Antifouling coating composition

Abstract

The object of the present invention is to provide an antifouling coating composition which can form an antifouling coating film having excellent adhesion to a substrate (base material) even in a low temperature environment and excellent antifouling properties. In addition, another object of the present invention is to provide an antifouling coating film, a laminated antifouling coating film, an antifouling tape, a substrate with an antifouling coating film, a method for producing the same, and an antifouling method formed by the antifouling coating composition. The antifouling coating composition of the present invention contains a photocurable organopolysiloxane (A), a slip agent (B), and a photopolymerization initiator (C), and the content of the photocurable organopolysiloxane (A) in the solid content of the antifouling coating composition is 50% by mass or more and 98% by mass or less.

Description

Technical Field

[0001] The present invention relates to an antifouling coating composition, an antifouling coating film using the antifouling coating composition, a laminated antifouling coating film, an antifouling tape, a substrate with an antifouling coating film, a method for producing the same, and an antifouling method. Background Art

[0002] Organopolysiloxane antifouling coatings are widely used to prevent aquatic organisms from attaching to ships, underwater structures, fishery materials, etc. Due to their low surface free energy, low elastic modulus and other characteristics, these antifouling coatings have the following advantages: they can prevent the attachment and fixation of macroscopic organisms such as barnacles and mussels, and they also have a lower burden on the environment than conventional antifouling coatings such as hydration-decomposition type and hydrolysis type that release coating components into the environment.

[0003] For example, Patent Document 1 discloses an antifouling coating film formed from a curable polysiloxane composition.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2014 / 077204 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The organopolysiloxane antifouling coating can reduce the adhesion of aquatic organisms, but on the other hand, the adhesion to the substrate is also low, and it is difficult to obtain a strong adhesion to the substrate. This tendency becomes particularly significant in a low temperature environment (e.g., 5° C.), and as in the aforementioned Patent Document 1, a special primer coating is required. Even if the antifouling coating is used, there are difficulties such as a long coating interval from the application of the primer to the application of the antifouling coating composition.

[0009] The object of the present invention is to provide an antifouling coating composition which can form an antifouling coating film having excellent adhesion to a substrate (base material) even under a low temperature environment and excellent antifouling properties. In addition, another object of the present invention is to provide an antifouling coating film, a laminated antifouling coating film, an antifouling tape, a substrate with an antifouling coating film, a method for producing the same, and an antifouling method formed from the antifouling coating composition.

[0010] Means for solving problems

[0011] The present inventors have conducted intensive studies in view of the above-mentioned problems and have found that a coating film formed by an antifouling coating composition containing a photocurable organopolysiloxane (A), a slip agent (B) and a photopolymerization initiator (C) has good adhesion to a substrate even at low temperatures and is excellent in antifouling properties, thereby completing the present invention.

[0012] The present invention relates to the following [1] to

[16] .

[0013] [1] An antifouling coating composition comprising a photocurable organopolysiloxane (A), a slip agent (B) and a photopolymerization initiator (C), wherein the content of the photocurable organopolysiloxane (A) in the solid content of the antifouling coating composition is 50% by mass or more and 98% by mass or less.

[0014] [2] The antifouling coating composition according to [1], wherein the photocurable organopolysiloxane (A) has a (meth)acryloyl group.

[0015] [3] The antifouling coating composition according to [1] or [2], wherein the photocurable organopolysiloxane (A) is represented by the following formula (I).

[0016] X p R 1 (3-p) SiO(SiR 1 2 O) m (SiX q R 1 (2-q) O) n SiX p R 1 (3-p) (I)

[0017] (In formula (I), R 1 Each independently represents an alkyl group, aryl group, aralkyl group, alkoxy group or halogenated alkyl group having 1 to 10 carbon atoms, each X independently represents a monovalent organic group having one or more (meth)acryloyl groups and containing no silicon atoms, m represents 10 to 10000, n represents 0 to 50, each p independently represents an integer of 0 to 2, each q independently represents 1 or 2, and at least one of p and n is 1 or more.)

[0018] [4] The antifouling coating composition according to any one of [1] to [3], wherein the weight average molecular weight (Mw) of the photocurable organopolysiloxane (A) is 10,000 or more and 100,000 or less.

[0019] [5] The antifouling coating composition according to any one of [1] to [4], wherein the functional group equivalent of the photocurable organopolysiloxane (A) is 300 g / mol or more and 50,000 g / mol or less.

[0020] [6] The antifouling coating composition according to any one of [1] to [5], wherein the slip agent (B) is at least one selected from phenyl-modified silicone, polyether-modified silicone and acrylic polymer having a hydrophilic group.

[0021] [7] The antifouling coating composition according to any one of [1] to [6], wherein the content of the slip agent (B) in the solid content of the antifouling coating composition is 0.1% by mass or more and 40% by mass or less.

[0022] [8] The antifouling coating composition according to any one of [1] to [7], wherein the total content of the photocurable organopolysiloxane (A) and the slip agent (B) in the solid content of the antifouling coating composition is 70% by mass or more and 99% by mass or less.

[0023] [9] The antifouling coating composition according to any one of [1] to [8], further comprising a silane coupling agent (D).

[0024]

[10] An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [9].

[0025]

[11] A laminated antifouling coating film comprising a primer coating film and the antifouling coating film according to

[10] .

[0026]

[12] An antifouling tape comprising the antifouling coating film described in

[10] or the laminated antifouling coating film described in

[11] and an adhesive layer.

[0027]

[13] A substrate with an antifouling coating film, comprising the antifouling coating film described in

[10] , the laminated antifouling coating film described in

[11] or the antifouling tape described in

[12] on the substrate.

[0028]

[14] The substrate with an antifouling coating according to

[13] , wherein the substrate is one selected from the group consisting of ships, underwater structures, fishery materials, and cables.

[0029]

[15] A method for producing a substrate with an antifouling coating film, comprising the steps of applying the antifouling coating composition according to any one of [1] to [9] to a substrate, and irradiating the applied coating film with active energy rays.

[0030]

[16] An antifouling method using the antifouling coating film described in

[10] , the laminated antifouling coating film described in

[11] , or the antifouling tape described in

[12] .

[0031] Effects of the Invention

[0032] According to the present invention, there can be provided an antifouling coating composition capable of forming an antifouling coating film having excellent adhesion to a substrate (base material) even under a low temperature environment and excellent antifouling properties. In addition, according to the present invention, there can be provided an antifouling coating film, a laminated antifouling coating film, an antifouling tape, a substrate with an antifouling coating film, a method for producing the same, and an antifouling method. DETAILED DESCRIPTION

[0033] Hereinafter, the antifouling coating composition of the present invention, the antifouling coating film using the antifouling coating composition, the laminated antifouling coating film, the antifouling tape, the substrate with the antifouling coating film, the production method thereof, and the antifouling method are described in detail.

[0034] It should be noted that in the following description, "(meth)acryloyl", "(meth)acrylate", "(meth)acrylic acid" and "(meth)acrylic acid" respectively refer to "acryloyl and / or methacryloyl", "acrylate and / or methacrylate", "acrylic acid and / or methacrylic acid" and "acrylic acid and / or methacrylic acid".

[0035] [Antifouling coating composition]

[0036] The antifouling coating composition of the present invention (hereinafter also referred to as "the present composition" or "coating composition") is characterized in that it contains a photocurable organopolysiloxane (A), a slip agent (B) and a photopolymerization initiator (C), and the content of the photocurable organopolysiloxane (A) in the solid content of the antifouling coating composition is 50% by mass or more and 98% by mass or less.

[0037] According to the present invention, an antifouling coating composition can be provided, which can form an antifouling coating film having excellent adhesion to a substrate (base material) even in a low temperature environment and excellent antifouling properties. In addition, if the antifouling coating of the present invention is used, antifouling construction including the formation of an antifouling coating film can be completed in a short time. In particular, in the construction operation of a ship, the economic burden of the dockage fee required according to the operation time can be reduced, which is a great advantage.

[0038] It should be noted that, although the detailed mechanism of action that can achieve the above-mentioned effect may not be clear, a part of it can be speculated as follows. That is, it can be considered that in order to inhibit biological attachment in water, the previous organopolysiloxane-based antifouling coating needs to be combined with a slip agent, which promotes the aquatic organisms to slide off the surface by using the water flow generated when the substrate moves in the water or the water flow generated in the water when the aquatic organisms come into contact with the coating surface and in the stage of growth on the surface after contact. On the other hand, the slip agent is usually liquid at room temperature (hereinafter 25°C) or becomes liquid due to interaction with water in the external environment. In addition, in order to function as a slip agent, it is necessary to have a certain difference in polarity with the curable organopolysiloxane used in combination. Therefore, even if the curable organopolysiloxane and the lubricant are in a certain mixed state or slightly separated state due to the mixing operation before applying the coating composition, phase separation will be promoted before the applied coating composition is dried and solidified, and the liquid lubricant will be concentrated near the base (substrate). In the worst case, a liquid layer is formed, which may hinder the adhesion to the base (substrate). In particular, under low temperature environment, the compatibility of components with different polarity decreases, and phase separation is easy to promote, so the influence caused by the above phenomenon becomes significant.

[0039] However, it is considered that the use of the photocurable organopolysiloxane (A) in the present composition can significantly shorten the drying and curing time, thereby suppressing the occurrence of the above-mentioned phase separation phenomenon and enabling good adhesion to the base (substrate).

[0040] <Photocurable organopolysiloxane (A)>

[0041] The present composition contains a photocurable organopolysiloxane (A) for the purpose of improving the substrate adhesion in a low-temperature environment (hereinafter also referred to as "low-temperature adhesion") and the antifouling property of the formed antifouling coating film.

[0042] The photocurable organopolysiloxane (A) is an organopolysiloxane compound that initiates polymerization using active species such as free radicals generated from a photopolymerization initiator (C) described later by irradiation with active energy rays. The proportion of the organopolysiloxane in the molecule of the photocurable organopolysiloxane (A) is preferably 50% by mass or more, and more preferably 70% by mass or more, from the viewpoint of good antifouling properties of the antifouling coating film formed.

[0043] As the photocurable organopolysiloxane (A), there can be mentioned a photoradical-curable organopolysiloxane in which the active species generated by irradiation with active energy rays for initiating polymerization are free radicals, a photocationic-curable organopolysiloxane in which the active species are cations, and a photoanion-curable organopolysiloxane in which the active species are anions. From the perspective of the curability of the coating composition, the strength and durability of the formed coating film, and the low environmental burden, a photoradical-curable organopolysiloxane is preferred, while from the perspective of better adhesion to the substrate and less susceptible to curing inhibition by oxygen, a photocationic-curable organopolysiloxane and a photoanion-curable organopolysiloxane are preferred.

[0044] When the photocurable organopolysiloxane (A) is a photoradical-curable organopolysiloxane, it is preferably an organopolysiloxane having a (meth)acryloyl group, for example, a compound represented by the following formula (I), from the viewpoint that the antifouling coating composition has suitable storage stability, usable life and curability, and the formed antifouling coating film exhibits good low-temperature adhesion and antifouling properties.

[0045] It should be noted that, as the photo-radical polymerizable group, vinyl, allyl etc. can also be exemplified, but from the viewpoint of curability, as the photo-radical polymerizable group, (meth) acryloyl is preferred. In addition, the free radical polymerizability of the vinyl directly bonded to the silicon atom is low, so in the present invention, the vinyl directly bonded to the silicon atom is not a group equivalent to the photo-radical polymerizable group.

[0046] X p R 1 (3-p) SiO(SiR 1 2 O) m (SiX q R 1 (2-q) O) n SiX p R 1 (3-p) (I)

[0047] (In formula (I), R 1 Each independently represents an alkyl group, aryl group, aralkyl group, alkoxy group or halogenated alkyl group having 1 to 10 carbon atoms, each X independently represents a monovalent organic group having one or more (meth)acryloyl groups and containing no silicon atoms, m represents 10 to 10000, n represents 0 to 50, each p independently represents an integer of 0 to 2, each q independently represents 1 or 2, and at least one of p and n is 1 or more.)

[0048] In formula (I), R 1 Each independently represents an alkyl group, aryl group, aralkyl group, alkoxy group or halogenated alkyl group having 1 to 10 carbon atoms.

[0049] R 1 The number of carbon atoms of the alkyl group in is 1 to 10, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl.

[0050] R 1 The aryl group in has 6 to 10 carbon atoms and may have a substituent such as an alkyl group on the aromatic ring. Examples thereof include phenyl, tolyl (methylphenyl), xylyl (dimethylphenyl) and naphthyl.

[0051] R 1 The aralkyl group in the group has 7 to 10 carbon atoms, and examples thereof include benzyl, 2-phenylethyl, 2-naphthylethyl, and diphenylmethyl.

