WO2016088630A1 - Resin composition, antifouling material and multilayer film - Google Patents

Abstract

Provided is a multilayer film which is capable of effectively preventing adhesion of aquatic organisms such as algae for a long period of time, while having little impact on the human body and the environment, and which is capable of ensuring sufficient adhesion between an antifouling layer and a base layer. Also provided is an antifouling material which can be used as a constituent material for the multilayer film. Additionally provided is a resin composition which can be used as a constituent material for the antifouling material. A resin composition according to the present invention contains a silicone resin and an oil component. The oil component contains silicone oils, and at least one of the silicone oils is a polyether-modified silicone oil. The content of the polyether-modified silicone oil relative to 100 parts by weight of the silicone resin is from 0.01 part by weight to 5 parts by weight.

Description

Resin composition, antifouling material, and laminated film

The present invention relates to a resin composition, an antifouling material, and a laminated film. More specifically, the present invention relates to, for example, aquatic organisms in underwater structures (ships, buoys, harbor facilities, offshore oilfield facilities, power plant cooling water channels, factory cooling water channels, water floating channels, etc.). The present invention relates to a laminated film that can be used to prevent the material from adhering and growing, an antifouling material that can be used as a constituent material thereof, and a resin composition that can be used as a constituent material thereof.

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

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. Adhesive growth of aquatic 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 painting, it is said that 10 to 20% by weight of the paint is scattered by the wind in addition to VOC emission into the atmosphere. 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 workers and the environment, and the peeled antifouling paint is treated as industrial waste, which is a big problem.

As described above, antifouling paints so far have an adhesion inhibiting effect on aquatic organisms, but have a great adverse effect on the human body and the environment, and the current situation is that many problems have not been solved. .

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 adverse effects on the environment because the adhesion of aquatic organisms is suppressed by a copper 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.

Further, an antifouling tape composed of two layers of a silicone rubber layer and an adhesive layer has been proposed (see Patent Document 3). However, although the silicone rubber layer responsible for the antifouling effect can suppress the attachment of aquatic organisms by its water repellency in the short term, the antifouling effect cannot be sustained in the long term. In addition, since such an antifouling tape is composed of two layers of a silicone rubber layer and an adhesive layer, 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.

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 Patent Document 4 has no description about the adhesive composition that can be used in the ocean and no description about the adhesive force, it can be used to prevent aquatic organisms from adhering to the underwater structure and breeding. When considering application to film, it is not realistic. In addition, when constructing a laminated film on an underwater structure, it is necessary to design it to be flexible and stretchable so that it can be constructed on a curved surface or an acute angle surface. However, since there is no such description in Patent Document 4, a laminate that can be used to prevent aquatic organisms from adhering to the underwater structure and propagating. When considering application to film, it is not realistic.

Recently, as a means to effectively prevent the attachment of aquatic organisms to underwater structures, an antifouling layer, a base material layer, and an adhesive layer are included in this order, and the antifouling layer contains a silicone resin to prevent aquatic organisms from attaching. An adhesive tape has been developed (Patent Document 5).

According to the aquatic organism adhesion-preventing pressure-sensitive adhesive tapes evaluated in Examples 1 to 13 of Patent Document 5, the antifouling effect can be maintained over a long period of time. In particular, the aquatic organism that is a typical aquatic organism causing various problems can be maintained. Adhesion can be effectively prevented.

Here, algae other than barnacles are well known as typical aquatic organisms that easily adhere to underwater structures and cause various problems. However, the aquatic organism adhesion-preventing pressure-sensitive adhesive tapes evaluated in Examples 1 to 13 of Patent Document 5 have a problem that sufficient effects cannot be exerted with respect to algae adhesion.

Furthermore, in the laminated film having a structure including the antifouling layer, the base material layer, and the adhesive layer in this order, it is required that the adhesion between the antifouling layer and the base material layer is sufficiently ensured. It is done. However, conventionally, the adhesion between the antifouling layer and the base material layer may not be sufficiently secured, and can be used to prevent aquatic organisms from adhering to the underwater structure and breeding. Application to laminated film may be difficult. In particular, when the antifouling layer contains a silicone resin, the adhesion to the base material layer may be low due to the low surface energy that is a characteristic of the silicone resin, and an antifouling layer that exhibits an antifouling effect is used. It peels off from the base material layer due to the impact and physical damage inside, and the original antifouling effect cannot be sustained.

Japanese Examined Patent Publication No. 63-62487 Japanese Patent Publication No. 1-54397 Japanese Patent No. 3000101 JP 2002-69246 A JP 2013-147629 A

The problem of the present invention is that it has little influence on the human body and the environment, can effectively prevent the attachment of aquatic organisms such as algae over a long period of time, and can sufficiently secure the adhesion between the antifouling layer and the base material layer. To provide a film. Moreover, it is providing the antifouling material which can be used as a constituent material of such a laminated film. Furthermore, it is providing the resin composition which can be used as a constituent material of such an antifouling material.

The resin composition of the present invention is
A resin composition comprising a silicone resin and an oil component,
The oil component comprises silicone oil;
At least one of the silicone oils is a polyether-modified silicone oil;
The content of the polyether-modified silicone oil with respect to 100 parts by weight of the silicone resin is 0.01 to 5 parts by weight.

In a preferred embodiment, the content of the silicone resin is 30 to 98 parts by weight with respect to 100 parts by weight of the resin composition.

In a preferred embodiment, the content is 50 to 95 parts by weight.

In a preferred embodiment, the content of the oil component is 0.01 to 120 parts by weight with respect to 100 parts by weight of the resin composition.

In a preferred embodiment, the content is 1 to 100 parts by weight.

In a preferred embodiment, the silicone resin is a two-component addition type silicone resin.

In a preferred embodiment, the content of the polyether-modified silicone oil with respect to 100 parts by weight of the silicone resin is 0.1 to 5 parts by weight.

In a preferred embodiment, the polyether-modified silicone oil is a side chain (linear type) polyether-modified silicone oil in which a polyoxyalkylene group is bonded to a side chain.

The antifouling material of the present invention has an antifouling layer made of a cured product of the resin composition of the present invention on a substrate.

The laminated film of the present invention has an adhesive layer on the surface opposite to the antifouling layer of the antifouling material of the present invention.

According to the present invention, there is little influence on the human body and the environment, the adhesion of aquatic organisms such as algae can be effectively prevented over a long period of time, and the adhesion between the antifouling layer and the base material layer can be sufficiently ensured. A film can be provided. Moreover, the antifouling material which can be used as a constituent material of such a laminated film can be provided. Furthermore, the resin composition which can be used as a constituent material of such an antifouling material can be provided.

