Antifouling coating agent, cured product, and laminate

Abstract

The invention provides an antifouling coating agent, a cured product, and a laminate. The antifouling coating agent comprises a silicone carbamate poly (meth) acrylate, wherein the silicone carbamate poly (meth) acrylate comprises a polysiloxane unit containing a hydroxyl group, a (poly) (meth) acrylate unit containing a hydroxyl group, a polyalkylene glycol unit containing a hydroxyl group at a single terminal, and a polyisocyanate unit.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an antifouling coating agent, a cured product, and a laminate. BACKGROUND

[0002] In order to impart surface functionality to various substrates, active energy ray-curable compositions have been developed. In recent years, from the viewpoint of global environmental protection, water-based active energy ray-curable compositions are needed. [Related Art Documents] [Patent Documents]

[0003] Patent Document 1: Japanese Patent Application Publication No. 2008-303258 SUMMARY [Problems to be Solved by the Invention]

[0004] The present invention provides an antifouling coating agent. The antifouling coating agent can produce a cured product having a good water contact angle, a marker erasing property, and a steel wool resistance. [Means of Solving the Problems]

[0005] According to the present disclosure, the following items are provided. (Item 1) An antifouling coating agent, The antifouling coating agent comprises: a silicone urethane poly(meth)acrylate, The silicone urethane poly(meth)acrylate comprises a hydroxyl group-containing polysiloxane unit, a hydroxyl group-containing (poly)(meth)acrylate unit, a single-hydroxyl group-containing polyalkylene glycol unit, and a polyisocyanate unit. (Item 2) The antifouling coating agent according to the item comprising a diol containing an ethynyl structure. (Item 3) A cured product of the antifouling coating agent according to any one of the items. (Item 4) A laminate comprising the cured product according to the item.

[0006] In the present disclosure, the one or more features can be further combined to provide, in addition to the explicit combinations. [Effects of the Invention]

[0007] The cured product of the present invention has a good water contact angle, a marker erasing property, and a steel wool resistance. DETAILED DESCRIPTION

[0008] In the entire present disclosure, the range of each physical property value, content, and the like can be appropriately set (for example, selected from the values described in each item below). Specifically, in the case where A3, A2, A1 (set as A3 > A2 > A1), and the like are cited as the value of α, the range of the value of α can be exemplified by A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, and the like.

[0009] Each component, condition, value, and the like is not particularly limited as long as the problem to be solved by the present application is solved.

[0010] The "amount of αβ (A / B)" means the amount (α) of A with respect to 100β of B. α exemplifies mass%, mole%, mass parts, and the like. The amount of β exemplifies content, use amount, and the like. The "content of mass% (A / B)" means the content (mass%) of A with respect to 100 mass% of B.

[0011] The "ratio of γ (A / B)" means the ratio of γ calculated by the formula "A ÷ B". The ratio of γ exemplifies mass ratio, mole ratio, and the like.

[0012] The "non-volatile component" means the total amount of mass of components other than organic solvents and water. In one embodiment, the "non-volatile component of A" means the total mass of components remaining when 1 g of A is heated at 105°C until the amount becomes constant.

[0013] The "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid". The "(meth)acrylate" means "acrylate and / or methacrylate". The "(meth)acryloyl group" means "acryloyl group and / or methacryloyl group".

[0014] The "poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0015] The "(poly)(meth)acrylate" means "poly(meth)acrylate and / or (meth)acrylate".

[0016] The "(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one of the group consisting of an alkylene oxide-modified (meth)acrylate, an epoxy-modified (meth)acrylate, and a (meth)acrylate".

[0017] "C..." indicates "having... carbon atoms". For example, "C1-6 alkyl" refers to alkyl groups with 1 to 6 carbon atoms. "C6 alkyl" refers to alkyl groups with 6 carbon atoms.

[0018] Alkyl groups include, for example, straight-chain alkyl groups, branched alkyl groups, and cycloalkyl groups.

[0019] Examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0020] Examples of branched alkyl groups include isopropyl, sec-butyl, isobutyl, tert-butyl, 2-ethylhexyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0021] Examples of cycloalkyl groups include monocyclic cycloalkyl groups, cross-linked cycloalkyl groups, and fused cycloalkyl groups. Furthermore, a cycloalkyl group in which at least one hydrogen atom is replaced by an alkyl group is also considered a cycloalkyl group.