[0052] R 1 The number of carbon atoms of the halogenated alkyl group is 1 to 10, and examples thereof include groups in which a part or all of the hydrogen atoms contained in the above alkyl group are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0053] Among them, R in formula (I) 1 An alkyl group, an aryl group, an aralkyl group, or a halogenated alkyl group is preferred, an alkyl group or an aryl group is more preferred, and a methyl group is further preferred.

[0054] It should be noted that in this manual, 1 When a plurality of the same groups exist, they may be the same or different.

[0055] In formula (I), X each independently represents a monovalent organic group having one or more (meth)acryloyl groups and containing no silicon atom, and is preferably a group having an acryloyl group, and more preferably a group having an acryloyloxy group, from the viewpoint of improving the curability of the coating composition.

[0056] X is preferably a group represented by the following formula (II).

[0057] [Chemistry 1]

[0058]

[0059] (In formula (II), R 2 Each independently represents a hydrogen atom or a methyl group, R 3 represents a (1+x)-valent hydrocarbon group having 2 to 100 carbon atoms, R 3Any methylene group of the hydrocarbon group may be replaced by an ether bond, an ester bond, a thioether bond, a carbamate bond or an amide bond, a part of the hydrogen atoms of the hydrocarbon group may be replaced by a hydroxyl group or a halogen atom, and x represents an integer of 1 to 10.

[0060] In formula (II), R 2 It is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0061] R 3 The (1+x)-valent hydrocarbon group having 2 to 100 carbon atoms preferably has 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and further preferably 2 to 10 carbon atoms.

[0062] R 3 Any methylene group in may be replaced by an ether bond, an ester bond, a thioether bond or an amide bond, preferably by an ether bond or an ester bond, more preferably by an ether bond.

[0063] x is an integer of 1 to 10, and is preferably 1 or 2.

[0064] Examples of X include the following (IIa) to (IIg).

[0065] [Chemistry 2]

[0066]

[0067] [Chemistry 3]

[0068]

[0069] Among them, (IIa) to (IIf) are preferred, and (IIb) and (IId) are more preferred.

[0070] It should be noted that, in this specification, when two or more different repeating units are described side by side between [], it means that these repeating units can be repeated in any form and order of random, alternating or block. 3 -Y 3 ]- (wherein X and Y represent repeating units), it can be a random form like -XXYXYY-, an alternating form like -XYXYXY-, or a block form like -XXXYYY- or -YYYXXX-.

[0071] In formula (I), m is 10 or more and 10000 or less, and is preferably 100 or more, more preferably 200 or more, and is preferably 1000 or less, more preferably 500 or less, from the viewpoint of improving the physical properties and antifouling properties of the antifouling coating film formed, such as flexibility, stretchability, substrate followability, strength, and impact resistance.

[0072] In formula (I), n represents 0 or more and 50 or less. In the case where p described later is 0, n is 1 or more and 50 or less. For the same reasons as above, n is preferably 2 or more and 20 or less, and n / m is preferably 0 or more and 1 / 5 or less, more preferably 0 or more and 1 / 20 or less, and further preferably 0 or more and 1 / 50 or less.

[0073] In addition, m and n refer to the average repetition number of the corresponding partial structure, and can be adjusted appropriately so as to satisfy the following weight average molecular weight.

[0074] In formula (I), p is independently an integer of 0 or more and 2 or less, and when n is 0, at least one p is 1 or 2.

[0075] On the other hand, when the photocurable organopolysiloxane (A) is a photocationic curable organopolysiloxane, an organopolysiloxane having a glycidyl group in the molecule can be used, and on the other hand, when it is a photoanionic curable organopolysiloxane, an organopolysiloxane having a glycidyl group or a cyanoacrylate group in the molecule can be used.

[0076] The weight average molecular weight (Mw) of the photocurable organopolysiloxane (A) is usually 5,000 or more and 200,000 or less, and is preferably 10,000 or more, more preferably 12,000 or more, and further preferably 15,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, and further preferably 50,000 or less, from the viewpoint of improving the production operability, coating operability, and curability of the coating composition and the strength of the antifouling coating film formed.

[0077] In addition, the number average molecular weight of the photocurable organopolysiloxane (A) is preferably 3,000 or more, more preferably 4,000 or more, and further preferably 5,000 or more, and is preferably 50,000 or less, more preferably 30,000 or less, and further preferably 20,000 or less, from the viewpoint of improving the production workability, coating workability, curability of the coating composition, and the strength of the antifouling coating film formed.

[0078] In the present invention, the "weight average molecular weight (Mw)" and "number average molecular weight (Mn)" of the photocurable organopolysiloxane (A), other oligomers described later, the polymer (N), etc. are measured using GPC (gel permeation chromatography) and calculated in terms of standard polystyrene having a known molecular weight.

[0079] The functional group equivalent (mass per 1 mol of curable functional groups) of the photocurable organopolysiloxane (A) is preferably 300 g / mol or more, more preferably 500 g / mol or more, further preferably 700 g / mol or more, further preferably 1000 g / mol or more, and is preferably 50000 g / mol or less, more preferably 30000 g / mol or less, further preferably 20000 g / mol or less, further preferably 15000 g / mol or less, and particularly preferably 10000 g / mol or less, from the viewpoint of improving the curability and the strength and antifouling properties of the antifouling coating film formed.

[0080] In addition, when using 2 or more types of photocurable organopolysiloxanes (A), it is preferable that the functional group equivalent of the photocurable organopolysiloxane (A) as a whole is in the above-mentioned range.

[0081] The functional group equivalent can be approximated by a value obtained by dividing the number average molecular weight by the number of functional groups per molecule.

[0082] In addition, the viscosity of the photocurable organopolysiloxane (A) at 23°C is preferably 100 mPa·s or more, more preferably 200 mPa·s or more, and is preferably 50000 mPa·s or less, more preferably 2000 mPa·s or less, from the viewpoint of improving the manufacturing operability, coating operability, curing properties of the coating composition and the strength of the antifouling coating film formed.

[0083] In addition, the viscosity of the photocurable organopolysiloxane (A) at 23° C. in this specification refers to the viscosity measured by a B-type rotational viscometer (for example, Model BM, manufactured by Tokyo Keiki Co., Ltd.).

[0084] The photocurable organopolysiloxane (A) may be used alone or in combination of two or more. In the following description, when two or more are used in combination, the preferred content is a preferred range of the total amount of the components.

[0085] The content of the photocurable organopolysiloxane (A) in the coating composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of improving the antifouling property and strength of the antifouling coating film formed.

[0086] The content of the photocurable organopolysiloxane (A) in the solid content of the antifouling coating composition is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and is 98% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less.

[0087] It should be noted that the "solid content of the coating composition" in this specification refers to the components other than the non-reactive solvent (E) described later and the volatile components contained as solvents in each component, and the "solid content of the coating composition" can be calculated as the content in the residue obtained by drying the coating composition in a hot air dryer at 125°C for 1 hour.

[0088] Therefore, the "solid content of the coating composition" is not necessarily in a solid state, and may be in a liquid state.

[0089] In addition, the total content of the photocurable organopolysiloxane (A) and the slip agent (B) described below in the solid content of the antifouling coating composition of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, from the viewpoint of improving the antifouling properties and strength of the antifouling coating film formed.

[0090] As the photocurable organopolysiloxane (A), a commercially available product can be used. Examples of the commercially available product include "TEGO Rad 2650" manufactured by Evonik Industries AG (in the formula (I), R 1 methyl, all p's are 1, n's are 0, X is a group represented by formula (IId) (a=3), Mw: 17000, viscosity (23°C): 380 mPa·s), "SILMEROH ACR C50" manufactured by Siltech (R 1 is methyl, all p is 0, q is 1, n is 3, X is a group represented by formula (IIb) (a=3), Mw: 24000, viscosity (23°C): 550 mPa·s), "SILMER OH ACR Di-400" (R 1 is a methyl group, all p's are 1, n's are 0, X is a group represented by formula (IIb) (a=3), Mw: 31000, viscosity (23°C): 1030 mPa·s), etc.

[0091] <Slip agent (B)>

[0092] The present composition contains a slip agent (B).

[0093] The slip agent (B) imparts slip properties to the antifouling coating film formed, thereby improving the adhesion barrier (antifouling property) of aquatic organisms. In addition, by making the present composition contain the slip agent (B), the surface of the antifouling coating film is easily smooth in water, thereby reducing damage to the substrate covered by the antifouling coating film when it comes into contact with floating objects, etc., and improving the workability when installing the substrate (antifouling coating of cables used in water, etc.).

[0094] The content of the slip agent (B) in the solid content of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of improving the antifouling property of the antifouling coating film formed.

[0095] The slip agent (B) preferably has fluidity at 25°C, and is more preferably in a liquid state. It is believed that by making the slip agent (B) fluid, the mobility in the antifouling coating film is high, and the effect of easy sliding on the surface (slipperiness) can be improved. In addition, the viscosity of the antifouling coating composition described later can be reduced to improve the coating property.

[0096] The lubricant (B) is preferably at least one selected from oils and polymers having a hydrophilic group.

[0097] Examples of the oils include silicone oils other than the photocurable organopolysiloxane (A), paraffin oils, and fats. Among them, silicone oils are preferred.

[0098] Examples of the paraffin oil include liquid paraffin and the like.

[0099] The fats and oils are esters of fatty acids and glycerol, and examples thereof include animal fats and oils and vegetable fats and oils.

[0100] Examples of the polymer having a hydrophilic group include acrylic polymers and polyalkylene glycols having a hydrophilic group, from the viewpoint of the antifouling properties and adhesion of the antifouling coating film to be formed. Preferably, the polymer has an acrylic polymer having a hydrophilic group.

[0101] Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, and alkyl ethers thereof.

[0102] That is, the lubricant (B) is preferably one or more selected from silicone oil, paraffin oil, grease, acrylic polymer having a hydrophilic group and polyalkylene glycol, more preferably one or more selected from silicone oil and acrylic polymer having a hydrophilic group, and further preferably one or more selected from phenyl-modified silicone, polyether-modified silicone and acrylic polymer having a hydrophilic group. In addition, from the viewpoint of excellent coating workability and good antifouling property and damage resistance of the formed antifouling coating film, it is also preferred to contain both silicone oil and acrylic polymer having a hydrophilic group.

[0103] Silicone oil and acrylic polymer having a hydrophilic group as suitable lubricant (B) are described in detail below.

[0104] 〔Silicone oil (B1)〕

[0105] Examples of the silicone oil (B1) used in the antifouling coating composition of the present invention include dimethyl silicone (polydimethylsiloxane, unmodified silicone) and modified silicone. Modified silicone is a material in which a part of the methyl groups of dimethyl silicone is replaced by an organic group other than a methyl group, and is a material that substantially does not contain a photocurable reactive group like the aforementioned photocurable organopolysiloxane (A).

[0106] Silicone oil has low surface tension and its properties are not easily changed even in low-temperature environments. Therefore, it easily migrates to the surface of the antifouling coating film and can effectively improve the adhesion prevention of aquatic organisms (antifouling properties) and damage resistance.

[0107] The viscosity of the silicone oil (B1) at 25°C is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, further preferably 40 mPa·s or more, further preferably 60 mPa·s or more, further preferably 80 mPa·s or more, and is preferably 50000 mPa·s or less, more preferably 20000 mPa·s or less, further preferably 10000 mPa·s or less, from the viewpoint of being able to improve the coating properties of the antifouling coating composition, imparting slip properties to the formed antifouling coating film, and improving the antifouling properties.

[0108] In addition, in this specification, the viscosity of the silicone oil (B1) at 25°C means the viscosity measured by a B-type rotational viscometer.

[0109] The kinematic viscosity of the silicone oil (B1) at 25° C. is preferably 10 mm / s from the viewpoint of improving the coating properties of the antifouling coating composition, imparting slidability to the formed antifouling coating film, and improving the antifouling properties. 2 / sec or more, more preferably 20 mm 2 / sec or more, more preferably 40 mm 2 / sec or more, more preferably 60 mm 2 / sec or more, more preferably 80 mm 2 / sec or more, and preferably 50000 mm 2 / sec or less, more preferably 20000 mm 2 / sec or less, more preferably 10000 mm 2 / second or less.

[0110] In addition, in this specification, the kinematic viscosity at 25 degreeC of silicone oil (B1) means the viscosity measured with the Ubbelohde viscometer based on JIS Z8803:2011.

[0111] Examples of the modified silicone include phenyl-modified silicone, polyether-modified silicone, long-chain alkyl-modified silicone, higher fatty acid ester-modified silicone, fluoroalkyl-modified silicone, carbinol-modified silicone, carboxyl-modified silicone, amino-modified silicone, mercapto-modified silicone, and phenol-modified silicone.