It is a schematic sectional drawing of an example of the laminated | multilayer film of this invention.

≪Resin composition≫
The resin composition of the present invention contains a silicone resin and an oil component.

The silicone resin contained in the resin composition of the present invention may be only one type or two or more types.

Any appropriate content ratio can be adopted as the content ratio of the silicone resin in the resin composition of the present invention as long as the effects of the present invention are not impaired. The content of the silicone resin in the resin composition of the present invention is preferably 30% to 98% by weight, more preferably 40% to 97% by weight, and still more preferably 45% to 96% by weight. Particularly preferred is 50 to 95% by weight. When the content ratio of the silicone resin in the resin composition of the present invention falls within the above range, the antifouling effect of the antifouling layer composed of a cured product of the resin composition can be more fully expressed, and algae and the like can be used over a long period of time. The adhesion of aquatic organisms can be more effectively prevented, and the mechanical properties of the antifouling layer can be fully expressed.

As the silicone resin, any appropriate silicone resin can be adopted as long as the effects of the present invention are not impaired. 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, the silicone resin is preferably a two-pack type silicone resin, more preferably a two-pack type addition silicone resin, from the viewpoint that the effects of the present invention can be more manifested. Examples of such two-pack type addition silicone resins include KE-1950-10 (A / B), KE-1950-20 (A / B), and KE-1950- manufactured by Shin-Etsu Chemical Co., Ltd. 30 (A / B), KE-1950-35 (A / B), KE-1950-40 (A / B), KE-1950-50 (A / B), KE-1950-60 (A / B) , KE-1950-70 (A / B), KE-1987 (A / B), KE-1988 (A / B), LR7665 series manufactured by Asahi Kasei Wacker Silicone Co., Ltd., LR3033 series, manufactured by Momentive Co., Ltd. Examples include TSE3032 series and LSR series.

The oil component contained in the resin composition of the present invention may be only one type or two or more types.

The content of the oil component with respect to 100 parts by weight of the resin composition of the present invention is preferably 0.01 parts by weight to 120 parts by weight, more preferably 0.05 parts by weight to 115 parts by weight, and even more preferably 0 parts by weight. .10 to 110 parts by weight, particularly preferably 0.5 to 105 parts by weight, and most preferably 1 to 100 parts by weight. When the content of the oil component with respect to 100 parts by weight of the resin composition of the present invention falls within the above range, the antifouling effect of the antifouling layer comprising a cured product of the resin composition can be more fully expressed, and aquatic Biological adhesion can be prevented more effectively.

Oil component contains silicone oil.

Any appropriate content ratio can be adopted as the content ratio of the silicone oil in the oil component as long as the effects of the present invention are not impaired. The content ratio of the silicone oil in the oil component is preferably 10% by weight to 120% by weight, more preferably 15% by weight to 115% by weight, and further preferably 20% by weight to 110% by weight. It is preferably 25% to 1100% by weight, and most preferably 30% to 90% by weight. When the content ratio of the silicone oil in the oil component is within the above range, the antifouling effect of the antifouling layer made of the cured product of the resin composition of the present invention can be expressed more sufficiently, and aquatic organisms such as algae can be obtained over a long period of time. Can be more effectively prevented.

In the present invention, at least one of the silicone oils is a polyether-modified silicone oil. Only one kind of polyether-modified silicone oil may be used, or two or more kinds may be used. When at least one of the silicone oils is a polyether-modified silicone oil, the antifouling effect of the antifouling layer comprising the cured product of the resin composition of the present invention can be sufficiently exhibited, and aquatic organisms such as algae can adhere for a long period of time. Can be effectively prevented.

In the present invention, the content of the polyether-modified silicone oil with respect to 100 parts by weight of the silicone resin is 0.01 part by weight to 5 parts by weight, more preferably 0.05 part by weight to 5 parts by weight, and still more preferably 0 part by weight. .1 to 5 parts by weight, particularly preferably 0.5 to 5 parts by weight. The antifouling effect of the antifouling layer comprising the cured product of the resin composition of the present invention by allowing the content of the polyether-modified silicone oil to be within a very narrow limited range as described above with respect to 100 parts by weight of the silicone resin. In the antifouling material having the antifouling layer comprising the cured product of the resin composition of the present invention on the base material, and capable of effectively preventing adhesion of aquatic organisms such as algae over a long period of time. Adhesiveness between the substrate and the base material layer can be sufficiently secured.

In the present invention, the polyether-modified silicone oil has an HLB of preferably 3 to 15, more preferably 3 to 10. By keeping the HLB of the polyether-modified silicone oil within the above range, the antifouling effect of the antifouling layer made of the cured product of the resin composition of the present invention can be fully exhibited, and aquatic organisms such as algae can adhere for a long time. Can be effectively prevented, and the appearance characteristics and mechanical characteristics of the antifouling layer can be sufficiently exhibited. HLB is a hydrophilic / lipophilic balance that numerically indicates the balance between the hydrophilicity and lipophilicity of oil, and is an abbreviation for Valau of Hydrophile and Liophile Balance. The HLB of the polyether-modified silicone oil includes, for example, selection of a chain length between a polyether polyoxyalkylene chain (group) and a dimethylsiloxane chain (group), and a hydrophilic polyethylene among the polyether polyoxyalkylene chains (group). It can be controlled by selection of chain lengths of oxide and hydrophobic hydrophobic oxide.

The polyether-modified silicone oil is a polysiloxane having a siloxane bond in the main chain and having one or more polyoxyalkylene groups as a substituent. The main chain may form a ring.

The bonding position of the polyoxyalkylene group in the polyether-modified silicone oil can be any appropriate bonding position. For example, a polyoxyalkylene group may be bonded to both ends of the main chain, a polyoxyalkylene group may be bonded to one end of the main chain, or a polyoxyalkylene group may be bonded to a side chain. May be.

In order to fully exhibit the effects of the present invention, a side-chain type (linear type) polyether-modified silicone oil in which a polyoxyalkylene group is bonded to a side chain is selected as the polyether-modified silicone oil. Is preferred.

The side chain type (linear type) polyether-modified silicone oil is preferably represented by the general formula (1).

In the general formula (1), each R independently represents an alkyl group having 1 to 3 carbon atoms, R ¹ represents an alkylene group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom or 1 to 15 carbon atoms. R ³ represents an alkyl group, R ³ is _a polyoxyalkylene group represented by — (C ₂ H ₄ O) _a — (C ₃ H ₆ O) _b —, a is 1 to 50, and b is 0 to 30, m is 1 to 7000, and n is 1 to 50.