[0022] A "monocyclic ring" refers to a ring structure formed by covalent bonds of carbon atoms without any bridging structures within the ring. A "fused ring" refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., they only share one edge of each ring). A "cross-linked ring" refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0023] Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0024] Cross-linked cycloalkyl groups include, for example, tricyclic decyl, adamantyl, norbornyl, etc.

[0025] Furthermore, alkyl groups also include those that combine straight-chain alkyl, branched alkyl, or cycloalkyl groups. Examples of such combined groups include cycloalkyl and alkyl groups.

[0026] [Antifouling coating agent: coating agent] This disclosure relates to an antifouling coating agent comprising: silicone urethane poly(meth)acrylate, wherein the silicone urethane poly(meth)acrylate comprises hydroxyl-containing polysiloxane units, hydroxyl-containing (poly(meth)acrylate) units, monohydroxyl-terminated polyalkylene glycol units, and polyisocyanate units.

[0027] <Silicone urethane poly(meth)acrylate> Silicone urethane poly(meth)acrylate can be used alone or in combination with two or more.

[0028] Examples of silicone urethane poly(meth)acrylates include reaction products of compounds containing hydroxyl-containing polysiloxanes, hydroxyl-containing (poly(meth)acrylates), and polyisocyanates.

[0029] (hydroxyl group-containing polysiloxane unit) The hydroxyl group-containing polysiloxane can be used alone or two or more kinds can be used.

[0030] The hydroxyl group-containing polysiloxane is exemplified by, for example, a full end hydroxyl group-containing polysiloxane, a partial end hydroxyl group-containing polysiloxane, a side chain hydroxyl group-containing polysiloxane, a hydroxyl group-containing dimethyl polysiloxane, a full end hydroxyl group-containing dimethyl polysiloxane, a partial end hydroxyl group-containing dimethyl polysiloxane, a side chain hydroxyl group-containing dimethyl polysiloxane, and the like.

[0031] "Full end A" means that the ends of the siloxane chain are all modified with a group containing A (hydroxyl group or the like).

[0032] "Partial end A" means that a part of the ends of the siloxane chain are modified with a group containing A (hydroxyl group or the like).

[0033] "Side chain A" means that (a part of) the organic group of the siloxane unit is modified with A (hydroxyl group or the like).

[0034] The product (full end hydroxyl group-containing polysiloxane) is exemplified by, for example, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

[0035] The product (partial end hydroxyl group-containing polysiloxane) is exemplified by, for example, X-22-170BX, X-22-170DX, X-22-176DX, X-22-176F, X-22-176GX-A" (manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0425, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA26 (manufactured by JNC Corporation), and the like.

[0036] The number average molecular weight (hydroxyl group-containing polysiloxane) is exemplified by, for example, 20000, 19000, 18000, 17000, 16000, 15000, 14000, 13000, 12000, 11000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1600, 1400, 1000, 800, 500, and the like. In one embodiment, the number average molecular weight is preferably exemplified by 500 to 20000, more preferably by 500 to 5000, and further preferably by 500 to 3000.

[0037] The hydroxyl equivalent weight (hydroxyl group-containing polysiloxane) is, for example, 20,000 g / mol, 19,000 g / mol, 18,000 g / mol, 17,000 g / mol, 16,000 g / mol, 15,000 g / mol, 14,000 g / mol, 13,000 g / mol, 12,000 g / mol, 11,000 g / mol, 10,000 g / mol, 9,000 g / mol, 8,000 g / mol, 7,000 g / mol, 6,000 g / mol, 5,000 g / mol, 4,000 g / mol, 3,000 g / mol, 2,000 g / mol, 1,600 g / mol, 1,400 g / mol, 1,000 g / mol, 800 g / mol, 500 g / mol, or the like. In one embodiment, the hydroxyl equivalent weight is preferably 500 g / mol to 20,000 g / mol, more preferably 500 g / mol to 5,000 g / mol, and further preferably 500 g / mol to 3,000 g / mol.

