressure-sensitive adhesive layer 11 to an adherend, with the surface 11A serving as the adhesive surface.

[0056] The tape for preventing the adhesion of aquatic organisms of the present invention may have a release sheet attached to the surface of the adhesive layer. The release sheet is preferably peeled from the adhesive layer before use to expose the adhesive layer, and the exposed adhesive layer is then attached to the adherend. More specifically, the release sheet is preferably attached to the surface of the adhesive layer opposite the surface on which the substrate is provided, i.e., surface 11A. As the release sheet, a resin film, release paper, or the like may be used, but it is preferable that the surface to be attached to the adhesive layer is a release-treated surface that has been subjected to a release treatment with a silicone release agent or the like.

[0057] (Method for manufacturing tape) The tape for preventing adhesion of aquatic organisms of the present invention can be obtained by laminating a pressure-sensitive adhesive layer on at least one surface of a substrate. Here, the substrate can be obtained, for example, by feeding the resin for forming the substrate, the antifouling material, and other additives that are blended as necessary into an extruder and melt-kneading them to obtain a resin composition for forming the substrate, and extruding the resin composition into a sheet using a T-die or the like. Furthermore, as described above, the surface of the substrate that will become the back surface of the tape may be release-treated as needed. The release treatment may be performed, for example, before laminating the pressure-sensitive adhesive layer on the substrate, or after laminating the pressure-sensitive adhesive layer on the substrate. Furthermore, in the case of a commercially available resin film that has been pre-release-treated, it is preferable to laminate the pressure-sensitive adhesive layer on the substrate so that at least the back surface of the tape is the release-treated surface.

[0058] The method for laminating a pressure-sensitive adhesive layer on a substrate is not particularly limited, but for example, when the pressure-sensitive adhesive composition is photocurable, the pressure-sensitive adhesive composition may be directly applied to a substrate and a release sheet may be applied as needed, or the substrate may be applied to the pressure-sensitive adhesive composition applied to the release sheet, and then photopolymerized to laminate the pressure-sensitive adhesive layer on the substrate. The tape for preventing the adhesion of aquatic organisms can also be produced by methods other than those described above, and may be produced by laminating a pressure-sensitive adhesive layer on a substrate by a known method, or by further laminating a substrate on a pressure-sensitive adhesive layer laminated on a release sheet.

[0059] (Uses and Methods of Use) The tape of the present invention is a tape for preventing the adhesion of aquatic organisms, and is preferably attached to marine or underwater structures to prevent the attachment of marine organisms such as barnacles. The structure is not particularly limited, and specific examples include underwater structures such as wharves, quays, ships, floats, piers, wave-breaking blocks, and fishing nets. When using the tape, it is advisable to attach it to at least the portion of the marine or underwater structure that comes into contact with seawater. The tape may also be attached to underwater devices such as sensors used on or under the sea. The location where the tape of the present invention is used is not limited to the sea, and it may be used in rivers, lakes, and other locations. Furthermore, the tape of the present invention protects the surface of the structure or underwater device to which it is attached, and can prevent the underwater structure or device from being deteriorated by seawater or the like.

[0060] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0061] [Evaluation Methods] In each of the Examples and Comparative Examples, the pressure-sensitive adhesive layer was evaluated by the following evaluation methods.

[0062] (Total Light Transmittance) The total light transmittance (total light transmittance (X)) of the substrate used in each of the Examples and Comparative Examples was measured by the following procedure. It was measured in accordance with JIS K7361-1. Specifically, it was measured using a haze meter (for example, Haze Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.) in an atmosphere of 23°C and humidity 50%.

[0063] (Total Light Transmittance per 1 μm Thickness) Using the total light transmittance (X) measured by the above method and the thickness T (μm) of the substrate, the total light transmittance per 1 μm thickness (total light transmittance (Y)) was calculated based on the following formula (1).

[0064] (Contact angle) 1 μL of distilled water was dropped using a micropipette to measure the contact angle of the substrate with water. A fully automatic contact angle meter (product name "DMo-701", manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle. The contact angle was measured on the back surface, which is the surface opposite to the surface on which the pressure-sensitive adhesive layer was provided.

[0065] (Adhesive Strength) The tapes obtained in each Example and Comparative Example were cut to a width of 25 mm and a length of 100 mm, and then bonded to a SUS plate (width 50 mm, length 125 mm) via the adhesive layer to prepare a measurement sample. The bonding to the SUS plate was performed by reciprocating a 2 kg roller twice at a speed of 10±0.5 mm / s. The measurement sample obtained by the above method was fixed to the chuck of a tensile tester ("Tensilon Universal Material Tester" manufactured by A&D Co., Ltd.). Then, in an environment of 23°C and 50% RH, the tape was pulled for 60 mm or more at a peel angle of 90° and a speed of 300 mm / min, and the average value of the load (N) detected by the load cell was recorded and used as the adhesive strength.

[0066] (Barnacle Larvae Adhesion Rate) The tapes obtained in each Example and Comparative Example were cut to a width of 50 mm and a length of 50 mm, and then attached to a glass plate (width 40 mm, length 40 mm) via the adhesive layer. The excess sheet was cut off to obtain a measurement sample. The attachment was performed by manual pressure bonding. The measurement sample obtained by the above method was placed in an aquarium (width 111 mm, length 81 mm, depth 46 mm) containing 100 barnacle larvae and water, with the tape completely submerged in water, and left for 12 days. The barnacle larvae adhesion rate was then calculated based on the following formula (2):

[0067] The barnacle larvae attachment rate was determined on the surface (back) and cross section of the tape, and based on the determined barnacle larvae attachment rate, an evaluation of the barnacle larvae attachment rate was carried out on each of the surface and cross section of the tape, as well as an overall evaluation. The evaluation criteria are as follows. (Surface, cross section) A: The barnacle larvae attachment rate was 0%. B: The barnacle larvae attachment rate exceeded 0%. (Overall evaluation) A: The barnacle larvae attachment rate was 0% on both the surface and cross section of the tape. B: The barnacle larvae attachment rate exceeded 0% on at least either the surface or cross section of the tape.