In general formula (1), R is preferably a methyl group.

Examples of the polyether-modified silicone oil include trade names “KF-6011” (HLB: 14.5), “KF-6011P” (HLB: 14.5), “KF-6012” manufactured by Shin-Etsu Silicone Co., Ltd. (HLB: 7.0), “KF-6013” (HLB: 10.0), “KF-6015” (HLB: 4.5), “KF-6016” (HLB: 4.5), “KF -6017 "(HLB: 4.5)," KF-6017P "(HLB: 4.5)," KF-6043 "(HLB: 14.5)," KF-6004 "(HLB: 9.0), KF351A, KF352A, KF353, KF354L, KF355A, KF615A, KF945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X22- Side chain type (linear type) polyether-modified silicone oil such as 515; trade names “KF-6028” (HLB: 4.0), “KF-6028P” (HLB: 4. 0) side chain type (branched chain type) polyether-modified silicone oil; manufactured by Shin-Etsu Silicone Co., Ltd., trade name “KF-6038” (HLB: 3.0), etc. Alkyl co-modified type) polyether-modified silicone oil; and the like.

In the present invention, the silicone oil may contain a non-reactive silicone oil other than the polyether-modified silicone oil. Only one kind of non-reactive silicone oil other than the polyether-modified silicone oil may be used, or two or more kinds thereof may be used.

In the present invention, when the silicone oil contains a non-reactive silicone oil other than the polyether-modified silicone oil, the antifouling effect of the antifouling layer comprising the cured product of the resin composition of the present invention can be expressed more sufficiently, and the long-term It is possible to more effectively prevent the attachment of aquatic organisms such as algae.

In the present invention, the silicone oil contains a non-reactive silicone oil other than the polyether-modified silicone oil, so that the silicone oil effectively stains the surface of the antifouling layer comprising the cured product of the resin composition of the present invention. The antifouling effect can be maintained for a longer period of time, and the antifouling effect can be more fully exhibited even after the aquatic organism is attached and then removed.

As the non-reactive silicone oil other than the polyether-modified silicone oil, the main chain is a polysiloxane composed of a siloxane bond and may have a substituent. The main chain may form a ring. Examples of non-reactive silicone oils other than polyether-modified silicone oil include straight silicone oil and modified silicone oil (excluding polyether-modified silicone oil).

The substituent in the straight silicone oil is preferably a methyl group or a phenyl group.

The bonding position of the substituent in the straight silicone oil can be any appropriate bonding position. For example, the substituent may be bonded to both ends of the main chain, the substituent may be bonded to one end of the main chain, or the substituent may be bonded to the side chain.

The non-reactive silicone oil other than the polyether-modified silicone oil is preferably represented by the general formula (2).

In general formula (2), 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 different Differently, it represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a polyether group or a fluoroalkyl group, and n represents an integer of 0 to 150. R ¹ in the general formula (I) is preferably a methyl group, a phenyl group, or a hydroxyl group. R ² in the general formula (I) is preferably a methyl group, a phenyl group, or a 4-trifluorobutyl group.

The silicone oil represented by the general formula (2) 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 (2) is preferably 10 centistokes to 10000 centistokes, more preferably 100 centistokes to 5000 centistokes.

As the silicone oil represented by the general formula (2) include, 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.

Non-reactive silicone oils other than the polyether-modified silicone oil include, for example, trade names “KF96L”, “KF96”, “KF69”, “KF99”, “KF50”, “KF54” manufactured by Shin-Etsu Silicone Co., Ltd. "KF410", "KF412", "KF414", "FL", "KF-6104", "KF-6100"; trade names "BY16-846", "SF8416", manufactured by Toray Dow Corning Co., Ltd., “SH200”, “SH203”, “SH230”, “SF8419”, “FS1265”, “SH510”, “SH550”, “SH710”, “FZ-2110”, “FZ-2203”, and the like.

In the present invention, the content of the non-reactive silicone oil other than the polyether-modified silicone oil with respect to 100 parts by weight of the silicone resin is preferably 10 parts by weight to 120 parts by weight, more preferably 15 parts by weight to 110 parts by weight. More preferably 20 to 100 parts by weight, and particularly preferably 25 to 95 parts by weight. When the content of the non-reactive silicone oil other than the polyether-modified silicone oil with respect to 100 parts by weight of the silicone resin falls within the above range, the antifouling effect of the antifouling layer comprising the cured product of the resin composition of the present invention is further improved. It can be fully expressed and can more effectively prevent the attachment of aquatic organisms over a long period of time, and the appearance characteristics and mechanical characteristics of the antifouling layer made of the cured product of the resin composition of the present invention can be fully expressed.

The oil component may contain any appropriate other oil as long as the effects of the present invention are not impaired. Examples of such other oils include liquid paraffin, surfactants, liquid hydrocarbons, fluorinated oils, antibacterial agents, waxes, petrolatum, animal fats, fatty acids, diatom adhesion inhibitors, agricultural chemicals, pharmaceuticals (medetomidine, etc. ), Enzyme activity inhibitors (alkylphenol, alkylresorcinol, etc.), biological repellents and the like. These may be only one type or two or more types.

When the resin composition of the present invention contains such other oil as an oil component, the antifouling effect of the antifouling layer comprising the cured product of the resin composition of the present invention may be more fully expressed, In some cases, adhesion of aquatic organisms can be more effectively prevented over a long period of time, and the appearance characteristics and mechanical characteristics of the antifouling layer made of the cured product of the resin composition of the present invention can be more fully expressed.

As the liquid paraffin, any appropriate liquid paraffin can be adopted as long as the effects of the present invention are not impaired. Examples of liquid paraffin include P-40, P-55, P-60, P-70, P-80, P-100, P-120, P-150, P-200, P manufactured by MORESCO. -260, P-350, hydrocarbon liquid paraffin manufactured by Wako Pure Chemical Industries, Ltd.

When the resin composition of the present invention contains liquid paraffin as an oil component, the antifouling effect of the antifouling layer composed of the cured product of the resin composition of the present invention may be more fully expressed, In some cases, the attachment of organisms can be more effectively prevented.

When the resin composition of the present invention contains liquid paraffin as an oil component, the content of liquid paraffin with respect to 100 parts by weight of the silicone resin is preferably 0.1 parts by weight to 50 parts by weight, more preferably 0. It is 5 to 30 parts by weight, more preferably 1 to 25 parts by weight, and particularly preferably 1 to 20 parts by weight. When the content of liquid paraffin with respect to 100 parts by weight of the silicone resin falls within the above range, the antifouling effect of the antifouling layer made of the cured product of the resin composition of the present invention can be more fully expressed, Adhesion can be prevented more effectively.