[0038] The mass % content (hydroxyl group-containing polysiloxane unit / silicone urethane poly(meth)acrylate) is, for example, 97 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, or the like. In one embodiment, the content is preferably 1 mass % to 97 mass %, more preferably 1 mass % to 50 mass %, and further preferably 1 mass % to 20 mass %.

[0039] The mole % content (hydroxyl group-containing polysiloxane unit / silicone urethane poly(meth)acrylate) is, for example, 97 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 1 mole %, or the like. In one embodiment, the content is preferably 1 mole % to 97 mole %, more preferably 1 mole % to 50 mole %, and further preferably 1 mole % to 20 mole %.

[0040] (hydroxyl group-containing (poly)(meth)acrylate unit) The hydroxyl group-containing (poly)(meth)acrylate can be used alone or two or more kinds thereof.

[0041] The hydroxyl group-containing (poly)(meth)acrylate is exemplified by a hydroxyl group-containing (meth)acrylate, a hydroxyl group-containing poly(meth)acrylate, and the like.

[0042] The hydroxyl group-containing (meth)acrylate is exemplified by hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyadamantyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and the like.

[0043] The hydroxyl group-containing poly(meth)acrylate is exemplified by a hydroxyl group-containing (poly)pentapolyol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, a hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, a hydroxyl group-containing (poly)glycerol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and the like.

[0044] In one embodiment, the hydroxyl group-containing (poly)(meth)acrylate is preferably exemplified by a hydroxyl group-containing poly(meth)acrylate, more preferably by a hydroxyl group-containing (poly)pentapolyol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and further more preferably by pentaerythritol tri(meth)acrylate.

[0045] The molecular weight (hydroxyl group-containing (poly)(meth)acrylate) is exemplified by 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, and the like. In one embodiment, the molecular weight is preferably exemplified by 100 to 1000, and more preferably by 200 to 850.

[0046] The (meth)acryloyl group number (hydroxyl group-containing (poly)(meth)acrylate) is exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1, and the like. In one embodiment, the (meth)acryloyl group number is preferably exemplified by 1 to 20.

[0047] The hydroxyl group number (hydroxyl group-containing (poly)(meth)acrylate) is exemplified by 5, 4, 3, 2, 1, and the like. In one embodiment, the hydroxyl group number is preferably exemplified by 1 to 5.

[0048] The hydroxyl value (hydroxyl group-containing (poly)(meth)acrylate) is, for example, 500 mgKOH / g, 450 mgKOH / g, 400 mgKOH / g, 350 mgKOH / g, 300 mgKOH / g, 250 mgKOH / g, 200 mgKOH / g, 150 mgKOH / g, 140 mgKOH / g, 130 mgKOH / g, 120 mgKOH / g, 110 mgKOH / g, 100 mgKOH / g, 90 mgKOH / g, 80 mgKOH / g, 70 mgKOH / g, 60 mgKOH / g, 50 mgKOH / g, 40 mgKOH / g, 30 mgKOH / g, 20 mgKOH / g, 10 mgKOH / g, 5 mgKOH / g, 1 mgKOH / g, or the like. In one embodiment, the hydroxyl value is preferably 1 mgKOH / g to 500 mgKOH / g, more preferably 10 mgKOH / g to 500 mgKOH / g, and further preferably 30 mgKOH / g to 300 mgKOH / g.

[0049] The hydroxyl value is a value determined in accordance with JIS K0070:1992 (neutralization titration method).

[0050] The mass % content (hydroxyl group-containing (poly)(meth)acrylate unit / silicone urethane poly(meth)acrylate) is, for example, 97 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 1 mass%, or the like. In one embodiment, the content is preferably 1 mass% to 97 mass%, more preferably 1 mass% to 70 mass%, and further preferably 15 mass% to 50 mass%.

[0051] The mole % content (hydroxyl group-containing (poly)(meth)acrylate unit / silicone urethane poly(meth)acrylate) is, for example, 97 mole%, 95 mole%, 90 mole%, 85 mole%, 80 mole%, 75 mole%, 70 mole%, 65 mole%, 60 mole%, 55 mole%, 50 mole%, 45 mole%, 40 mole%, 35 mole%, 30 mole%, 25 mole%, 20 mole%, 15 mole%, 10 mole%, 5 mole%, 1 mole%, or the like. In one embodiment, the content is preferably 1 mole% to 97 mole%, more preferably 1 mole% to 70 mole%, and further preferably 15 mole% to 50 mole%.