[0112] Among such modified silicones, from the viewpoint of imparting appropriate thixotropy to the antifouling coating composition, improving coating properties, and improving antifouling properties and scratch resistance of the formed antifouling coating film, the silicone oil (B1) is preferably at least one selected from phenyl-modified silicones and polyether-modified silicones, more preferably polyether-modified silicones, and preferably a combination of phenyl-modified silicones and polyether-modified silicones.

[0113] Examples of the structure of the modified silicone include a side chain modified type, a double terminal modified type, a single terminal modified type, a block type, and a side chain and double terminal modified type.

[0114] As the dimethyl silicone, a commercially available product can be used. Examples of the commercially available product include "KF-96-1000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25° C.): 1000 mm 2 / second) etc.

[0115] The phenyl modification rate of the phenyl-modified silicone is preferably 3% or more, more preferably 4% or more, and preferably 50% or less, more preferably 20% or less, and further preferably 10% or less, from the viewpoint of facilitating the formation of the antifouling coating film and improving the antifouling property of the formed antifouling coating film. The phenyl modification rate is a value expressing the number of phenyl groups relative to the total number of phenyl groups and methyl groups bonded to silicon as a percentage.

[0116] The kinematic viscosity of the phenyl-modified silicone at 25° C. is preferably 10 mm / s from the viewpoint of improving the coating workability of the antifouling coating composition and the antifouling property of the formed antifouling coating film. 2 / sec or more, more preferably 30 mm 2 / sec or more, more preferably 50 mm 2 / sec or more, and preferably 50000 mm 2 / sec or less, more preferably 10000 mm 2 / sec or less, more preferably 6000 mm 2 / second or less.

[0117] As the phenyl-modified silicone, a commercially available product can be used. Examples of the commercially available product include "KF-50-1000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25° C.): 1000 mm 2 / sec), "KF-50-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25°C): 100 mm 2 / second) etc.

[0118] When the present composition contains phenyl-modified silicone, the content in the solid content of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of improving the antifouling properties, formation efficiency, and scratch resistance of the antifouling coating film.

[0119] Examples of the structure of the polyether-modified silicone include a side chain modified type, a double terminal modified type, a block type, and a side chain and double terminal modified type. A side chain modified type and a double terminal modified type are preferred.

[0120] Examples of the polyether (polyalkylene glycol) constituting the polyether group (polyalkylene glycol group) of the polyether-modified silicone include polyethylene glycol, polypropylene glycol, and a copolymer of ethylene glycol and propylene glycol, and polyethylene glycol is preferred.

[0121] In the polyether-modified silicone, from the viewpoint of facilitating the formation of an antifouling coating film and improving the antifouling property of the formed antifouling coating film, the proportion of the polyether partial structure in the structure is preferably 10% by mass or more, more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less.

[0122] When the antifouling coating composition contains a polyether-modified silicone, the content of the polyether-modified silicone in the solid content of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less, from the viewpoint of facilitating the formation of an antifouling coating film and improving the antifouling properties of the formed antifouling coating film.

[0123] The composition contains ethyleneoxy (-C 2 H 4 O-) structural unit and / or the polyether-modified silicone having a vinyloxy group (-C 2 H 4 In the case of an acrylic polymer (B2) having a hydrophilic group having a polysiloxane structure (-(CH 3 ) 2 Si-O-) 100 parts by mass, ethyleneoxy (-C 2 H 4 The total mass of the (O-) partial structures is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

[0124] The dimethylsiloxane partial structure includes dimethylsiloxane partial structures derived from the aforementioned photocurable organopolysiloxane (A), silicone oil (B1), the organopolysiloxane (N1) described below, and other photocurable oligomers and polymers (N2).

[0125] The kinematic viscosity of the polyether-modified silicone at 25° C. is preferably 10 mm / s from the viewpoint of improving the coating workability of the antifouling coating composition and the antifouling property of the formed antifouling coating film. 2 / sec or more, preferably 50 mm 2 / sec or more, more preferably 100 mm 2 / sec or more, and preferably 5000 mm 2 / sec or less, more preferably 2000 mm 2 / sec or less, more preferably 500 mm 2 / second or less.

[0126] Commercially available products can be used as polyether-modified silicones. Examples of such commercially available products include "X-22-4272" (manufactured by Shin-Etsu Chemical Co., Ltd., dual-end type, kinematic viscosity (25° C.): 270 mm 2 / sec), “KF-6020” (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type, ratio of polyether partial structure = 20 mass%, kinematic viscosity (25° C.): 180 mm 2 / sec), "FZ-2203" (manufactured by Dow Corning Toray Co., Ltd., side chain type), "FZ-2160" (manufactured by Dow Corning Toray Co., Ltd., block type), etc.

[0127] When the present composition contains the silicone oil (B1), the content in the solid content of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, from the viewpoint of facilitating the formation of the antifouling coating film and improving the antifouling properties of the formed antifouling coating film.

[0128] [Acrylic polymer having a hydrophilic group (B2)]

[0129] The acrylic polymer (B2) having a hydrophilic group used in the present composition preferably contains a structural unit derived from a monomer having a hydrophilic group, more preferably contains a structural unit derived from a monomer having a hydrophilic group and a structural unit derived from a hydrophobic monomer, and further preferably consists of a structural unit derived from a monomer having a hydrophilic group and a structural unit derived from a hydrophobic monomer.

[0130] The content of the structural unit derived from the monomer having a hydrophilic group in the acrylic polymer having a hydrophilic group (B2) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 20% by mass or more, and is 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less.

[0131] It is believed that by providing the acrylic polymer with a hydrophilic group, when the formed antifouling coating is placed in water, the hydrophilic part of the acrylic polymer dissolves or swells and slowly moves to the surface of the antifouling coating, thereby effectively preventing the attachment of aquatic organisms. It is also believed that since it has an acrylic structure, it slowly hydrolyzes and changes its affinity for water, thereby slowly moving the acrylic polymer to the surface of the antifouling coating, and maintaining the antifouling property for a long time.

[0132] The hydrophilic group of the monomer having a hydrophilic group is preferably an ether group or a hydroxyl group, more preferably an ether group, further preferably a polyether group, and further preferably a polyethyleneoxy group, from the viewpoint of improving the antifouling property and scratch resistance of the antifouling coating film to be formed.

[0133] The content of the structural unit derived from the hydrophobic monomer in the acrylic polymer (B2) having a hydrophilic group is preferably 99% by mass or less, more preferably 97% by mass or less, further preferably 95% by mass or less, further preferably 90% by mass or less, particularly preferably 80% by mass or less, and is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more.

[0134] It is considered that by including a hydrophobic monomer in the acrylic polymer, the acrylic polymer has a high affinity with the photocurable organopolysiloxane (A) or the like, which is another component of the antifouling coating composition, and that the antifouling coating film surface can exhibit uniform slip properties.

[0135] As the monomer having a hydrophilic group, from the viewpoint of improving the antifouling property and scratch resistance of the antifouling coating film to be formed, a monomer having a polyalkylene glycol group and a monomer having a hydroxyl group are preferred, and a monomer having a polyalkylene glycol group is more preferred.

[0136] Specifically, from the viewpoint of improving antifouling properties, preferably at least one selected from polyalkylene glycol (meth)acrylate, hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloylmorpholine and vinylpyrrolidone, more preferably at least one selected from polyalkylene glycol (meth)acrylate and hydroxyalkyl (meth)acrylate, and still more preferably polyalkylene glycol (meth)acrylate.

[0137] Examples of the polyalkylene glycol (meth)acrylate include polyalkylene glycol (meth)acrylates in which one terminal of the polyalkylene glycol is directly ester-bonded to (meth)acrylic acid or is bonded via a linking group, and the remaining terminal is a hydroxyl group or an alkoxy group. Preferred polyalkylene glycol (meth)acrylates include polyalkylene glycol (meth)acrylates in which one terminal of the polyalkylene glycol is directly ester-bonded to (meth)acrylic acid or is bonded via a linking group, and the remaining terminal is an alkoxy group.

[0138] Among them, polyalkylene glycol (meth)acrylates in which one terminal of the polyalkylene glycol is directly ester-bonded to (meth)acrylic acid are preferred, and polyalkylene glycol (meth)acrylates in which the remaining one terminal is an alkoxy group are more preferred.

[0139] The (meth)acrylic acid at the terminal is preferably acrylic acid or methacrylic acid, and more preferably acrylic acid.

[0140] Examples of the terminal alkoxy group include a methoxy group, a phenoxy group, and an octyloxy group. A methoxy group and a phenoxy group are preferred, and a methoxy group is more preferred.

[0141] The polyalkylene glycol constituting the polyalkylene glycol (meth)acrylate is preferably polyethylene glycol, polypropylene glycol, or a copolymer of ethylene glycol and propylene glycol, and more preferably polyethylene glycol.

[0142] The average number of alkylene glycol units constituting the polyalkylene glycol in the polyalkylene glycol (meth)acrylate is preferably 2 or more, more preferably 3 or more, and even more preferably 5 or more, and is preferably 25 or less, more preferably 15 or less, and even more preferably 12 or less.

[0143] Specific examples of the polyalkylene glycol (meth)acrylate include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-butylene glycol) mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, allyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, phenoxypoly(ethylene glycol-propylene glycol) methacrylate, octyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, dodecyloxypolyethylene glycol mono(meth)acrylate, octadecyloxypolyethylene glycol mono(meth)acrylate, nonylphenoxypolypropylene glycol acrylate, and the like, preferably methoxypolyethylene glycol mono(meth)acrylate.

[0144] Commercially available products can be used as polyalkylene glycol (meth)acrylates. Examples of such commercially available products include NK ESTER AM-90G (methoxy polyethylene glycol #400 acrylate), NK ESTERAM-130G (methoxy polyethylene glycol #550 acrylate), NK ESTER M-90G (methoxy polyethylene glycol #400 methacrylate), and NK ESTER M-230G (methoxy polyethylene glycol #1000 methacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.; LIGHT ACRYLATE MTG-A (methoxy-triethylene glycol acrylate), LIGHT ACRYLATE EC-A (ethoxy-diethylene glycol acrylate), LIGHT ACRYLATE EHDG-AT (2-ethylhexyl-diethylene glycol acrylate), and LIGHT ESTER041MA (methoxy polyethylene glycol methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.; and BLEMMER manufactured by NOF Corporation. ANP-300 (nonylphenoxy polypropylene glycol acrylate), BLEMMER AP-400 (polypropylene glycol monoacrylate), BLEMMER 70PEP-350B (polyethylene glycol polypropylene glycol monomethacrylate), BLEMMER 55PET-800 (polyethylene glycol butylene glycol monomethacrylate), BLEMMER 50POEP-800B (octyloxy polyethylene glycol polypropylene glycol methacrylate); VISCOAT#MTG (methoxy polyethylene glycol acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., etc.

[0145] Examples of the hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

[0146] Commercially available products may be used as the hydroxyalkyl (meth)acrylate, and examples of such commercial products include LIGHT ESTER HOA(N) (2-hydroxyethyl acrylate), LIGHT ESTER HO-250(N) (2-hydroxyethyl methacrylate), and LIGHT ESTER HOP(N) (2-hydroxypropyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.

[0147] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate and the like.

[0148] As tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate are preferred, and tetrahydrofurfuryl acrylate is more preferred.

[0149] As 4-(meth)acryloylmorpholine, 4-acryloylmorpholine and 4-methacryloylmorpholine are preferred, and 4-acryloylmorpholine is more preferred.

[0150] Examples of the vinyl pyrrolidone include 1-vinyl-2-pyrrolidone (N-vinyl-2-pyrrolidone), 3-acetyl-1-vinylpyrrolidone, and 3-benzoyl-1-vinylpyrrolidone. Among them, 1-vinyl-2-pyrrolidone is preferred.

[0151] Moreover, as the monomer which has a hydrophilic group mentioned above, (meth)acrylic acid can be mentioned besides this.

[0152] Examples of the hydrophobic monomer include alkyl (meth)acrylates having a branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, aryl (meth)acrylates having an aromatic group having 6 to 10 carbon atoms, and silicones containing a (meth)acrylate group. Alkyl (meth)acrylates and silicones containing a (meth)acrylate group are preferred, and alkyl (meth)acrylates are more preferred.

[0153] The carbon number of the alkyl group of the (meth)acrylic acid alkyl ester is preferably 1 to 30, more preferably 4 to 18, further preferably 4 to 8, and still further preferably 4 to 6.

[0154] The alkyl group is branched, linear or cyclic, preferably branched or linear, and more preferably branched.

[0155] Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. Among them, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred.