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

As the anionic surfactant, any appropriate anionic surfactant can be adopted as long as the effects of the present invention are not impaired. Such anionic surfactants include, for example, alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acid or ester salts, alkane sulfonates, Examples thereof include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. Only one type of anionic surfactant may be used, or two or more types may be used.

As the nonionic surfactant, any appropriate nonionic surfactant can be adopted as long as the effects of the present invention are not impaired. Examples of such nonionic surfactants include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester. Examples thereof include esters and alkylamine oxides. Only one nonionic surfactant may be used, or two or more nonionic surfactants may be used.

As the amphoteric surfactant, any appropriate amphoteric surfactant can be adopted as long as the effects of the present invention are not impaired. Examples of such amphoteric surfactants include carboxy type or sulfobetaine type amphoteric surfactants. Only one amphoteric surfactant may be used, or two or more amphoteric surfactants may be used.

As the cationic surfactant, any appropriate cationic surfactant can be adopted as long as the effects of the present invention are not impaired. Examples of such cationic surfactants include quaternary ammonium salts. Only one type of cationic surfactant may be used, or two or more types may be used.

As the antibacterial agent, any appropriate antibacterial agent can be adopted as long as the effects of the present invention are not impaired. Examples of such antibacterial agents include so-called antibacterial agents and herbicides.

The resin composition of the present invention may contain any appropriate other additive as long as the effects of the present invention are not impaired. Examples of such other additives include a UV absorber as a weathering agent. Specific examples of such ultraviolet absorbers include trade names “TINUVIN 571”, “TINUVIN 460”, “TINUVIN 213”, “TINUVIN 234”, “TINUVIN 329”, “TINUVIN 326” manufactured by BASF, and the like. The addition amount of such an ultraviolet absorber is preferably 0.5 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the silicone resin. By adjusting the amount of the ultraviolet absorber added to the silicone resin within the above range, the effect as a weathering agent can be sufficiently exhibited without inhibiting the formation of the antifouling layer. Moreover, a light stabilizer is mentioned as another additive. Specific examples of such light stabilizers include trade names “TINUVIN 123”, “TINUVIN 292”, and “TINUVIN 5100” manufactured by BASF. The addition amount of such a light stabilizer is preferably 0.5 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the silicone resin. By adjusting the amount of the light stabilizer added to the silicone resin within the above range, the effect as the light stabilizer can be sufficiently exhibited without inhibiting the formation of the antifouling layer.

In the antifouling layer, a filler or the like can be added to improve the strength. Examples of the filler include silica particles and diatomaceous earth. Moreover, as a filler, the particle | grains by which the surface was hydrophobized from a dispersible viewpoint are preferable. Examples of such a surface treatment method include a surface treatment method using dimethylpolysiloxane, dimethyldichlorosilane, hexamethylenedisilazane, cyclic dimethylsiloxane, and the like. As the size of the particles whose surface is subjected to hydrophobic treatment, the average particle size is preferably 5 nm to 300 nm. By adjusting the size of the particles whose surface has been subjected to hydrophobic treatment within the above range, sufficient strength can be imparted to the antifouling layer, and the particles can be uniformly dispersed in the antifouling layer. When an impact is applied to the antifouling layer, cracks can hardly occur. In addition, the adhesion between the antifouling layer and the substrate can be improved. The amount of such particles whose surface has been subjected to hydrophobic treatment is preferably 0.1% by weight to 10% by weight with respect to the silicone resin. By adjusting the addition amount of particles whose surface has been subjected to hydrophobic treatment within the above range, it is possible to impart sufficient strength to the antifouling layer and to uniformly disperse added materials such as an antifouling agent. In the case of coating on the base material layer, it can be applied precisely.

Examples of such particles whose surface has been subjected to hydrophobic treatment include hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd., specifically, trade name “AEROSIL (registered trademark) RX” manufactured by Nippon Aerosil Co., Ltd. "Series" (RX50, RX200, RX300, etc.), "AEROSIL (registered trademark) RY series" (RY50, RY200, RY200S, etc.), "AEROSIL (registered trademark) NY50 series", "AEROSIL (registered trademark) NAX series", " AEROSIL (registered trademark) R series "and the like.

≪Anti-fouling material≫
The antifouling material of the present invention has an antifouling layer made of a cured product of the resin composition of the present invention on a substrate. As long as the antifouling material of the present invention has an antifouling layer composed of a cured product of the resin composition of the present invention on the base material, any appropriate other layer is used as long as the effect of the present invention is not impaired. You may have.

The base material is composed of at least one base material layer. That is, the base material layer may be a single layer or a laminate of two or more layers. When the substrate layer is a laminate of two or more layers, the laminate may be formed by, for example, a laminate or may be formed by coextrusion.

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.), acrylic Resin etc. are mentioned. The material of such a base material layer may be only one type or two or more types.

As the base material layer, polyurethane resin is particularly preferable. Examples of such polyurethane resins include ether-based polyurethanes, ester-based polyurethanes, carbonate-based polyurethanes, and the like, and carbonate-based polyurethanes from the viewpoint of excellent durability and strength and sufficient effects of the present invention. Polyurethane is particularly preferred. Moreover, as a grade of a polyurethane resin, a non-yellowing grade and a non-yellowing grade are preferable, and a non-yellowing grade is more preferable.

The base material has an elongation at break of preferably 5% to 1000%, more preferably 20% to 900%, and further preferably 50% to 800%. By adjusting the elongation at break of the base material within the above range, the antifouling material of the present invention, and further, the laminated film of the present invention having the antifouling material of the present invention (described later) can have various shapes of adherends. In addition to being able to follow well, it can be affixed to a flat surface as well as a curved surface portion, a 90-degree angle portion, an acute angle portion, and the like.

The base material has a stress at break of preferably 20 MPa or more, more preferably 25 MPa or more, further preferably 30 MPa or more, and particularly preferably 35 MPa or more. By adjusting the breaking point stress of the base material within the above range, for example, when the antifouling material of the present invention affixed to the adherend and further the laminated film of the present invention (described later) is peeled off from the adherend It can suppress that a base material layer is cut | disconnected by this.

The elongation at break and the stress at break are, for example, in accordance with JIS 7161, JIS 7162, and JIS 7127, a tensile tester (AUTOGRAPH AGS-X, manufactured by Shimadzu Corporation) and analysis software (TRAPEZIUM X, Shimadzu Corporation). Can be used.