[0052] (polyisocyanate unit) The polyisocyanate can be used alone or two or more kinds can be used.

[0053] The "polyisocyanate" refers to a compound having two or more isocyanate groups (-N=C=O).

[0054] The polyisocyanate is exemplified by, for example, linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and biuret bodies, isocyanurate bodies, allophanate bodies, adduct bodies, and the like thereof.

[0055] The linear aliphatic polyisocyanate is exemplified by, for example, methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like.

[0056] The branched aliphatic polyisocyanate is exemplified by, for example, diethyl pentylene diisocyanate, trimethyl butylene diisocyanate, trimethyl pentylene diisocyanate, trimethyl hexamethylene diisocyanate, and the like.

[0057] The alicyclic polyisocyanate is exemplified by, for example, monocyclic alicyclic polyisocyanates, cross-linked cyclic alicyclic polyisocyanates, fused ring alicyclic polyisocyanates, and the like.

[0058] The monocyclic alicyclic polyisocyanate is exemplified by, for example, hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, and the like.

[0059] The cross-linked cyclic alicyclic polyisocyanate is exemplified by, for example, tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

[0060] The fused ring alicyclic polyisocyanate is exemplified by, for example, bicyclodecylene diisocyanate, and the like.

[0061] The aromatic polyisocyanate is exemplified by, for example, monocyclic aromatic polyisocyanates, fused ring aromatic polyisocyanates, and the like.

[0062] The monocyclic aromatic polyisocyanate is exemplified by, for example, dialkyl diphenyl methane diisocyanates such as 4,4'-diphenyl dimethyl methane diisocyanate, tetraalkyl diphenyl methane diisocyanates such as 4,4'-diphenyl tetramethyl methane diisocyanate, 4,4'-diphenyl methane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, and the like.

[0063] Fused ring aromatic polyisocyanate is exemplified by 1,5-naphthalene diisocyanate and the like.

[0064] Isocyanate group number (polyisocyanate) is exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, and the like. In one embodiment, the isocyanate group number is preferably exemplified by 2 to 20, more preferably by 3 to 20.

[0065] Number average molecular weight (polyisocyanate) is exemplified by 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, and the like. In one embodiment, the number average molecular weight is preferably exemplified by 100 to 5000.

[0066] Mass % content (polyisocyanate unit / silicone urethane poly(meth)acrylate) is exemplified by 97 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, and the like. In one embodiment, the content is preferably exemplified by 1 mass % to 97 mass %, more preferably by 5 mass % to 60 mass %, further preferably by 15 mass % to 40 mass %.

[0067] Mole % content (polyisocyanate unit / silicone urethane poly(meth)acrylate) is exemplified by 97 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 1 mole %, and the like. In one embodiment, the content is preferably exemplified by 1 mole % to 97 mole %, more preferably by 5 mole % to 60 mole %, further preferably by 15 mole % to 40 mole %.

[0068] (Single end-hydroxyl group-containing polyalkylene glycol unit) In one embodiment, the silicone urethane poly(meth)acrylate can optionally contain a single end-hydroxyl group-containing polyalkylene glycol unit. The single end-hydroxyl group-containing polyalkylene glycol can be used alone or two or more kinds can be used.

[0069] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0070] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0071] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0072] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0073] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0074] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0075] Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polyethylene glycol polypropylene glycol monoalkyl ether, polyethylene glycol polytetramethylene glycol monoalkyl ether, polypropylene glycol polytetramethylene glycol monoalkyl ether, and the like.

[0076] In one embodiment, the mono-terminal hydroxyl group-containing polyalkylene glycol is represented by the following formula. H-(OCR PA1 HCH2) pa -OR PA2 (R PA1 represents a hydrogen atom or a methyl group. R PA2 represents a C1-4 alkyl group, an allyl group, a (meth)acryl group, or a C1-4 acyl group. pa represents an integer of 2 to 125.