[0156] The number of carbon atoms in the aromatic group of the aryl (meth)acrylate is preferably 6 or more and 10 or less, more preferably 6 or more and 7 or less.

[0157] Specific examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0158] Examples of the (meth)acrylic group-containing silicone include methacrylic group-containing silicone and acrylic group-containing silicone, and methacrylic group-containing silicone is preferred.

[0159] The (meth)acrylic group-containing silicone is preferably a (meth)acrylic group bonded to one end of the silicone main chain via a linking group and a (meth)acrylic group-containing silicone is directly bonded to one end of the silicone main chain, and more preferably a (meth)acrylic group-containing silicone is bonded to one end of the silicone main chain via a linking group.

[0160] The above-mentioned linking group is preferably a trimethylene group.

[0161] The silicone main chain is preferably formed of linear or branched dimethyl silicone (polydimethylsiloxane), and more preferably formed of linear dimethyl silicone.

[0162] Furthermore, it is more preferred that an alkyl group having 1 to 6 carbon atoms be present at the terminal on the opposite side to the (meth)acryloyl group, and it is even more preferred that a butyl group be present.

[0163] As the silicone containing a (meth)acrylic group, commercially available products can be used. Examples of such commercial products include Silaplane TM-0701T (tris(trimethylsiloxy)silylpropyl methacrylate), Silaplane FM-0711 (dimethylpolysiloxane containing a methacrylic group, number average molecular weight 1000), and Silaplane FM-0721 (dimethylpolysiloxane containing a methacrylic group, number average molecular weight 5000) manufactured by JNC Corporation.

[0164] By including a (meth)acrylic group-containing silicone, the antifouling property of the antifouling coating film to be formed can be improved.

[0165] The acrylic polymer (B2) having a hydrophilic group can be obtained by polymerizing the above-mentioned hydrophilic monomer and hydrophobic monomer, and a known method using a polymerization initiator can be employed as the polymerization method.

[0166] The weight average molecular weight (Mw) of the acrylic polymer (B2) having a hydrophilic group is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and further preferably 7,000 or more, and is preferably 30,000 or less, and more preferably 15,000 or less, from the viewpoint of improving the viscosity of the antifouling coating composition and the antifouling property of the formed antifouling coating film.

[0167] When the weight average molecular weight (Mw) of the acrylic polymer (B2) having a hydrophilic group is within the above range, it is preferred from the viewpoint of being able to impart good antifouling properties and scratch resistance to the formed antifouling coating film.

[0168] When the present composition contains an acrylic polymer (B2) having a hydrophilic group, the content in the solid content of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of the antifouling property and damage resistance of the antifouling coating film formed.

[0169] <Photopolymerization Initiator (C)>

[0170] The present composition contains a photopolymerization initiator (C). The photopolymerization initiator (C) may be any initiator as long as it generates active species such as radicals upon irradiation with active energy rays.

[0171] As the initiator that generates free radicals by irradiation with active energy rays, for example, conventionally known photopolymerization initiators such as phosphine oxide polymerization initiators, acetophenone polymerization initiators, benzoin polymerization initiators, benzophenone polymerization initiators, and thioxanthone polymerization initiators can be used. Among them, phosphine oxide polymerization initiators are preferably used from the viewpoint that the coating composition has good curing properties even with ultraviolet light of a longer wavelength.

[0172] Examples of the phosphine oxide polymerization initiator include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide; and bisacylphosphine oxides such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-(2,4-dipentyloxyphenyl)phosphine oxide.

[0173] Examples of the acetophenone-based polymerization initiator include benzil dimethyl ketal (also known as 2,2-dimethoxy-2-phenylacetophenone), diethoxyacetophenone, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 4-tert-butyl-trichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone.

[0174] Examples of the benzoin-based polymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenyl-1-ethanone.

[0175] Examples of the benzophenone-based polymerization initiator include benzophenone, [4-(methylphenylthio)phenyl]phenyl ketone, 4-hydroxybenzophenone, 4-phenylbenzophenone, and 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone.

[0176] Examples of the thioxanthone-based polymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0177] On the other hand, examples of initiators that generate cations upon irradiation with active energy rays include sulfonium salt compounds and iodonium salt compounds, and examples of initiators that generate anions include 1,5,7-triazabicyclo[4.4.0]dec-5-ene-2-(9-oxoxanthene-2-yl)propanoate.

[0178] A photopolymerization initiator (C) may be used alone or in combination of two or more.

[0179] In the present composition, the content of the photopolymerization initiator (C) in the solid content of the antifouling coating composition is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 1.5 parts by mass or more, and is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total solid content of the components (A) and (B).

[0180] <Optional Ingredients>

[0181] The present composition may contain, in addition to the photocurable organopolysiloxane (A), the slip agent (B) and the photopolymerization initiator (C), a silane coupling agent (D), a non-reactive solvent (E), a polymerization inhibitor (F), a defoaming agent (G), a light stabilizer (H), an ultraviolet absorber (I), an inorganic filler (J), an organic coloring pigment (K), a photosensitizer (L), a photopolymerizable monomer (M), other oligomers, a polymer (N), a biorepellent (O), a dehydrating agent (P), an anti-sagging and anti-settling agent (Q), a curing catalyst (R), an organosilicon crosslinking agent (S), an antistatic agent (T), an enzyme (U), a flame retardant (V), a thermal conductivity improver (W) and an anti-fogging agent (X) as needed within a range not impairing the effects of the present invention.

[0182] 〔Silane coupling agent (D)〕

[0183] The present composition may contain a silane coupling agent (D) for the purpose of improving the adhesion between the formed antifouling coating film and a substrate or base.

[0184] The silane coupling agent (D) is a compound having a silane to which a hydrolyzable group is bonded and a reactive group, or a partial condensate thereof. For example, a compound represented by the following formula (D1) or a partial condensate thereof is preferably used.

[0185] [Chemistry 4]

[0186] (R 21 O) W R 22 (3-W) Si-R 23 -Z (D1)

[0187] In formula (D1), R 21 and R 22 Each independently represents an alkyl group, alkenyl group, aryl group or halogenated alkyl group having 1 to 10 carbon atoms, and is preferably a methyl group or an ethyl group.

[0188] In formula (D1), R 23 It is a divalent hydrocarbon group having 1 to 20 carbon atoms which may be interposed with an amino group (-NR-, R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), an ether group (-O-), a thioether group (-S-), an ester group (-C(=O)-O-) or an amide group (-C(=O)-NR-, R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and is preferably a propylene group.

[0189] In formula (D1), Z is a reactive group, and among them, from the viewpoint of good antifouling property of the formed coating film, preferably a (meth)acryloyloxy group, more preferably an acryloyloxy group.

[0190] In formula (D1), w is an integer of 2 or 3, and preferably 3.

[0191] Examples of such silane coupling agents (D) include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. Preferably, 3-acryloxypropyltrimethoxysilane is used.

[0192] As the silane coupling agent (D), a commercially available product can be used, and for example, "KBM-5103" (3-acryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

[0193] These silane coupling agents (D) may be used alone or in combination of two or more.

[0194] When the present composition contains a silane coupling agent (D), the content of the silane coupling agent (D) in the solid content of the coating composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of improving the adhesion of the formed antifouling coating film to the substrate or the primer coating film.

[0195] [Non-reactive solvent (E)]

[0196] The present composition may contain a non-reactive solvent (E) for the purpose of improving the production workability and coating workability of the composition.

[0197] Examples of the non-reactive solvent (E) include aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents, alicyclic hydrocarbon organic solvents, ketone organic solvents and ester organic solvents. Among them, aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents and alicyclic hydrocarbon organic solvents are preferred.

[0198] Examples of the aromatic hydrocarbon organic solvent include toluene, xylene, and mesitylene.

[0199] Examples of the aliphatic hydrocarbon-based organic solvent include pentane, hexane, heptane, octane, and mineral spirits.

[0200] Examples of the alicyclic hydrocarbon organic solvent include cyclohexane, methylcyclohexane, and ethylcyclohexane.

[0201] Examples of the ketone organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone (also known as 2-heptanone), and dimethyl carbonate.

[0202] Examples of the ester organic solvent include propylene glycol monomethyl ether acetate and the like.

[0203] These non-reactive solvents (E) may be used alone or in combination of two or more.

[0204] When the present composition contains a non-reactive solvent (E), the content of the non-reactive solvent (E) in the coating composition can be appropriately adjusted according to the viscosity of the coating composition, but is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and from the viewpoint of suppressing sagging during coating, it is preferably 40% by mass or less, more preferably 25% by mass or less, and even more preferably 15% by mass or less.

[0205] The non-reactive solvent may be added during the preparation of the antifouling coating composition, or may be mixed in advance with other components.

[0206] In the present invention, it is preferred that the content of the non-reactive solvent (E) is reduced because the photocuring step can be performed without performing a drying step, and an antifouling coating film can be formed in a shorter time.

[0207] 〔Polymerization inhibitor (F)〕

[0208] The present composition may contain a polymerization inhibitor (F) for the purpose of improving the storage stability, production workability, and coating workability of the coating composition.

[0209] Examples of the polymerization inhibitor (F) include quinones such as p-benzoquinone, naphthoquinone, methylbenzoquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-tert-butylhydroquinone, methylhydroquinone, and mono-tert-butylhydroquinone, aromatics such as 4-methoxyphenol and 2,6-di-tert-butylcresol (also known as dibutylhydroxytoluene, BHT), and p-tert-butylcatechol. Among them, aromatics are preferred, and 4-methoxyphenol and 2,6-di-tert-butylcresol are particularly preferred. These may be used alone or in combination of two or more.

[0210] When the present composition contains a polymerization inhibitor (F), the content of the polymerization inhibitor (F) in the solid content of the coating composition is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, and is preferably 0.1 mass % or less, more preferably 0.05 mass % or less.

[0211] 〔Defoaming agent (G)〕

[0212] The present composition may contain a defoaming agent (G) for the purpose of improving the production workability and coating workability of the composition and improving the strength and antifouling property of the antifouling coating film formed.

[0213] As the defoaming agent (G), fluorine-based, silicone-based, and acrylic-based defoaming agents can be used, and fluorine-based defoaming agents are particularly preferred. In addition, two or more defoaming agents (G) can be used in combination.

[0214] As the defoaming agent (G), a commercially available product may be used, and examples thereof include “BYK-066N” (fluorine-based defoaming agent) manufactured by BYK-Chemie Japan Co., Ltd., and the like.

[0215] When the present composition contains a defoaming agent (G), the content of the defoaming agent (G) in the solid content of the coating composition is preferably 0.001 mass % or more, more preferably 0.01 mass % or more, and is preferably 5 mass % or less, more preferably 1 mass % or less.

[0216] 〔Light stabilizer (H)〕

[0217] The present composition may contain a light stabilizer (H) for the purpose of further suppressing yellowing of the antifouling coating film due to ultraviolet rays such as sunlight.

[0218] Examples of the light stabilizer (H) include hindered amine-based light stabilizers, modified light stabilizers thereof, and oligomerized light stabilizers. These may be used alone or in combination of two or more.

[0219] As the hindered amine light stabilizer, commercially available products can be used, for example, "TINUVIN 123" manufactured by BASF Japan Co., Ltd. (a mixture of a reaction product of bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) sebacate, 1,1-dimethylethyl hydroperoxide and octane, and a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol), "TINUVIN "111FDL" (N,N',N",N"'-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine), "TINUVIN144" (bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate), "TINUVIN292" (a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate), "Adakastab LA-82" (methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidinyl ester) manufactured by ADEKA Co., Ltd.), "Adakastab LA-87" (2,2,6,6-pentamethyl-4-piperidinyl methacrylate), Clariant Japan Co., Ltd. "HOSTAVIN 3058" (1-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-3-dodecylpyrrolidine-2,5-dione), and the like.

[0220] When using the light stabilizer (H), the content thereof is not particularly limited, but is preferably 0.1% by mass or more and 5% by mass or less in the solid content of the coating composition.

[0221] 〔Ultraviolet light absorber (I)〕

[0222] The present composition may contain an ultraviolet absorber (I) for the purpose of maintaining good antifouling properties of the antifouling coating film formed and good adhesion to a substrate or base.

[0223] Examples of the ultraviolet absorber (I) include benzotriazole ultraviolet absorbers such as 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole;

[0224] Benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone;

[0225] Hydroxyphenyltriazine-based UV absorbers;

[0226] Salicylate-based UV absorbers such as phenyl salicylate and 4-tert-butylphenyl salicylate;

[0227] Cyanoacrylate ultraviolet absorbers such as ethyl 2-cyano-3,3-diphenylcyanoacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylcyanoacrylate.