Any appropriate thickness can be adopted as the thickness of the base material depending on the application and use environment. The thickness of the substrate is preferably 1 μm to 1000 μm, more preferably 10 μm to 800 μm, and still more preferably 20 μm to 500 μm. By adjusting the thickness of the substrate within the above range, the antifouling material of the present invention, and further, the laminated film of the present invention having the antifouling material of the present invention (described later) can have various shapes of adherends. It can follow well and can be well affixed to a flat surface, but can also be affixed well to a curved surface portion, a 90-degree angle portion, an acute angle portion, and the like.

The substrate 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.).

In order to improve the weather resistance of the antifouling material of the present invention, and further the laminated film (described later) of the present invention having the antifouling material of the present invention, the substrate preferably contains an ultraviolet absorber.

In order to further improve the adhesion to the antifouling layer, a primer may be applied in advance to the substrate, or a silane coupling agent or a reactive additive may be added in advance. .

Only one type of primer may be used, or two or more types of primers may be used. A specific primer is X-33-518 (A / B) manufactured by Shin-Etsu Chemical Co., Ltd. For example, X-33-518 (A / B) manufactured by Shin-Etsu Chemical Co., Ltd. is uniformly mixed in advance (mixing ratio A / B = 100/10 parts by weight), and uniformly applied onto the substrate, and the room temperature atmosphere Air dry for about 30 minutes and then dry at 80 ° C. for 10 minutes. The adhesiveness between the substrate and the antifouling layer can be further improved by applying the resin composition containing the compound to the treated surface and drying it.

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

When the substrate contains a silane coupling agent, the content of the silane coupling agent in the substrate is preferably 0.01% by weight to 10% by weight. By adjusting the content ratio of the silane coupling agent in the substrate within the above range, the adhesion between the substrate and the antifouling layer can be further improved.

Only one type of reactive additive may be used, or two or more types may be used. Specific reaction additives include, for example, trade names “KF99” and “KF9901” which are reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.

The content ratio of the reactive additive in the substrate is preferably 0.01% by weight to 5% by weight. By adjusting the content ratio of the reactive additive in the substrate within the above range, the adhesion between the substrate and the antifouling layer can be further improved.

The antifouling material of the present invention can be produced by any appropriate method as long as the antifouling layer comprising the cured product of the resin composition of the present invention can be provided on the substrate. As such a method, preferably, a method for providing an antifouling layer comprising a cured product of the resin composition of the present invention on a substrate by applying the resin composition of the present invention on a substrate and drying it. Is mentioned.

Examples of the method for applying the resin composition of the present invention on a substrate include spraying, brushing, roller, curtain flow, roll, dip, and coater. The antifouling layer is formed by applying the resin composition of the present invention on the substrate by these methods and drying, for example, at a temperature from room temperature to 250 ° C. (preferably from room temperature to 180 ° C.). can do. In particular, it is one of preferred embodiments that a precision coater such as a comma coater is used to apply the resin composition of the present invention to the base material layer.

The thickness of the antifouling layer may be any appropriate thickness depending on the use of the antifouling material of the present invention and the laminated film of the present invention (described later), the usage environment, and the like. The thickness of the antifouling layer is preferably 10 μm to 500 μm, more preferably 20 μm to 500 μm, and still more preferably 50 μm to 500 μm. By adjusting the thickness of the antifouling layer within the above range, the antifouling effect is effective for a sufficiently long time and has excellent handling properties.

The thickness of the antifouling material of the present invention can be any suitable thickness depending on the application and use environment. The thickness of the antifouling material of the present invention is preferably 50 μm to 1000 μm, more preferably 70 μm to 800 μm, and still more preferably 100 μm to 700 μm. By adjusting the thickness of the antifouling material of the present invention within the above range, the antifouling material of the present invention, and further, the laminated film of the present invention having the antifouling material of the present invention (described later) can be applied in various ways. It can follow the shape of the body well and can be affixed not only to a flat surface but also to a curved surface portion, a 90-degree angle portion, an acute angle portion, and the like.

≪Laminated film≫
The laminated film of the present invention has an adhesive layer on the surface opposite to the antifouling layer of the antifouling material of the present invention. That is, the laminated film of the present invention includes an antifouling layer, a base material layer, and an adhesive layer in this order.

The thickness of the laminated film of the present invention is set to any appropriate thickness within a range that does not impair the effects of the present invention, depending on the thickness of each layer included therein. The thickness of the laminated film of the present invention is preferably 100 μm to 2000 μm, more preferably 100 μm to 800 μm, and further preferably 150 μm to 800 μm. By adjusting the thickness of the laminated film of the present invention within the above range, it is possible to provide a laminated film having a sufficient strength and good application workability.

The laminated film of the present invention may have any appropriate other layer as long as the antifouling layer, the base material layer, and the adhesive layer are included in this order, as long as the effects of the present invention are not impaired. .

FIG. 1 shows a schematic sectional view of an example of the laminated film of the present invention. In FIG. 1, the laminated film 100 of this invention contains the antifouling layer 2, the base material layer 3, and the adhesive 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 pressure-sensitive adhesive layer 4.

In an example of the laminated film of the present invention shown in FIG. 1, the laminated film of the present invention includes an antifouling layer, a base material layer, and an adhesive layer in this order, and preferably the antifouling layer, the base material layer, and the adhesive. The layers are laminated directly in this order.

As the pressure-sensitive adhesive layer, any appropriate pressure-sensitive 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. Examples thereof include a pressure-sensitive adhesive and a silicone resin-based pressure-sensitive adhesive. The material of the pressure-sensitive adhesive layer may be only one type or two or more types.

The pressure-sensitive adhesive layer has a 180-degree peel adhesive strength at 23 ° C. and a tensile speed of 300 mm / min, preferably 30 N / 20 mm or less, more preferably 20 N / 20 mm or less, and further preferably 15 N / 20 mm or less. . The laminated film of the present invention can be easily peeled off from the adherend by adjusting the 180 ° peel adhesive strength of the pressure-sensitive adhesive layer at 23 ° C. and a tensile speed of 300 mm / min within the above range. The lower limit of the 180-degree peel adhesive force at 23 ° C. and a tensile speed of 300 mm / min of the pressure-sensitive adhesive layer is preferably 3 N / 20 mm or more from the viewpoint of maintaining sufficient adhesive force. In addition, as a measuring method of 180 degree peel adhesive force, for example, the pressure-sensitive adhesive in the pressure-sensitive adhesive layer of the laminated film to be tested is handed to a polyester film (trade name “S-10”, manufactured by Toray Industries, Inc., thickness 38 μm). Transfer using a roller to make an adhesive sheet with a base material, cut it into a size of 80 mm x 20 mm to make a test piece, and put a glass cloth in an epoxy resin of 30 mm x 100 mm x thickness 2 mm as an adherend Using a plastic FRP plate reinforced, the test piece was attached to the adherend by reciprocating once with a 2 kg roller, and left at 23 ° C. for 30 minutes, and then the initial 180 ° peel adhesive strength was determined as the tensile speed = 300 mm / A method of measuring in min is mentioned.