[0077] ​The product (a single-end hydroxyl group-containing polyalkylene glycol) is exemplified by Uniox M-400, Uniox M-550, Uniox M-1000, Uniox M-2000, Uniox M-2500, Uniox M-3000, Uniox M-4000, Blemmer PE-90, Blemmer PE-200, Blemmer PE-300, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400 (Nippon Oil & Fats Corporation), and the like.

[0078] The number average molecular weight (a single-end hydroxyl group-containing polyalkylene glycol) is exemplified by 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, and the like. In one embodiment, the number average molecular weight is preferably selected from the range of 100 to 5000, more preferably from the range of 200 to 3000, and further preferably from the range of 300 to 2000.

[0079] The hydroxyl value (a single-end hydroxyl group-containing polyalkylene glycol) is exemplified by 500 mgKOH / g, 450 mgKOH / g, 400 mgKOH / g, 350 mgKOH / g, 300 mgKOH / g, 250 mgKOH / g, 200 mgKOH / g, 150 mgKOH / g, 140 mgKOH / g, 130 mgKOH / g, 120 mgKOH / g, 110 mgKOH / g, 100 mgKOH / g, 90 mgKOH / g, 80 mgKOH / g, 70 mgKOH / g, 60 mgKOH / g, 50 mgKOH / g, 40 mgKOH / g, 30 mgKOH / g, 20 mgKOH / g, 10 mgKOH / g, and the like. In one embodiment, the hydroxyl value is preferably selected from the range of 10 mgKOH / g to 500 mgKOH / g.

[0080] The mass % content (a single-end hydroxyl group-containing polyalkylene glycol unit / silicone urethane poly(meth)acrylate) is exemplified by 97 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0 mass %, and the like. In one embodiment, the content is preferably selected from the range of 0 mass % to 97 mass %, more preferably from the range of 1 mass % to 97 mass %, further preferably from the range of 10 mass % to 80 mass %, and particularly preferably from the range of 20 mass % to 60 mass %.

[0081] The mole % content (hydroxyl group-containing polyalkylene glycol unit having a single end / silicone urethane poly(meth)acrylate) is exemplified by 97 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 1 mole %, 0 mole %, etc. In one embodiment, the content is preferably exemplified by 0 mole % to 97 mole %, more preferably by 1 mole % to 97 mole %, further preferably by 10 mole % to 80 mole %, particularly preferably by 20 mole % to 60 mole %.

[0082] (the unit not in conformity with any of the above: other unit) The silicone urethane poly(meth)acrylate can optionally contain the unit not in conformity with any of the above (other unit).

[0083] The other unit is exemplified by a monoisocyanate unit, etc.

[0084] In one embodiment, the mass part content (other unit / silicone urethane poly(meth)acrylate) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0085] In one embodiment, the mass part content (other unit / hydroxyl group-containing polysiloxane unit) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0086] In one embodiment, the mass part content (other unit / hydroxyl group-containing (poly) (meth) acrylate unit) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0087] In one embodiment, the mass part content (other unit / hydroxyl group-containing polyalkylene glycol unit having a single end) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0088] In one embodiment, the mass part content (other unit / polyisocyanate unit) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0089] The silicone urethane poly(meth)acrylate can be produced by reacting raw materials, using a solvent and / or a catalyst as necessary.

[0090] The solvent is exemplified by, for example, the following monometh)l acrylate, the following organic solvent, and the like.

[0091] The catalyst is exemplified by, for example, organotin (tin octoate, tin octyl dilaurate, and the like), organozirconium (zirconium tetraacetylacetonate, and the like), organotitanium (titanium tetraisopropylate, titanium acetylacetonate, and the like), organobismuth (bismuth octoate, and the like), and the like.

[0092] The reaction temperature is preferably exemplified by 60°C to 90°C.

[0093] The (meth)acryloyl group number (silicone urethane poly(meth)acrylate) is exemplified by, for example, 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, and the like. In one embodiment, the (meth)acryloyl group number is preferably exemplified by 2 to 20.

[0094] The mass% content (silicone urethane poly(meth)acrylate / antifouling coating agent nonvolatile matter) is exemplified by, for example, 99.5 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 1 mass%, 0.99 mass%, 0.5 mass%, 0.1 mass%, and the like. In one embodiment, the content is preferably exemplified by 0.1 mass% to 99.5 mass%.