[0228] The ultraviolet absorber (I) may also be an ultraviolet absorber having a functional group that reacts with other components in the coating composition when irradiated with active energy rays.

[0229] The ultraviolet absorber (I) may be used alone or in combination of two or more.

[0230] As the ultraviolet absorber (I), a commercially available product can be used. Examples of the benzotriazole-based ultraviolet absorber include “RUVA-93” (2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole) manufactured by Otsuka Chemical Co., Ltd., “DAINSORBT-84” (2-(4-allyloxy-2-hydroxyphenyl)-2H-benzotriazole) manufactured by Yamato Chemical Co., Ltd., and “Tinuvin 928” (2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3,-tetramethylbutyl)phenol) manufactured by BASF Japan Co., Ltd.; examples of the benzophenone-based ultraviolet absorber include “Chimassorb 81” (2-hydroxy-4-octyloxybenzophenone) manufactured by BASF Japan Co., Ltd.; and examples of the hydroxyphenyltriazine-based ultraviolet absorber include “Tinuvin 928” (2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3,-tetramethylbutyl)phenol) manufactured by BASF Japan Co., Ltd. "Tinuvin 400" (a mixture of 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine), "Tinuvin 460" (2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine), "Tinuvin 405" (2-[4-[(2-hydroxy-3-(2-ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine), "Tinuvin 460" (2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine), 479" (2-(2-hydroxy-4-(isooctyloxycarbonylethoxy)phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine), etc.

[0231] When the present composition contains the ultraviolet absorber (I), the content of the ultraviolet absorber (I) in the solid content of the coating composition is 10% by mass or less, more preferably 5% by mass or less.

[0232] 〔Inorganic filler (J)〕

[0233] The present composition may contain an inorganic filler (J) for the purpose of improving the strength, antifouling properties and visibility of the antifouling coating film to be formed.

[0234] Examples of the inorganic filler (J) include silica, alumina, titanium oxide, iron oxide, zinc oxide, zirconium oxide, indium oxide, vanadium oxide, cerium oxide, antimony oxide, talc, tungsten carbide, titanium carbide, silicon carbide, calcium carbonate, magnesium carbonate, aluminum sulfate, barium sulfate, calcium sulfate, magnesium sulfate, glass fiber, glass flakes, and the like, among which silica is preferably contained.

[0235] Among the inorganic fillers (J), for inorganic fillers with high transmittance of active energy rays such as silicon dioxide, from the viewpoint of making the curability of the coating composition and the adhesion of the formed antifouling coating film to the substrate and the base good, it is preferred to use particles with an average particle diameter of 1 nm or more and 200 nm or less, more preferably 10 nm or more and 100 nm or less. It should be noted that the average particle diameter is the median particle diameter (d50) of the volume-based particle size distribution measured by dynamic light scattering, for example, it can be measured using a laser diffraction particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation). Alternatively, it can also be calculated as the average value of the diameter of the particles when observing the cured film using a scanning electron microscope or a transmission electron microscope.

[0236] In the case where the present composition contains silica, it is possible to use hydrophilic silica with untreated surface, or it is possible to use silica that has been surface treated. As silica that has been surface treated, for example, silica that has been surface treated by reaction with methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, a coupling agent or a polymer can be cited. If such surface treatment is performed, silica will be hydrophobized, thereby preventing the coagulation in the antifouling coating composition and improving storage stability. As silica that has been surface treated, for example, reactive silica having (meth) acryloyl groups on the silica surface can be used. The above-mentioned reactive silica can be obtained, for example, by reacting silica with hydrolyzable silanes having (meth) acryloyl groups and methoxyl groups, ethoxyl groups in the molecule. If this is the case, when the present composition is cured by irradiation with active energy rays, the strength of the formed coating can be improved by reacting reactive silica with component (A) and then embedding it into the coating.

[0237] As the inorganic filler (J), a powdered inorganic filler may be used, or an inorganic fine particle sol in which fine particles of the inorganic filler are dispersed in a dispersion medium may be used.

[0238] As the dispersion medium of the inorganic microparticle sol, for example, water; monohydric alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; polyhydric alcohol solvents such as ethylene glycol and propylene glycol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and cyclohexanone. Among them, water, methanol, ethanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether are preferred from the perspective of ease of manufacture of the coating composition.

[0239] It should be noted that the content of the inorganic filler (J) in the present composition does not include the above-mentioned dispersion medium.

[0240] Such an inorganic filler (J) may be used alone or in combination of two or more.

[0241] Commercially available products can be used as the inorganic filler (J). Examples of the inorganic filler in powder form include "Aerosil 50" (average primary particle diameter of 30 nm, no surface-treated silica), "Aerosil 300" (average primary particle diameter of 7 nm, no surface-treated silica), "Aerosil R972" (average primary particle diameter of 7 nm, dimethyldichlorosilane surface-treated silica), "Aerosil R202" (average primary particle diameter of 14 nm, dimethyl silicone oil surface-treated silica), "Alu C" (average primary particle diameter of 13 nm, alumina), "TiO 2 P25" (average primary particle diameter 21 nm, titanium oxide), etc.

[0242] Examples of the inorganic fine particle sol include "MIBK-SD" (silica sol dispersed in methyl isobutyl ketone, 30% silica content, particle size 10 to 15 nm), "PGM-AC-4130Y" (silica sol dispersed in propylene glycol monomethyl ether, 30% silica content, particle size 40 to 50 nm), "MEK-ST-ZL" (silica sol dispersed in methyl ethyl ketone, 30% silica content, particle size 70 to 100 nm), CIK Nanotech Co., Ltd. produces "SIRMIBK30WT%-H24" (methyl isobutyl ketone dispersed silica sol, silica component 30%), "SIRPA15WT%-H10" (methyl isobutyl ketone dispersed silica sol, silica component 15%), "SIRPGM30WT%-E80" (propylene glycol monomethyl ether dispersed silica sol, silica component 30%), "RTTMIBK20WT%-H36" (methyl isobutyl ketone dispersed titanium oxide sol, titanium oxide component 15%), "ZNMIBK15WT%-E05" (methyl isobutyl ketone dispersed zinc oxide sol, zinc oxide component 15%), etc.

[0243] When the present composition contains an inorganic filler (J), the content of the inorganic filler (J) in the solid content of the coating composition is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and is preferably 20 mass % or less, more preferably 10 mass % or less.

[0244] [Organic coloring pigment (K)]

[0245] The present composition may contain an organic coloring pigment (K) for the purpose of improving the visibility of the antifouling coating composition and the antifouling coating film formed, thereby improving the production workability and coating workability.

[0246] Specific examples of the organic coloring pigment (K) include soluble azo pigments such as Color Lake Red C and Brilliant Carmine 6B, insoluble azo pigments such as Toluidine Red, Permanent Carmine FB, Fast Yellow G, Disazo Yellow AAA, and Disazo Orange PMP, condensed azo pigments such as Chromophthal Yellow 3G, chelate azo pigments, phthalocyanine pigments such as Phthalocyanine Blue and Phthalocyanine Green, condensed polycyclic pigments such as Indanthrone Blue, Quinacridone Red, and Dioxazine Violet, basic blue, aniline black, daylight fluorescent pigments, nitro pigments, nitroso pigments, and organic pigments such as carbon black.

[0247] The organic coloring pigment (K) may be used alone or in combination of two or more.

[0248] When the present composition contains an organic coloring pigment (K), the content of the organic coloring pigment (K) in the solid content of the coating composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less.

[0249] 〔Photosensitizer (L)〕

[0250] The present composition may contain a photosensitizer (L) for the purpose of improving the curability of the antifouling coating composition.

[0251] The present composition may use a photosensitizer (L) together with the above-mentioned photopolymerization initiator (C). Specific examples of the photosensitizer (L) include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 4,4-dimethylaminobenzophenone, and 4,4-diethylaminobenzophenone.

[0252] The photosensitizer (L) may be used alone or in combination of two or more.

[0253] When the present composition contains a photosensitizer (L), the content of the photosensitizer (L) in the solid content of the coating composition is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, and is preferably 10 mass % or less, more preferably 5 mass % or less.

[0254] [Photopolymerizable monomer (M)]

[0255] The present composition may contain a photopolymerizable monomer (M) other than the components described in the preceding paragraphs for the purpose of improving the production workability and coating workability of the antifouling coating composition, the antifouling property of the formed coating film, and the adhesion to the substrate and base, and for the purpose of serving as a diluent for other components.

[0256] Examples of the photopolymerizable monomer (M) include: monofunctional monomers such as those listed as the monomers that are the source of the acrylic polymer (B2);

[0257] Monofunctional monomers containing an isocyanate group, such as 2-acryloyloxyethyl isocyanate;

[0258] 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(meth)acrylate of ethylene oxide adduct of neopentyl glycol, di(meth)acrylate of propylene oxide adduct of neopentyl glycol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylate of ethylene oxide adduct of bisphenol A, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Polyfunctional monomers such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetra(meth)acrylate of ethylene oxide adduct of pentaerythritol, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexa(meth)acrylate of ε-caprolactone adduct of dipentaerythritol, and hexa(meth)acrylate of ethylene oxide adduct of dipentaerythritol.

[0259] Among them, from the viewpoint of improving adhesion within a short period of time after curing (active energy ray irradiation), a photopolymerizable monomer having a polar group is preferred, a photopolymerizable monomer having at least any one of a carboxylic acid group, an isocyanate group, a hydroxyl group and an amino group is more preferred, and acrylic acid is further preferred.

[0260] The photopolymerizable monomer (M) may be used alone or in combination of two or more.

[0261] When the present composition contains a photopolymerizable monomer (M), the content of the photopolymerizable monomer (M) in the solid content of the coating composition is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 30% by mass or less, more preferably 15% by mass or less.

[0262] 〔Other oligomers and polymers (N)〕

[0263] The present composition may contain other oligomers or polymers (N) in addition to the components (A) and (B) for the purpose of improving the strength of the antifouling coating film formed and the adhesion to the substrate or base.

[0264] The other oligomers and polymers (N) other than the components (A) and (B) may be used alone or in combination of two or more.

[0265] Examples of other oligomers and polymers (N) include organopolysiloxane (N1) which is not photocurable (hereinafter also referred to as “organopolysiloxane (N1)”). The proportion of the organopolysiloxane in the molecule of the organopolysiloxane (N1) is preferably 50% by mass or more.

[0266] As such an organopolysiloxane (N1), for example, an organopolysiloxane formed as follows can be cited, that is, having reactive groups in the molecule, and the reactive groups react with each other or react with the reactive groups of the above-mentioned photocurable organopolysiloxane (A) and the organosilicon crosslinking agent (S) described later, thereby forming a three-dimensional crosslinked structure and curing. It should be noted that as examples of the reactions of these reactive groups, condensation reactions and addition reactions can be cited, and as condensation reactions, dealcoholization reactions, deoxime reactions, and deacetonization reactions can be cited.

[0267] As such an organopolysiloxane (N1), commercially available products can be used, and examples thereof include "DMS-S35" manufactured by GELEST Co., Ltd. and "KE-441" and "KE-445" manufactured by Shin-Etsu Chemical Co., Ltd.

[0268] When the present composition contains an organopolysiloxane (N1), the content of the organopolysiloxane (N1) in the solid content of the coating composition is preferably 1% by mass or more, more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less.

[0269] As other oligomers and polymers (N), among the compounds that initiate polymerization by active species such as free radicals generated from the photopolymerization initiator (C) by irradiation with active energy rays, other photocurable oligomers and polymers (N2) other than the photocurable organopolysiloxane (A) can also be cited. The proportion of organopolysiloxane in the molecule of the other photocurable oligomer and polymer (N2) is less than 50% by mass.

[0270] Examples of such other photocurable oligomers and polymers (N2) include urethane (meth)acrylates, polyester (meth)acrylates, and epoxy (meth)acrylates.

[0271] Urethane (meth)acrylate is an oligomer or polymer having one or more (meth)acryloyloxy groups and urethane bonds in the molecule, and can be obtained, for example, by the reaction of a (meth)acrylate having a hydroxyl group in the molecule with a polyisocyanate, or by the reaction of a hydroxyl-containing polyester with a (meth)acrylate having an isocyanate group.

[0272] As other photocurable oligomers and polymers (N2), commercially available products can be used, for example, "CN991" manufactured by Sartomer (aliphatic urethane acrylate, number of functional groups: 2, weight average molecular weight: 1500), "KRM8200" manufactured by DaicelAllnex Co., Ltd. (aliphatic urethane acrylate, number of functional groups: 6, weight average molecular weight: 1000), "EBECRYL220" (aromatic urethane acrylate, number of functional groups: 6, weight average molecular weight: 1000), "Aronix M-8560" (polyester acrylate) manufactured by Toagosei Co., Ltd., and "VR-77" (epoxy acrylate, number of functional groups: 1.9, weight average molecular weight: 510) manufactured by Showa Denko K.K.