[0068] [Components Used] The following materials were used in each of the Examples and Comparative Examples.

[0069] (Base material resin) Styrene-based elastomer: Product name "AR-FL60", manufactured by Aron Kasei Co., Ltd. (Anti-fouling material) Diiodomethyl paratolyl sulfone: Product name "Pacific Beam Mold Marine II", manufactured by Pacific Beam Co., Ltd.

[0070] (Film) Release PET: Product name "SP4107", manufactured by Lintec Corporation, thickness 50 μm PET film: Product name "Lumirror S10", manufactured by Toray Industries, Inc., thickness 50 μm Acrylic film: Product name "Soft Acrylic Sheet", manufactured by Tatsuta Chemical Co., Ltd., soft acrylic resin film, thickness 200 μm

[0071] (Adhesive layer) 2-ethylhexyl acrylate, n-butyl acrylate, acrylic acid, olefin polymer: product name "L-1253" manufactured by Kuraray Co., Ltd., hydrogenated polybutadiene having a (meth)acryloyl group at one end. Tackifier resin 1: product name "Arcon P100" manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin, softening point 100°C. Tackifier resin 2: product name "Arcon P140" manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin, softening point 140°C. Fine particles: product name "Cellstar Z-27" manufactured by Tokai Kogyo Co., Ltd., glass balloons. Crosslinker: product name "TEAI-1000" manufactured by Nippon Soda Co., Ltd. Polymerization initiator: 2,2-dimethoxy-2-phenylacetophenone.

[0072] Example 1 100 parts by mass of a styrene-based elastomer and 5 parts by mass of an antifouling material were fed into an extruder and melt-kneaded at 180°C to obtain a resin composition for a substrate. The resin composition was then extruded from the extruder to a thickness of 200 μm to obtain a substrate. A pressure-sensitive adhesive composition was also prepared according to the formulation shown in Table 1. Nitrogen was purged into this pressure-sensitive adhesive composition to remove dissolved oxygen. The pressure-sensitive adhesive composition was then applied to the substrate using an applicator so that the pressure-sensitive adhesive layer would have a thickness of 600 μm after light irradiation. A release sheet was then coated onto the applied pressure-sensitive adhesive composition, with the release-treated surface in contact with the pressure-sensitive adhesive composition. A silicone release-treated PET film (thickness: 50 μm) was used as the release sheet. In this state, the ultraviolet irradiation intensity on the coated side of the release sheet was 5 mW / cm. ２ The lamp intensity of the chemical lamp was adjusted so that the adhesive layer was 100% and the adhesive layer was 100%. The adhesive layer was irradiated from one side for 15 minutes to obtain a tape in which the adhesive layer and the release sheet were laminated in this order on the substrate. Each evaluation was carried out after peeling off the release sheet.

[0073] Examples 2 to 11, Comparative Example 1 The same procedures as in Example 1 were carried out except that the formulation of the resin composition for the substrate, the thickness of the substrate, and the thickness of the adhesive layer were as shown in Tables 1 and 2.

[0074]

[0075] *In Tables 1 and 2, the content of the antifouling material is the content per 100 parts by mass of resin.

[0076] As is clear from the above results, the tapes produced in the Examples contained an antifouling material in the substrate, which enabled the prevention of barnacle adhesion not only on the back surface of the tape but also on the cross section of the tape. In contrast, the tapes produced in the Comparative Examples did not contain an antifouling material in the substrate, which meant that the adhesion of barnacles was not sufficiently prevented, and even if it had been possible, the adhesion was prevented only on the back surface of the tape, and the adhesion of barnacles on the cross section of the tape could not be prevented.

[0077] 10 Tape 11 Adhesive layer 11A Surface of adhesive layer 12 Substrate

Claims

1. A tape for preventing the adhesion of aquatic organisms, comprising a substrate and an adhesive layer provided on at least one surface of the substrate, wherein the substrate contains an antifouling material.

2. The tape for preventing adhesion of aquatic organisms according to claim 1, wherein the total light transmittance per 1 μm of thickness of the substrate is 99.97% or less.

3. A tape for preventing the adhesion of aquatic organisms according to claim 1 or 2, wherein the substrate has a contact angle with water of 100° or more.

4. A tape for preventing the adhesion of aquatic organisms according to claim 1 or 2, wherein the thickness of the substrate is 50 to 1000 μm.

5. A tape for preventing adhesion of aquatic organisms according to claim 1 or 2, wherein the antifouling material is a methyl-para-tolyl sulfone halogen compound.

6. The tape for preventing the adhesion of aquatic organisms according to claim 1 or 2, wherein the substrate comprises a thermoplastic elastomer.

7. The tape for preventing the adhesion of aquatic organisms according to claim 1 or 2, wherein the thickness of the adhesive layer is 20 to 3000 μm.

8. A tape for preventing the adhesion of aquatic organisms according to claim 1 or 2, wherein the adhesive strength of the tape for preventing the adhesion of aquatic organisms is 10 N / 25 mm or more.

9. A tape for preventing adhesion of aquatic organisms according to claim 1 or 2, wherein the adhesive layer is made of an acrylic adhesive.

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