When the pressure-sensitive adhesive layer is brought into contact with seawater, the compression elastic modulus of the portion of the pressure-sensitive adhesive layer in contact with seawater is preferably 1. It is 1 time or more, More preferably, it is 1.2 times or more, More preferably, it is 1.5 times or more. When the pressure-sensitive adhesive layer is brought into contact with seawater, the compression elastic modulus of the portion of the pressure-sensitive adhesive layer in contact with seawater is 1.1 times or more the compression elastic modulus of the pressure-sensitive adhesive layer before seawater contact. Good adhesiveness can be expressed even in water. When the pressure-sensitive adhesive layer is contacted with seawater, the upper limit of the magnification of the compression elastic modulus of the portion of the pressure-sensitive adhesive layer that is in contact with seawater with respect to the compression elastic modulus of the pressure-sensitive adhesive layer before seawater contact is From the viewpoint, it is preferably 100 times or less. In addition, seawater here means the simulated seawater (artificial seawater) marketed.

As the thickness of the pressure-sensitive adhesive layer, any appropriate thickness can be adopted depending on the use or use environment of the laminated film of the present invention. The thickness of the pressure-sensitive adhesive layer is preferably 10 μm or more. By adjusting the thickness of the pressure-sensitive adhesive layer within the above range, the shape of the adherend can be sufficiently followed, the adhesion area can be secured, and sufficient adhesive strength can be expressed. The upper limit of the thickness of the pressure-sensitive adhesive layer is preferably 200 μm or less from the viewpoint of handleability.

The laminated film of the present invention can be manufactured by any appropriate method. As such a method, for example, (1) after sticking an adhesive layer to a separately prepared base material (becomes a base material layer), the resin composition of the present invention is used as the base material (becomes a base material layer). A method of forming an antifouling layer by coating on the surface opposite to the pressure-sensitive adhesive layer, and (2) applying a pressure-sensitive adhesive layer-forming material on one surface of the base material (which becomes the base material layer) A method of forming an agent layer, and applying the resin composition of the present invention to the other surface of the substrate (becomes a substrate layer) to form an antifouling layer, (3) a substrate layer forming material and an adhesive After the layer forming material is coextruded to form a base material layer / adhesive layer laminate, the resin composition of the present invention is applied onto the surface of the base material layer opposite to the adhesive layer. And a method of forming an antifouling layer.

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

<Anti-fouling test>
The laminated film was cut into a size of 10 cm × 15 cm and attached to a vinyl chloride plate (10 cm × 15 cm). This panel was installed on the pier at the yacht harbor of Harima Pass near the Seto Inland Sea Himeji so that the top surface of the panel overlaps the seawater surface, and all sample attachment surfaces were placed in the daytime. . It was put in from the end of February, and this state was maintained for two and a half months, and then the panel was pulled up and visually observed.
Plant stains such as algae such as green algae and diatoms were observed and evaluated according to the following criteria.
A: Dirt with a thickness of 0.5 mm or more, or the area covered with green algae is less than 20% of the total area of the antifouling film.
○: Dirt having a thickness of 0.5 mm or more, or the area covered with green algae is 20% or more and less than 50% of the entire area of the antifouling film.
Δ: Dirt having a thickness of 0.5 mm or more, or the area covered with green algae is 50% or more and less than 70% of the entire area of the antifouling film.
ΔΔ: Dirt having a thickness of 0.5 mm or more, or the area covered with green algae is 70% or more and less than 90% of the total area of the antifouling film.
X: Dirt with a thickness of 0.5 mm or more, or an area covered with green algae covers 90% or more of the antifouling film.

<Adhesion test>
The state of the cross section when the laminated film was cut with a cutter (depth: depth of the antifouling layer reaching the base material layer, length: about 1.5 cm) was visually observed.
Evaluation was made according to the following criteria.
○: The base material layer and the antifouling layer do not peel off.
X: A base material layer and an antifouling layer peel.

[Example 1]
(Resin composition)
Ultraviolet absorber (Tinvin 571, manufactured by BASF): 2 parts by weight, catalyst (CATPL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.25 parts by weight, polyether-modified silicone oil (trade names “KF6017”, Shin-Etsu Silicone ( 1 part by weight, dimethyl silicone oil (trade name “KF96-100Cs”, manufactured by Shin-Etsu Chemical Co., Ltd.): 79 parts by weight, liquid paraffin (manufactured by Kishida Chemical Co., Ltd.): 5 parts by weight After stirring, the silicone resin (Product A “KE-1950-50”, Liquid A, manufactured by Shin-Etsu Chemical Co., Ltd.) and the silicone resin (Product Name “KE-1950-50”, Liquid B, Shin-Etsu Chemical ( 100 parts by weight in total of A liquid and B liquid were added and stirred to obtain a resin composition (1).

(Anti-fouling material)
The obtained resin composition (1) is coated on the surface of a 100 μm thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 1) An antifouling material (1) having an antifouling layer (1) thereon was obtained. The antifouling layer (1) had a thickness of 100 μm.

(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 illuminance: 3.4 mW / cm ² , cumulative irradiation amount: 2000 mJ / cm ² ) gave a pressure-sensitive adhesive layer (1) having a thickness of 50 μm.

(Laminated film)
The obtained adhesive layer (1) was bonded to the base material layer (1) side of the antifouling material (1) with a hand roller to obtain a laminated film (1).
The configuration of the laminated film (1) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

[Example 2]
(Resin composition)
Other than changing the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as polyether-modified silicone oil to 3 parts by weight, and the product name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as 77 parts by weight as dimethyl silicone oil. Obtained a resin composition (2) in the same manner as in Example 1.

(Anti-fouling material)
The obtained resin composition (2) was applied to the surface of a 100 μm thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 2) An antifouling material (2) having an antifouling layer (2) thereon was obtained. The antifouling layer (2) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (2).