[0273] When the present composition contains other photocurable oligomers and polymers (N2), the content of the photocurable oligomers and polymers (N2) in the solid component of the coating composition is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 40% by mass or less, more preferably 25% by mass or less.

[0274] As other oligomers and polymers (N), other oligomers and polymers (N3) other than the above-mentioned organopolysiloxane (N1) and other photocurable oligomers and polymers (N2) may be mentioned.

[0275] Examples of such other oligomers and polymers (N3) include poorly water-soluble or water-insoluble resins other than component (B), such as acrylic resins, acrylic silicone resins, unsaturated polyester resins, fluororesins, polybutene resins, urethane resins (rubbers), polyamide resins, vinyl chloride copolymer resins, chlorinated rubber (resins), chlorinated olefin resins, styrene-butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, and petroleum resins.

[0276] 〔Biorepellent(O)〕

[0277] The present composition may contain a biorepellent (O) for the purpose of further improving the antifouling property of the antifouling coating film to be formed.

[0278] Examples of the biorepellent (O) include 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT), (+ / -)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (also known as medetomidine), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (also known as bromopyrrolecarbonitrile), borane-nitrogen base adducts (pyridine triphenylborane, 4-isopropylpyridine diphenylmethylborane, etc.), N,N-dimethyl-N'-(3,4-dichlorophenyl)urea. (Also known as DCMU), N-(2,4,6-trichlorophenyl)maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, chloromethyl-n-octyl disulfide, N,N-dimethyl-N′-phenyl-(N′-fluorodichloromethylthio)sulfonamide, tetraalkylthiuram disulfide, 2,3-dichloro-N-(2′,6′-diethylphenyl)maleimide, 2,3-dichloro-N-(2′-ethyl-6′-methylphenyl)maleimide and other organic biological repellents;

[0279] Inorganic biorepellents such as cuprous oxide, copper rhodanite, and copper;

[0280] Organic-inorganic composite biorepellents such as copper pyrithione, zinc pyrithione, bis(dimethyldithiocarbamoyl)ethylenebis(dithiocarbamate)zinc, dimethyldithiocarbamate, and ethylenebis(dithiocarbamate)zinc are preferably used from the viewpoint of improving the curability of the antifouling coating composition and the adhesion of the formed antifouling coating film to the substrate, and DCOIT and medetomidine are more preferably used.

[0281] The biorepellent (O) may be used alone or in combination of two or more.

[0282] When an inorganic biorepellent or an organic-inorganic composite biorepellent is used as the biorepellent (O), it is preferred to use fine particles.

[0283] When the present composition contains a biorepellent (O), the content of the biorepellent (O) in the solid component of the coating composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of improving the antifouling properties of the antifouling coating film formed.

[0284] 〔Dehydrating agent (P)〕

[0285] The present composition may contain a dehydrating agent (P) for the purpose of improving the storage stability of the coating composition.

[0286] As the dehydrating agent (P), for example, zeolite generally known as "molecular sieve", porous alumina, orthoesters such as alkyl orthoformate, orthoboric acid, isocyanate, etc. can be used. These dehydrating agents can be used alone or in combination of two or more.

[0287] When the present composition contains a dehydrating agent (P), the content of the dehydrating agent (P) in the solid content of the coating composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving the storage stability of the coating composition.

[0288] 〔Anti-sagging and anti-settling agent (Q)〕

[0289] The present composition may contain an anti-sagging-anti-settling agent (Q).

[0290] Examples of the anti-sagging and anti-settling agent (Q) include organic clay waxes (stearate salts, lecithin salts, alkyl sulfonates of Al, Ca, Zn, etc.), organic waxes (polyethylene wax, oxidized polyethylene wax, amide wax, polyamide wax, hydrogenated castor oil wax, etc.), and mixtures of organic clay waxes and organic waxes.

[0291] As the anti-sagging / anti-settling agent (Q), commercially available products may be used, and examples thereof include "DISPARLON 305", "DISPARLON 4200-20", and "DISPARLON A630-20X" manufactured by Kusumoto Chemicals Co., Ltd.

[0292] In the case where the present composition contains an anti-sagging / anti-settling agent (Q), the content of the anti-sagging / anti-settling agent (Q) in the solid component of the coating composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and is preferably 10% by mass or less, more preferably 3% by mass or less.

[0293] [Curing catalyst (R)]

[0294] The present composition may contain a curing catalyst (R) for the purpose of improving the curability of the composition and the coating film strength of the antifouling coating film to be formed.

[0295] Particularly when the present composition contains the above-mentioned component (N1), it is preferred to contain a curing catalyst (R).

[0296] Examples of the curing catalyst (R) include tin catalysts such as dibutyltin dilaurate when a condensation reaction curable organopolysiloxane is contained as the component (N1), and platinum catalysts when an addition reaction curable organopolysiloxane is contained as the component (N1).

[0297] 〔Organic silicon crosslinking agent (S)〕

[0298] The present composition may contain an organosilicon crosslinking agent (S) other than the components described in the preceding paragraph for the purpose of improving the curability of the composition and the coating film strength of the antifouling coating film to be formed.

[0299] The organosilicon crosslinking agent (S) is preferably a compound represented by the following formula (S1) and / or a partial condensate thereof.

[0300] R 51 d S Y (4-d) (S1)

[0301] (In formula (S1), R 51 represents a hydrocarbon group having 1 to 6 carbon atoms, Y each independently represents a hydrolyzable group, and d represents an integer of 0 to 2.)

[0302] In formula (S1), R 51 Each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include linear or branched alkyl groups such as methyl, ethyl, and propyl groups, cyclic alkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups, and aryl groups such as phenyl groups. Among them, methyl and ethyl groups are preferred.

[0303] It should be noted that when d is 2, there are multiple R 51 Each may be the same or different.

[0304] In formula (S1), Y each independently represents a hydrolyzable group. Examples of the hydrolyzable group include alkoxy groups such as a methoxy group and an ethoxy group, and oxime groups such as an ethylmethylketoxime group.

[0305] d represents an integer of 0 or more and 2 or less, and is preferably 0 from the viewpoint of improving the curability and film strength of the antifouling coating film.

[0306] As the silicone crosslinking agent (S), commercially available products can be used, for example, "Ethyl Silicate 28" (tetraethyl orthosilicate) manufactured by Colcoat, "WACKER SiLICATETES 40 WN" (condensate of tetraethyl orthosilicate) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., "KBM-13" (trimethoxymethylsilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0307] The silicone crosslinking agent (S) may be used alone or in combination of two or more.

[0308] When the antifouling coating composition of the present invention contains an organosilicon crosslinking agent (S), the content of the organosilicon crosslinking agent (S) in the solid content of the coating composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of adjusting the curing rate of the composition and improving the coating film strength of the antifouling coating film formed.

[0309] 〔Antistatic Agent (T)〕

[0310] The present composition may contain an antistatic agent (T).

[0311] Specific examples of antistatic agents include cationic antistatic agents such as amidinium salts, guanidinium salts and quaternary ammonium salts, anionic antistatic agents such as sulfonates, higher alcohol sulfates, higher alcohol alkylene oxide adduct sulfates, higher alcohol phosphates, higher alcohol alkylene oxide adduct phosphates, and nonionic antistatic agents such as higher alcohol alkylene oxide adducts and polyol fatty acid esters. The antistatic agent (T) may be used alone or in combination of two or more.

[0312] When the present composition contains an antistatic agent (T), the content of the antistatic agent (T) in the solid content of the composition is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and is preferably 10 mass % or less, more preferably 5 mass % or less.

[0313] 〔Enzyme(U)〕

[0314] The present composition may contain an enzyme (U) for the purpose of improving the antifouling property of the antifouling coating film to be formed.

[0315] Examples of the enzyme (U) include serine protease, cysteine ​​protease, metalloprotease, cellulase, hemicellulase, pectinase, and glucosidase.

[0316] When the present composition contains an enzyme (U), the content of the enzyme (U) in the solid content of the coating composition is preferably 0.0005 mass % or more, more preferably 0.01 mass % or more, and is preferably 5 mass % or less, more preferably 0.1 mass % or less.

[0317] 〔Flame retardant (V)〕

[0318] The present composition may contain a flame retardant (V). Examples of the flame retardant (V) include antimony oxide and paraffin oxide.

[0319] The flame retardant (V) may be used alone or in combination of two or more.

[0320] When the present composition contains a flame retardant (V), the content of the flame retardant (V) in the solid content of the coating composition is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and is preferably 20 mass % or less, more preferably 1 mass % or less.

[0321] 〔Thermal conductivity improver (W)〕

[0322] The present composition may contain a thermal conductivity improver (W). Examples of the thermal conductivity improver (W) include boron nitride and the like.

[0323] The thermal conductivity improver (W) may be used alone or in combination of two or more.

[0324] When the present composition contains a thermal conductivity improver (W), the content of the thermal conductivity improver in the solid content of the coating composition is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and is preferably 20 mass % or less, more preferably 1 mass % or less.

[0325] 〔Anti-fog agent (X)〕

[0326] The present composition may contain an anti-fogging agent (X). Examples of the anti-fogging agent (X) include nonionic surfactants such as fatty acid esters of polyols, amines of higher fatty acids, amides of higher fatty acids, sucrose fatty acid esters, and ethylene oxide adducts of amines and amides of higher fatty acids.

[0327] The anti-fogging agent (X) may be used alone or in combination of two or more.

[0328] When the present composition contains an antifogging agent (X), the content of the antifogging agent (X) in the solid content of the coating composition is preferably 0.1% by mass or more and 10% by mass or less.

[0329] [Method for preparing antifouling coating composition]

[0330] The present composition can be prepared by mixing the respective components at a given ratio and, if necessary, dissolving or dispersing the components in each other.

[0331] The present composition may be a one-component paint composed of one component, or may be a multi-component paint composed of two or more components.

[0332] In the case of a multi-component coating, each component (each agent) preferably contains one or more ingredients, and is packaged separately and stored in a container such as a can. The antifouling coating composition can be prepared by mixing the contents of each component during coating.

[0333] [Antifouling coating film and method for forming the same]

[0334] The antifouling coating film of the present invention is a film obtained by curing the antifouling coating composition of the present invention.

[0335] The antifouling coating film formed by the present composition is preferably used for the purpose of preventing fouling of a substrate in water. That is, the present composition is preferably an antifouling coating composition for preventing fouling of a substrate in water.

[0336] Examples of the stain on the substrate include stain by aquatic organisms, and the present composition is preferably a coating composition for forming an antifouling coating film used for the purpose of preventing stain by aquatic organisms.

[0337] Specifically, the antifouling coating film of the present invention can be obtained, for example, by the following operation, that is, including a coating step of applying the present composition to a substrate, etc., and a curing step of curing the applied coating film (present composition) by irradiating it with active energy rays, and further, if necessary, a drying step and a step of attaching a covering film, etc., can be combined to obtain an antifouling coating film.

[0338] <Painting process>

[0339] Examples of methods for applying the composition include known methods such as brush coating, roller coating, spraying, roll coater coating, flow coater coating, slit coater coating, groove roll coater coating, spin coater coating, curtain roll coater coating, electrostatic coating, dip coating, screen printing, and spin coating.

[0340] The thickness of the antifouling coating film of the present invention is set so that the antifouling coating film finally formed has a thickness described below. The coating film may be formed by coating once or by coating two or more times (coating two or more times).

[0341] The thickness of the antifouling coating of the present invention is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 50 μm or more, and is preferably 1000 μm or less, more preferably 500 μm or less, and further preferably 300 μm or less. If the antifouling coating of the present invention is in this form, it becomes an antifouling coating having excellent antifouling properties.

[0342] <Curing process>

[0343] The present composition can be cured to form an antifouling coating film by irradiating with active energy rays. The active energy rays may be any active energy rays as long as they can act on the photopolymerization initiator (C) to generate active species such as radicals.

[0344] As the above-mentioned active energy rays, there can be mentioned far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays and the like, in addition to electromagnetic waves such as X-rays and gamma rays, electron beams, proton beams, neutron beams and the like, preferably light rays, among which ultraviolet rays are preferred from the perspectives of curing speed, ease of obtaining irradiation equipment, price and the like.

[0345] In one embodiment, examples of the light source used for light irradiation include LED lamps, ultra-high pressure, high pressure, medium pressure or low pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, fluorescent lamps, tungsten lamps, chemical lamps, electrodeless lamps, and sunlight.