[0095] <silicone urethane-free poly(meth)acrylate> In one embodiment, the antifouling coating agent can optionally contain a silicone urethane-free poly(meth)acrylate. The silicone urethane-free poly(meth)acrylate can be used alone or two or more kinds thereof.

[0096] The silicone urethane-free poly(meth)acrylate is exemplified by, for example, a reaction product of a compound group containing a hydroxyl group-containing (poly)(meth)acrylate and a polyisocyanate, and the like.

[0097] (hydroxyl group-containing (poly)(meth)acrylate) The hydroxyl group-containing (poly)(meth)acrylate can be used alone or two or more kinds thereof.

[0098] The hydroxyl group-containing (poly)(meth)acrylate is exemplified by, for example, the compound, and the like.

[0099] The content (mass %) of the (poly) (meth) acrylate unit containing a hydroxyl group / silicone non-urethane poly (meth) acrylate is, for example, 98 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, or the like. In one embodiment, the content is preferably 1 mass % to 98 mass %.

[0100] The content (mole %) of the (poly) (meth) acrylate unit containing a hydroxyl group / silicone non-urethane poly (meth) acrylate is, for example, 98 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 1 mole %, or the like. In one embodiment, the content is preferably 1 mole % to 98 mole %.

[0101] (polyisocyanate) The polyisocyanate can be used alone or two or more kinds can be used.

[0102] The polyisocyanate is, for example, the compound or the like.

[0103] The content (mass %) of the polyisocyanate unit / silicone non-urethane poly (meth) acrylate is, for example, 98 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, or the like. In one embodiment, the content is preferably 1 mass % to 98 mass %.

[0104] The content (mole %) of the polyisocyanate unit / silicone non-urethane poly (meth) acrylate is, for example, 98 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 1 mole %, or the like. In one embodiment, the content is preferably 1 mole % to 98 mole %.

[0105] (mono-terminal hydroxyl group-containing polyalkylene glycol) In one embodiment, the silicone urethane-free poly(meth)acrylate optionally contains a mono-terminal hydroxyl group-containing polyalkylene glycol unit. The mono-terminal hydroxyl group-containing polyalkylene glycol can be used alone or two or more kinds thereof can be used.

[0106] The mono-terminal hydroxyl group-containing polyalkylene glycol is exemplified by, for example, the compound.

[0107] The mass % content (mono-terminal hydroxyl group-containing polyalkylene glycol unit / silicone urethane-free poly(meth)acrylate) is exemplified by, for example, 98 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0 mass %, and the like. In one embodiment, the content is preferably exemplified by 0 mass % to 98 mass %, more preferably by 1 mass % to 98 mass %.

[0108] The mole % content (mono-terminal hydroxyl group-containing polyalkylene glycol unit / silicone urethane-free poly(meth)acrylate) is exemplified by, for example, 98 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, 10 mole %, 5 mole %, 1 mole %, 0 mole %, and the like. In one embodiment, the content is preferably exemplified by 0 mole % to 98 mole %, more preferably by 1 mole % to 98 mole %.

[0109] (the unit which does not match any of the above: other unit) The silicone urethane-free poly(meth)acrylate optionally contains the unit which does not match any of the above (other unit).

[0110] The other unit is exemplified by, for example, a mono-isocyanate unit.

[0111] In one embodiment, the mass part content (other unit / silicone urethane-free poly(meth)acrylate) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, and the like.

[0112] In one embodiment, the mass part content (other unit / hydroxyl group-containing (poly) (meth) acrylate unit) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, and the like.

[0113] In one embodiment, the mass content (other units / units containing hydroxyl group-containing polyalkylene glycol units) is preferably selected from the group consisting of less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.

[0114] In one embodiment, the mass content (other units / polyisocyanate units) is preferably selected from the group consisting of less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.

[0115] The production method (silicone urethane-free poly(meth)acrylate) is exemplified by the method described above, and the like.

[0116] The (meth)acryloyl group number (silicone urethane-free poly(meth)acrylate) is exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, and the like. In one embodiment, the (meth)acryloyl group number is preferably selected from the range of 2 to 20.