(Laminated film)
The obtained pressure-sensitive adhesive layer (2) was bonded to the base material layer (2) side of the antifouling material (2) with a hand roller to obtain a laminated film (2).
The configuration of the laminated film (2) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 3
(Resin composition)
Other than changing the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as polyether-modified silicone oil to 5 parts by weight, and changing the product name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as 75 parts by weight as dimethyl silicone oil. Obtained a resin composition (3) in the same manner as in Example 1.

(Anti-fouling material)
The obtained resin composition (3) was applied to the surface of a 100 μm thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 3) An antifouling material (3) having an antifouling layer (3) thereon was obtained. The antifouling layer (3) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (3).

(Laminated film)
The obtained adhesive layer (3) was bonded to the base material layer (3) side of the antifouling material (3) with a hand roller to obtain a laminated film (3).
The configuration of the laminated film (3) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 4
(Resin composition)
0.5 weight part of the trade name “KF6016” manufactured by Shin-Etsu Silicone Co., Ltd. as the polyether-modified silicone oil, and 79.5 parts by weight of the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as the dimethyl silicone oil. A resin composition (4) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (4) was applied to the surface of a 100 μm thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 4) An antifouling material (4) having an antifouling layer (4) thereon was obtained. The antifouling layer (4) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (4).

(Laminated film)
The obtained pressure-sensitive adhesive layer (4) was bonded to the base material layer (4) side of the antifouling material (4) with a hand roller to obtain a laminated film (4).
The configuration of the laminated film (4) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 5
(Resin composition)
0.5 weight part of trade name “KF6013” manufactured by Shin-Etsu Silicone Co., Ltd. as polyether-modified silicone oil, and 79.5 parts by weight of trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as dimethyl silicone oil. A resin composition (5) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (5) was applied to the surface of a 100 μm-thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.), and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 5) An antifouling material (5) having an antifouling layer (5) was obtained. The antifouling layer (5) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (5).

(Laminated film)
The obtained adhesive layer (5) was bonded to the base material layer (5) side of the antifouling material (5) with a hand roller to obtain a laminated film (5).
The configuration of the laminated film (5) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 6
(Resin composition)
0.5 weight part of the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as the polyether-modified silicone oil, and 79.5 parts by weight of the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as the dimethyl silicone oil. A resin composition (6) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (6) was applied to the surface of a 100 μm-thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 6) An antifouling material (6) having an antifouling layer (6) thereon was obtained. The antifouling layer (6) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (6).

(Laminated film)
The obtained adhesive layer (6) was bonded to the base material layer (6) side of the antifouling material (6) with a hand roller to obtain a laminated film (6).
The configuration of the laminated film (6) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 7
(Resin composition)
0.1 weight part of trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as polyether-modified silicone oil, and 79.9 weight part of trade name “KF96-100Cs” of Shin-Etsu Chemical Co., Ltd. as dimethyl silicone oil. A resin composition (7) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (7) was applied to the surface of a 100 μm-thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( 7) An antifouling material (7) having an antifouling layer (7) thereon was obtained. The antifouling layer (7) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (7).

(Laminated film)
The obtained adhesive layer (7) was bonded to the base material layer (7) side of the antifouling material (7) with a hand roller to obtain a laminated film (7).
The composition of the laminated film (7) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 8
(Resin composition)
As a polyether-modified silicone oil, 0.05 part by weight of trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd., and 79.95 parts by weight of trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as dimethyl silicone oil are used. A resin composition (8) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (8) was coated on the surface of a 100 μm-thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 8) An antifouling material (8) having an antifouling layer (8) thereon was obtained. The thickness of the antifouling layer (8) was 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (8).

(Laminated film)
The obtained adhesive layer (8) was bonded to the base material layer (8) side of the antifouling material (8) with a hand roller to obtain a laminated film (8).
The composition of the laminated film (8) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 9
(Resin composition)
As a polyether-modified silicone oil, 0.01 part by weight of the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. and 79.99 parts by weight of a trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as the dimethyl silicone oil. A resin composition (9) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (9) was coated on the surface of a 100 μm thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 9) An antifouling material (9) having an antifouling layer (9) thereon was obtained. The thickness of the antifouling layer (9) was 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (9).

(Laminated film)
The obtained adhesive layer (9) was bonded to the base material layer (9) side of the antifouling material (9) with a hand roller to obtain a laminated film (9).
The configuration of the laminated film (9) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 10
(Resin composition)
0.5 weight part of trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as polyether-modified silicone oil, and 29.5 parts by weight of trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as dimethyl silicone oil. A resin composition (10) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (10) was applied to the surface of a 100 μm thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 10) An antifouling material (10) having an antifouling layer (10) thereon was obtained. The antifouling layer (10) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (10).

(Laminated film)
The obtained adhesive layer (10) was bonded to the base material layer (10) side of the antifouling material (10) with a hand roller to obtain a laminated film (10).
The composition of the laminated film (10) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 11
(Resin composition)
0.5 weight part of the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as the polyether-modified silicone oil, and 59.5 parts by weight of the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as the dimethyl silicone oil. A resin composition (11) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (11) was applied to the surface of a 100 μm-thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( 11) An antifouling material (11) having an antifouling layer (11) thereon was obtained. The antifouling layer (11) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (11).

(Laminated film)
The obtained adhesive layer (11) was bonded to the base material layer (11) side of the antifouling material (11) with a hand roller to obtain a laminated film (11).
The configuration of the laminated film (11) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 12
(Resin composition)
A resin composition (12) was obtained in the same manner as in Example 1 except that the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. was changed to 99 parts by weight as dimethyl silicone oil.

(Anti-fouling material)
The obtained resin composition (12) was coated on the surface of a 100 μm-thick TPU substrate (product name: Higress DUS451, manufactured by Seadam Co., Ltd.), and dried at 140 ° C. for 2 minutes, whereby a substrate layer ( 12) An antifouling material (12) having an antifouling layer (12) thereon was obtained. The antifouling layer (12) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (12).

(Laminated film)
The obtained adhesive layer (12) was bonded to the base material layer (12) side of the antifouling material (12) with a hand roller to obtain a laminated film (12).
The configuration of the laminated film (12) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 13
(Resin composition)
0.5 weight part of the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as the polyether-modified silicone oil, and 79.5 parts by weight of the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as the dimethyl silicone oil. A resin composition (13) was obtained in the same manner as in Example 1 except that liquid paraffin (manufactured by Kishida Chemical Co., Ltd.) was changed to 10 parts by weight.

(Anti-fouling material)
The obtained resin composition (13) was applied to the surface of a 100 μm-thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( 13) An antifouling material (13) having an antifouling layer (13) thereon was obtained. The antifouling layer (13) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (13).