[0346] The irradiation intensity of active energy rays is usually 10mW / cm 2 Above and 10000mW / cm 2 Below, the cumulative exposure is usually 50mJ / cm 2 Above and 10000mJ / cm 2 the following.

[0347] In the curing step, in order to suppress the influence of oxygen as active species generated by active energy rays on the curing inhibition, it is preferred to irradiate with active energy rays in an inert gas atmosphere such as nitrogen with a cover film, a spacer, etc. as described later attached.

[0348] <Drying process>

[0349] When the present composition contains volatile components such as the non-reactive solvent (E), a drying step may be included in the formation of the antifouling coating film for the purpose of volatilizing the volatile components in the applied coating composition.

[0350] The drying step may be performed under any conditions as long as the volatile components can be volatilized. For example, the drying may be performed by heating at a temperature of 30° C. or higher and 120° C. or lower.

[0351] The drying step may be performed before the curing step or after the curing step. Alternatively, the drying step may be partially performed before the curing step and then performed after the curing step.

[0352] <Pasting process>

[0353] When forming the antifouling coating film, a step of attaching a cover film, a spacer (release film, release paper), a casting film, etc. to the wet coating film of the applied coating composition or the cured antifouling coating film may be included for the purpose of improving the curability of the curing process, protecting the antifouling coating film, and forming a surface shape.

[0354] <Antifouling coating with surface microstructure>

[0355] The antifouling coating film of the present invention may have a surface microstructure for the purpose of improving water flow resistance or the like.

[0356] The antifouling coating film having a surface microstructure can be formed, for example, by applying a coating composition to a substrate, bringing the coating composition into contact with a casting film or a casting roll having an inverse structure of the surface microstructure to be formed, and irradiating the coating film with active energy rays in this state to cause a curing reaction, thereby forming the antifouling coating film.

[0357] As such a surface uneven structure, a rib structure as described in International Publication No. 2019 / 189412 is preferred.

[0358] The formation of such an antifouling coating film having a fine surface structure is often produced on a production line, but since the present composition has very fast curing properties, it can be produced on a production line at a higher speed, which is preferred from this point of view. In addition, since the present composition can be designed to have a low content of volatile components such as a non-reactive solvent (E), even in a curing reaction under closed conditions in contact with a mold film, it is not easy to cause undesirable conditions such as the generation of bubbles in the coating film due to the volatilization of volatile components, which is preferred from this point of view.

[0359] [Laminated antifouling coating]

[0360] The laminated antifouling coating film of the present invention comprises the aforementioned antifouling coating film and a primer coating film in contact with at least a portion of the antifouling coating film. The primer coating film of the present invention can be formed by curing a primer coating composition.

[0361] <Primer coating composition>

[0362] The primer coating composition of the present invention may be an active energy ray-curable composition, or may be a composition of another curable type such as a condensation reaction-curable composition or an addition reaction-curable composition.

[0363] When an active energy ray-curable composition is used as the primer coating composition of the present invention, the composition may be the same as that of the antifouling coating film of the present invention, for example, the composition of the components may be adjusted to give more importance to adhesion than antifouling properties, weather resistance, etc. By using such a laminated antifouling coating film using a primer coating composition, the antifouling coating film and the primer coating film can complement each other's features to form a well-balanced laminated antifouling coating film.

[0364] The primer coating film may be a single layer or may be a plurality of layers of two or more identical or different layers.

[0365] As the primer coating composition of the present invention, other curing types such as condensation reaction curing type and addition reaction curing type can be used. If a laminated antifouling coating film using such a primer coating composition is used, a laminated antifouling coating film having functions that are difficult to impart in a photocurable coating film due to poor curing caused by shielding of active energy rays, etc. can be formed. As such a primer coating composition, for example, if an inorganic filler having a low transmittance of active energy rays among the above-mentioned inorganic filler (J) is contained, a laminated antifouling coating film having light resistance and hiding properties that cannot be obtained using a single antifouling coating film can be formed.

[0366] For such a primer coating composition, from the viewpoint of improving the adhesion between the antifouling coating film and the primer coating film, it is preferred to contain the above-mentioned non-photocurable organopolysiloxane (N1), and from the viewpoint of being able to exert high antifouling properties for a long time by gradually penetrating the antifouling coating film, it is also preferred to contain a biorepellent (O).

[0367] [Anti-fouling tape]

[0368] The antifouling tape of the present invention comprises the antifouling coating film or the laminated antifouling coating film and the adhesive layer (v), and has an adhesive layer (v) on one side of the antifouling coating film or the side of the primer coating film of the laminated antifouling coating film opposite to the side in contact with the antifouling coating film, optionally with an intermediate layer (w) interposed therebetween. The antifouling coating film or the primer coating film of the laminated antifouling coating film and the adhesive layer (v) may be directly laminated, or the antifouling coating film or the primer coating film of the laminated antifouling coating film and the adhesive layer (v) may be laminated with the intermediate layer (w) interposed therebetween.

[0369] <Middle layer (w)>

[0370] As the intermediate layer (w), at least one selected from a bonding layer, a shielding layer and a substrate layer can be cited. The bonding layer has a function of improving the bonding force between the upper layer and the lower layer of the intermediate layer, the shielding layer has a function of reducing the movement of water and other liquid substances penetrating the intermediate layer, and the substrate layer has a function of improving the strength of the laminated antifouling coating. In the intermediate layer (w), a single layer may have two or more of these functions.

[0371] When the intermediate layer (w) is provided between the primer coating film of the antifouling coating film or the laminated antifouling coating film and the adhesive layer (v), it may be one layer or two or more layers. When two or more layers are laminated, each layer may be the same or different and may be laminated in any order.

[0372] As the intermediate layer (w), any layer having a function as a tie layer can be used without limitation as long as it has excellent adhesion to the upper layer and the lower layer of the intermediate layer, and examples thereof include layers obtained by drying and curing commercially available tie coatings and primers. In particular, when the intermediate layer is in contact with an antifouling coating film containing a curable organopolysiloxane in the upper layer, a silicone resin-based tie coating or a silicone primer is preferably used.

[0373] As the intermediate layer (w), any layer having the function of a barrier layer can be used without limitation as long as it has an excellent function of reducing the movement of water or other liquid substances passing through the intermediate layer. Examples thereof include commercially available anti-corrosion coatings and materials described as water vapor barrier layers in Japanese Patent Gazette No. 2015-224334.

[0374] As the intermediate layer (w), any layer having a function as a base layer can be used without limitation as long as it has a function of improving the strength of the laminated antifouling coating film, and for example, materials described in Japanese Patent Application Laid-Open No. 2013-194124 can be used.

[0375] Examples of the intermediate layer (w) include coatings, films, and sheets made of materials such as resin, metal, paper, nonwoven fabric, cloth, and glass, or composite materials combining these materials.

[0376] The resin used as the material of the intermediate layer (w) includes, for example, silicone resin; acrylic resin; polyolefin resin; polyvinyl resin; (co)polymers of unsaturated monomers such as polystyrene; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyurethane resin; epoxy resin; polyacetal; polycarbonate; acetyl cellulose; and composites thereof.

[0377] Examples of the metal constituting the intermediate layer (w) include materials composed of one or more metal elements selected from iron, aluminum, titanium, copper and the like.

[0378] Examples of the paper constituting the middle layer (w) include uncoated printing papers such as premium paper and medium-quality paper, coated papers such as art paper and coated paper, and papers called Japanese paper and thin leaf paper.

[0379] Among them, in the intermediate layer (w) that mainly functions as a bonding layer, from the viewpoint of adhesion and ease of manufacturing, it is preferably made of resin as the material, preferably silicone resin or (co)polymer of unsaturated monomers as the material. In the intermediate layer (w) that mainly functions as a shielding layer, from the viewpoint of water resistance and ease of manufacturing, it is preferably made of resin as the material, preferably silicone resin, (co)polymer of unsaturated monomers, and epoxy resin as the material. In the intermediate layer (w) that mainly functions as a substrate layer, it is preferably made of resin, metal, or paper as the material. When using resin as the substrate, (co)polymer of unsaturated monomers and polyurethane resin are preferred.

[0380] <Adhesive layer (v)>

[0381] As the adhesive layer (v), any appropriate adhesive layer can be used within the scope that does not damage the effect of the present invention, for example, an adhesive layer as described in Japanese Patent Publication No. 2013-194124 can be used. As the material of such adhesive layer (v), for example, acrylic resin adhesives, epoxy resin adhesives, amino resin adhesives, vinyl resin (vinyl acetate polymers, etc.) adhesives, curing type acrylic resin adhesives, silicone resin adhesives, etc. can be cited. The material of the adhesive layer can be one or more than two.

[0382] In addition, a commercially available substrate-free adhesive tape may be used as the adhesive layer (v), and examples thereof include substrate-free silicone tape "NSD-100" manufactured by Nippa Corporation.

[0383] The thickness of the adhesive layer (v) is preferably 10 μm or more, more preferably 20 μm or more, and is preferably 150 μm or less, more preferably 100 μm or less, from the viewpoint of adhesive strength and handling properties.

[0384] The adhesive strength of the adhesive layer (v) of the antifouling tape of the present invention is preferably 5 N / 25 mm or more and 30 N / 25 mm or less. The adhesive strength of the adhesive layer is the adhesive strength to the adherend SUS304 at a peeling angle of 180° in accordance with JIS Z0237:2009.

[0385] For example, a tape having a structure described in Japanese Patent Application Laid-Open No. 2013-194124 or Japanese Patent Application Laid-Open No. 2016-124994 can be used as the antifouling tape.

[0386] The antifouling tape of the present invention can be manufactured by applying the present composition to an adhesive tape pre-formed with an intermediate layer (w) and an adhesive layer (v) and curing it. Commercially available products can be used as such adhesive tapes, for example, "Polyester Film Adhesive Tape 631S#100" (a tape with a total thickness of 0.15 mm consisting of a polyester film with a thickness of 0.1 mm and an acrylic adhesive layer), "Glass Cloth Adhesive Tape 540S 0.18" (a tape consisting of a glass cloth with a thickness of 0.13 mm and a silicone adhesive layer), "Kapton (registered trademark) Adhesive Tape 650S#50" (a tape with a total thickness of 0.08 mm consisting of a polyimide film with a thickness of 0.05 mm and a silicone adhesive layer), "Silicone Rubber Adhesive Tape 9013 0.1" (a tape with a total thickness of 0.1 mm obtained by sequentially laminating silicone rubber, polyester film, and acrylic adhesive), etc. can be cited.

[0387] In the antifouling tape of the present invention, since the composition is photocurable, the curing time is short, and when it is produced in a production line, it can be produced at a high speed, which is very economically advantageous.

[0388] [Substrate with antifouling coating and method for producing the same]

[0389] The substrate with an antifouling coating film of the present invention has the antifouling coating film, the laminated antifouling coating film or the antifouling tape of the present invention on a substrate.

[0390] The method for producing the substrate with an antifouling coating of the present invention is not particularly limited, but it can be obtained, for example, by a method of directly applying the present composition to a substrate and curing it, a method of bonding a preformed antifouling coating or a laminated antifouling coating to a substrate, or a method of attaching an antifouling tape to a substrate.

[0391] The above-mentioned substrate is preferably a substrate used in water. Since it is more preferably used in a wide range of industrial fields such as ships, fisheries, and underwater structures for the purpose of long-term antifouling of the substrate, for example, ships (hull plates of large steel ships such as container ships and tankers, fishing boats, FRP ships, wooden ships, and yachts. Also including any type of new ships or repair ships.), fishery materials (ropes, fishing nets, fishing gear, floats and buoys, etc.), oil pipelines, water pipes, circulating water pipes, diving suits, underwater goggles, oxygen cylinders, swimsuits, torpedoes, thermal power plants, nuclear power plants, water supply and drainage outlets and other structures, submarine cables, power transmission cables, seawater utilization equipment (seawater pumps, etc.), ultra-large floating marine structures, bay coastal roads, submarine tunnels, port equipment, and various marine civil engineering structures in canals and aqueducts. Underwater structures.

[0392] Among them, ships, underwater structures, and fishery materials are preferred, and ships and underwater structures are more preferred.

[0393] There are no particular restrictions on the material of the above-mentioned substrate, and examples include polyester resins such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), polyolefin resins such as polyethylene, chlorinated polyethylene, and polypropylene, polycarbonate, polyamide, polyimide, ABS resin, polystyrene resin, polyurethane, acrylic resin, etc. as the main body of plastics, natural rubber, butyl rubber, halogenated butyl rubber, ethylene propylene rubber, chloroprene rubber, styrene butadiene rubber, nitrile rubber, chlorosulfonated polyethylene, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluororubber, urethane rubber, glass, ceramic materials, glass fiber reinforced plastics and other composite materials, wood, paper, etc.

[0394] In order to improve the adhesion with the above-mentioned substrate and primer film, the surface treatment of the coated object can be performed before applying the coating composition of the present invention. Examples of such surface treatment include corona discharge treatment, plasma treatment, ultraviolet light, electron beam treatment such as excimer laser, photocleaning treatment, flame treatment, ozone treatment, cleaning treatment using water or organic solvent, acid treatment, alkali treatment, polishing treatment, etc.

[0395] [Antifouling method]

[0396] The antifouling method of the present invention is a method using the above-mentioned antifouling coating film, laminated antifouling coating film or antifouling tape. It is a method of performing antifouling by providing an antifouling coating film, laminated antifouling coating film or antifouling tape on various substrates to be antifouled.

[0397] Example

[0398] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Hereinafter, "parts" means parts by mass unless otherwise specified.

[0399] It should be noted that the "solid content" of each component or the present composition in this specification means the component after removing the volatile component contained as a solvent in each component or the present composition, and is synonymous with the substance obtained by drying each component or the present composition in a hot air dryer at 125°C for 1 hour.

[0400] [Components of the antifouling coating composition]

[0401] Table 1 shows the components used in the coating composition.

[0402] [Table 1]

[0403] Table 1

[0404]

[0405] <Acrylic polymer having a hydrophilic group (B2)>

[0406] (Synthesis Example 1: Synthesis of polymer (B21))

[0407] 42.9 parts by mass of methyl amyl ketone was added to a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel, and the mixture was heated to a liquid temperature of 100° C. while stirring under normal pressure and a nitrogen atmosphere. While the temperature of the reaction mixture was maintained at 100±5° C., a mixture containing 40.0 parts by mass of NK ESTER AM-90G (methoxypolyethylene glycol acrylate, average number of polyethylene glycol units: 9, manufactured by Shin-Nakamura Chemical Co., Ltd.), 60.0 parts by mass of isobutyl acrylate, and 4.0 parts by mass of 2,2'-azobis(2-methylbutyronitrile) was added dropwise to the reaction vessel over 4 hours. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 100±5° C. to obtain a solution of a polymer (B21). The solid content of the obtained solution was 70.3% by mass, the viscosity was 109 mPa·s, and the weight average molecular weight (Mw) of the polymer (B21) was 9100.

[0408] (Synthesis Example 2: Synthesis of polymer (B22))

[0409] 42.9 parts by mass of methyl amyl ketone was added to a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel, and heated to a liquid temperature of 100° C. while stirring under normal pressure and a nitrogen atmosphere. While the temperature of the reaction mixture was maintained at 100±5° C., a mixture containing 30.0 parts by mass of VISCOAT#MTG (methoxypolyethylene glycol acrylate, average number of polyethylene glycol units: 3, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 70.0 parts by mass of Silaplane FM-0711 (manufactured by JNC Corporation, dimethylpolysiloxane containing a methacrylate group, number average molecular weight: 1000), and 4.0 parts by mass of 2,2′-azobis(2-methylbutyronitrile) was added dropwise to the reaction vessel over 4 hours. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 100±5° C. to obtain a solution of a polymer (B22). The obtained solution had a solid content of 69.0% by mass and a viscosity of 35 mPa·s. The weight average molecular weight (Mw) of the polymer (B22) was 11,100.

[0410] (Solid content of polymer solution)

[0411] The polymer solution was dried at 125° C. and 1 atmosphere for 1 hour, and the mass of the obtained solid content was divided by the mass of the polymer solution before drying to determine the solid content (mass %).

[0412] (Viscosity of polymer solution)

[0413] The viscosity (mPa·s) of the polymer solution at a liquid temperature of 25° C. was measured using an E-type viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd.).

[0414] (Average molecular weight of polymer)

[0415] The weight average molecular weight (Mw) of the polymer was measured using gel permeation chromatography (GPC) under the following conditions.

[0416] (GPC conditions)

[0417] Device: "HLC-8320GPC" (manufactured by Tosoh Co., Ltd.)

[0418] Column: "TSKgel guardcolumn SuperMPHZ-M" (manufactured by Tosoh Co., Ltd.) x 1 + "TSKgel SuperMultiporeHZ-M" (manufactured by Tosoh Co., Ltd.) x 2

[0419] Eluent: Tetrahydrofuran (THF)

[0420] Flow rate: 0.35mL / min

[0421] Detector: RI

[0422] Chromatographic column thermostat temperature: 40°C

[0423] Standard material: polystyrene

[0424] Sample preparation method: An eluent was added to each obtained polymer solution and then filtered using a membrane filter. The resulting filtrate was used as a GPC measurement sample.

[0425] [Examples 1 to 16 and Comparative Examples 1 and 2]

[0426] <Manufacturing of Antifouling Coating Composition>

[0427] The components were mixed and stirred according to the blending amounts (parts by mass) described in Table 2 to prepare antifouling coating compositions.

[0428] <Preparation of Test Plate with Coating>

[0429] An epoxy-based anticorrosion primer ("BANNOH 500", manufactured by China Paint Co., Ltd.) was applied to a sandblasted steel plate (100 mm in length × 70 mm in width × 2.3 mm in thickness) so that the dry film thickness was about 100 μm, and dried for 1 day to form a primer film. Thereafter, a silicone-based mid-coat ("CMP BioClean R") was applied at 5°C so that the dry film thickness was 100 μm, and dried at 5°C for 2 hours to form a mid-coat film. Then, the antifouling coating compositions of Examples 1 to 16 and Comparative Examples 1 and 2 were applied to the mid-coat film at 5°C using a coating machine so that the cured film thickness was 200 μm, a spacer was attached, and ultraviolet irradiation was performed (LED-UV with a wavelength of 365 nm and an irradiation intensity of about 500 mW / cm 2 , irradiation time 3 seconds) to produce a test plate with a coating film.

[0430] <Adhesion Evaluation>

[0431] 12 hours after the test plate was prepared, a straight groove reaching the base coating film was cut using a single-edged blade specified in JIS K5600-5-6 on the coating surface of the test plate prepared using the antifouling coating composition of Examples 1 to 10 and Comparative Examples 1 and 2. Thereafter, the groove was wiped 10 times in a vertical direction with a wiping paper, and the occurrence of interlayer peeling with the base coating film and the intermediate coating film was evaluated according to the following criteria (standard).

[0432] (score)

[0433] 3: Interlayer delamination occurs within a range of less than 1 mm from the cut groove;

[0434] 2: Interlayer delamination occurs within a range of 1 mm to less than 3 mm from the cut groove;

[0435] 1: Interlayer delamination occurs continuously in a range of 3 mm or more from the cut groove;

[0436] 0: Already peeled off and no coating film exists.

[0437] <Antifouling Evaluation>

[0438] 24 hours after the test plates were prepared using the antifouling coating compositions of Examples 1 to 16 and Comparative Examples 1 and 2, the test plates were immersed in the sea (Hiroshima Bay, Seto Inland Sea) at a depth of 1 m relative to the sea surface so that the test surface (antifouling coating film) of the test plates faced the seabed, and the ratio of the adhesion area of ​​barnacles to the entire test surface after 3 months was evaluated by visual observation according to the following evaluation criteria.

[0439] (score)

[0440] 5: no barnacles attached;

[0441] 4: The attachment area of ​​barnacles is less than 10% of the entire test surface;

[0442] 3: The attachment area of ​​barnacles is more than 10% and less than 30% of the entire test surface;

[0443] 2: The attachment area of ​​barnacles is more than 30% and less than 80% of the entire test surface;

[0444] 1: The attachment area of ​​barnacles is 80% or more of the entire test surface.

[0445] <Adhesion Evaluation (Immediately after Irradiation)>

[0446] An epoxy anticorrosion primer ("BANNOH 500", manufactured by China Paint Co., Ltd.) was applied to a sandblasted steel plate (100 mm in length × 70 mm in width × 2.3 mm in thickness) to a dry film thickness of about 100 μm, and dried for 1 day to form a primer film. Thereafter, the antifouling coating compositions of Examples 11 to 16 were applied to the film at 5°C using a coating machine to a film thickness of 200 μm after curing, a spacer was attached, and ultraviolet irradiation (LED-UV with a wavelength of 365 nm and an irradiation intensity of about 500 mW / cm 2 , irradiation time 3 seconds), to prepare a test plate for evaluating adhesion immediately after irradiation.

[0447] Ten seconds after the test plate was prepared, a straight groove reaching the primer coating film was cut on the coating surface of the test plate using a single-edged blade specified in JIS K5600-5-6. Thereafter, the groove was wiped 10 times in a vertical direction with a wipe paper, and the adhesion (standard) was evaluated based on the following criteria for the occurrence of interlayer peeling with the primer coating film.

[0448] (score)

[0449] 3: Interlayer delamination occurs within a range of less than 1 mm from the cut groove;

[0450] 2: Interlayer delamination occurs within a range of 1 mm to less than 3 mm from the cut groove;

[0451] 1: Interlayer delamination occurs continuously in a range of 3 mm or more from the cut groove;

[0452] 0: Already peeled off and no coating film exists.

[0453]

[0454] [Table 2-2]

[0455] Table 2-2

[0456]

[0457] As is clear from the results of Examples and Comparative Examples, the present composition can form an antifouling coating film having excellent low-temperature adhesion and antifouling properties.

Claims

1. An antifouling coating composition comprising a photocurable organopolysiloxane A, a slip agent B and a photopolymerization initiator C, The content of the photocurable organopolysiloxane A in the solid content of the antifouling coating composition is 50% by mass or more and 98% by mass or less, The photocurable organopolysiloxane A has a (meth)acryloyl group, The lubricant B is one or more selected from phenyl-modified silicone, polyether-modified silicone and acrylic polymer having a hydrophilic group. The content of the slip agent B in the solid content of the antifouling coating composition is 0.1 mass % or more and 40 mass % or less, The antifouling coating composition further contains at least one of a compound represented by the following formula D1 as a silane coupling agent D, a partial condensate thereof, and a photopolymerizable monomer M. In formula (D1), R 21 and R 22 each independently represents an alkyl group, an alkenyl group, an aryl group, or a halogenated alkyl group having 1 to 10 carbon atoms, R 23 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which is optionally interposed with an amino group -NR-, an ether group -O-, a thioether group -S-, an ester group -C(=O)-O-, or an amide group -C(=O)-NR-, wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Z is a (meth)acryloyloxy group, w is an integer of 2 or 3.

2. The antifouling coating composition according to claim 1, wherein The photocurable organopolysiloxane A is represented by the following formula (I): X p R 1 （3-p） SiO(SiR 1 2O) m (SiX q R 1 （2-q） O) n SiX p R 1 （3-p） (I) In formula (I), R 1 Each independently represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group or a halogenated alkyl group having 1 to 10 carbon atoms, X each independently represents a monovalent organic group having one or more (meth)acryloyl groups and not containing a silicon atom, m represents 10 to 10000, n represents 0 to 50, p each independently represents an integer of 0 to 2, q each independently represents 1 or 2, and at least one of p and n is 1 or more.

3. The antifouling coating composition according to claim 1 or 2, wherein: The weight average molecular weight Mw of the photocurable organopolysiloxane A is 10,000 or more and 100,000 or less.

4. The antifouling coating composition according to claim 1 or 2, wherein The functional group equivalent of the photocurable organopolysiloxane A is 300 g / mol or more and 50000 g / mol or less.

5. The antifouling coating composition according to claim 1 or 2, wherein: The total content of the photocurable organopolysiloxane A and the slip agent B in the solid content of the antifouling coating composition is 70% by mass or more and 99% by mass or less. The antifouling coating composition according to claim 1 or 2, comprising a photopolymerizable monomer M. 7 . An antifouling coating film formed from the antifouling coating composition according to claim 1 . 8 . A laminated antifouling coating film comprising a primer coating film and the antifouling coating film according to claim 7 . 9 . An antifouling tape comprising the antifouling coating film according to claim 7 or the laminated antifouling coating film according to claim 8 and an adhesive layer.

10. A substrate with an antifouling coating film, comprising the antifouling coating film according to claim 7, the laminated antifouling coating film according to claim 8 or the antifouling tape according to claim 9 on the substrate.

11. The substrate with an antifouling coating according to claim 10, wherein: The substrate is one selected from ships, underwater structures, fishery materials and cables.

12. A method for producing a substrate with an antifouling coating film, comprising the steps of applying the antifouling coating composition according to any one of claims 1 to 6 to a substrate, and irradiating the applied coating film with active energy rays.

13. An antifouling method using the antifouling coating film according to claim 7, the laminated antifouling coating film according to claim 8 or the antifouling tape according to claim 9.

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