(Laminated film)
The obtained adhesive layer (13) was bonded to the base material layer (13) side of the antifouling material (13) with a hand roller to obtain a laminated film (13).
The configuration of the laminated film (13) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 14
(Resin composition)
As a polyether-modified silicone oil, the product name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. is 1.5 parts by weight, and as the dimethyl silicone oil, the product name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. is 58.5 parts by weight. A resin composition (14) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (14) was coated on the surface of a 100 μm-thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( 14) An antifouling material (14) having an antifouling layer (14) thereon was obtained. The antifouling layer (14) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (14).

(Laminated film)
The obtained adhesive layer (14) was bonded to the base material layer (14) side of the antifouling material (14) with a hand roller to obtain a laminated film (14).
The structure of the laminated film (14) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

Example 15
(Resin composition)
0.5 weight part of the trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. as the polyether-modified silicone oil, and 79.5 parts by weight of the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as the dimethyl silicone oil. A resin composition (15) was obtained in the same manner as in Example 1 except that liquid paraffin (manufactured by Kishida Chemical Co., Ltd.) was changed to 15 parts by weight.

(Anti-fouling material)
The obtained resin composition (15) was applied to the surface of a 100 μm-thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( 15) An antifouling material (15) having an antifouling layer (15) thereon was obtained. The antifouling layer (15) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (15).

(Laminated film)
The obtained adhesive layer (15) was bonded to the base material layer (15) side of the antifouling material (15) with a hand roller to obtain a laminated film (15).
The configuration of the laminated film (15) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

[Comparative Example 1]
(Resin composition)
In the same manner as in Example 1, except that the polyether-modified silicone oil was not used and the trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. was changed to 80 parts by weight as dimethyl silicone oil. C1) was obtained.

(Anti-fouling material)
The obtained resin composition (C1) was coated on the surface of a 100 μm thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( An antifouling material (C1) having an antifouling layer (C1) on C1) was obtained. The antifouling layer (C1) had a thickness of 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (C1).

(Laminated film)
The obtained adhesive layer (C1) was bonded to the base material layer (C1) side of the antifouling material (C1) with a hand roller to obtain a laminated film (C1).
The configuration of the laminated film (C1) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

[Comparative Example 2]
(Resin composition)
Other than changing the brand name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. to 6 parts by weight as polyether-modified silicone oil, and the product name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. to 74 parts by weight as dimethyl silicone oil. In the same manner as in Example 1, a resin composition (C2) was obtained.

(Anti-fouling material)
The obtained resin composition (C2) was coated on the surface of a 100 μm thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.) and dried at 140 ° C. for 2 minutes, whereby a base material layer ( An antifouling material (C2) having an antifouling layer (C2) on C2) was obtained. The thickness of the antifouling layer (C2) was 100 μm.

(Adhesive layer)
It carried out similarly to Example 1 and obtained the adhesive layer (C2).

(Laminated film)
The obtained pressure-sensitive adhesive layer (C2) was bonded to the base material layer (C2) side of the antifouling material (C2) with a hand roller to obtain a laminated film (C2).
The configuration of the laminated film (C2) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

[Comparative Example 3]
(Resin composition)
As a polyether-modified silicone oil, 0.005 parts by weight of a trade name “KF6017” manufactured by Shin-Etsu Silicone Co., Ltd. and 79.995 parts by weight of a trade name “KF96-100Cs” manufactured by Shin-Etsu Chemical Co., Ltd. as a dimethyl silicone oil. A resin composition (C3) was obtained in the same manner as in Example 1 except for changing to.

(Anti-fouling material)
The obtained resin composition (C3) was coated on the surface of a 100 μm thick TPU base material (product name: Higress DUS451, manufactured by Seadam Co., Ltd.), and dried at 140 ° C. for 2 minutes, whereby a base material layer ( An antifouling material (C3) having an antifouling layer (C3) on C3) was obtained. The antifouling layer (C3) had a thickness of 100 μm.

(Adhesive layer)
It carried out like Example 1 and obtained an adhesive layer (C3).

(Laminated film)
The obtained pressure-sensitive adhesive layer (C3) was bonded to the base material layer (C3) side of the antifouling material (C3) with a hand roller to obtain a laminated film (C3).
The configuration of the laminated film (C3) was antifouling layer (thickness = 100 μm) / base material layer (thickness = 100 μm) / adhesive layer (thickness = 50 μm).
The evaluation results are shown in Table 1.

[Comparative Example 4]
A vinyl chloride plate (trade name “Hishi Plate”, manufactured by Mitsubishi Plastics, Inc.) was evaluated.
The evaluation results are shown in Table 1.

The resin composition of the present invention, the antifouling material of the present invention, and the laminated film of the present invention can prevent underwater organisms from attaching and breeding, so that underwater structures (ships, buoys, harbor facilities, offshore oil fields) Facilities, power plant cooling water channels, factory cooling water channels, water floating passages, etc.).

DESCRIPTION OF SYMBOLS 1 Release film 2 Antifouling layer 3 Base material layer 4 Adhesive layer 100 Laminated film

Claims (10)

1. A resin composition comprising a silicone resin and an oil component,
   The oil component comprises silicone oil;
   At least one of the silicone oils is a polyether-modified silicone oil;
   The content of the polyether-modified silicone oil with respect to 100 parts by weight of the silicone resin is 0.01 to 5 parts by weight.
   Resin composition.
2. 2. The resin composition according to claim 1, wherein the content of the silicone resin relative to 100 parts by weight of the resin composition is 30 to 98 parts by weight.
3. The resin composition according to claim 2, wherein the content is 50 to 95 parts by weight.
4. 2. The resin composition according to claim 1, wherein the content of the oil component is 0.01 to 120 parts by weight with respect to 100 parts by weight of the resin composition.
5. The resin composition according to claim 4, wherein the content is 1 to 100 parts by weight.
6. The resin composition according to claim 1, wherein the silicone resin is a two-pack type addition silicone resin.
7. 2. The resin composition according to claim 1, wherein a content of the polyether-modified silicone oil is 0.1 to 5 parts by weight with respect to 100 parts by weight of the silicone resin.
8. The resin composition according to claim 1, wherein the polyether-modified silicone oil is a side-chain type (linear type) polyether-modified silicone oil in which a polyoxyalkylene group is bonded to a side chain.
9. An antifouling material having an antifouling layer comprising a cured product of the resin composition according to any one of claims 1 to 8 on a substrate.
10. A laminated film having an adhesive layer on the surface opposite to the antifouling layer of the antifouling material according to claim 9.

Images