[0117] The mass % content (silicone urethane-free poly(meth)acrylate / antifouling coating agent nonvolatile matter) is exemplified by 98 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0 mass %, and the like. In one embodiment, the content is preferably selected from the range of 0 mass % to 98 mass %.

[0118] <urethane bond-free poly(meth)acrylate> In one embodiment, the antifouling coating agent can optionally contain a urethane bond-free poly(meth)acrylate. The urethane bond-free poly(meth)acrylate can be used alone or two or more kinds thereof.

[0119] The urethane bond-free poly(meth)acrylate is exemplified by (poly) pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)glycerol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, multifunctional (meth)acrylamide, poly(meth)acrylate containing an oxygen-hydrogen bond, and the like.

[0120] ((poly) pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate) "(Poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one of the group consisting of trimethylolpropane poly(meth)acrylate, trimethylolpropane polyalkylene oxide-modified (meth)acrylate, trimethylolpropane polyepoxy-modified (meth)acrylate, polytrimethylolpropane poly(meth)acrylate, polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate, and polytrimethylolpropane polyepoxy-modified (meth)acrylate."

[0121] Trimethylolpropane poly(meth)acrylate is exemplified by trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tetra(meth)acrylate, and the like.

[0122] Trimethylolpropane polyalkylene oxide-modified (meth)acrylate is exemplified by trimethylolpropane di(ethylene oxide-modified (meth)acrylate), trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), trimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), trimethylolpropane di(propylene oxide-modified (meth)acrylate), trimethylolpropane tri(propylene oxide-modified (meth)acrylate), trimethylolpropane tetra(alkylene oxide-modified (meth)acrylate), and the like.

[0123] Trimethylolpropane polyepoxy-modified (meth)acrylate is exemplified by trimethylolpropane di(epoxy (meth)acrylate), trimethylolpropane tri(epoxy (meth)acrylate), trimethylolpropane tetraalkylene (meth)acrylate, and the like.

[0124] Polytrimethylolpropane poly(meth)acrylate is exemplified by dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and the like.

[0125] Polymeric pentaerythritol polyalkylene oxide-modified (meth)acrylates such as, for example, dipentaerythritol di(ethylene oxide-modified (meth)acrylate), dipentaerythritol tri(ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide-modified (meth)acrylate), dipentaerythritol penta(ethylene oxide-modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide-modified (meth)acrylate), dipentaerythritol di(propylene oxide-modified (meth)acrylate), dipentaerythritol tri(propylene oxide-modified (meth)acrylate), dipentaerythritol tetra(propylene oxide-modified (meth)acrylate), dipentaerythritol penta(propylene oxide-modified (meth)acrylate), dipentaerythritol hexa(propylene oxide-modified (meth)acrylate), tri-pentaerythritol di(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol tri(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol penta(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol hexa(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol hepta(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol octa(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol di(propylene oxide-modified (meth)acrylate), tri-pentaerythritol tri(propylene oxide-modified (meth)acrylate), tri-pentaerythritol tetra(propylene oxide-modified (meth)acrylate), tri-pentaerythritol penta(propylene oxide-modified (meth)acrylate), tri-pentaerythritol hexa(propylene oxide-modified (meth)acrylate), tri-pentaerythritol hepta(propylene oxide-modified (meth)acrylate), tri-pentaerythritol octa(propylene oxide-modified (meth)acrylate), and the like.

[0126] Polymeric pentaerythritol polyalkylene oxide-modified (meth)acrylates such as, for example, dipentaerythritol di(ethylene oxide-modified (meth)acrylate), dipentaerythritol tri(ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide-modified (meth)acrylate), dipentaerythritol penta(ethylene oxide-modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide-modified (meth)acrylate), dipentaerythritol di(propylene oxide-modified (meth)acrylate), dipentaerythritol tri(propylene oxide-modified (meth)acrylate), dipentaerythritol tetra(propylene oxide-modified (meth)acrylate), dipentaerythritol penta(propylene oxide-modified (meth)acrylate), dipentaerythritol hexa(propylene oxide-modified (meth)acrylate), tri-pentaerythritol di(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol tri(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol penta(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol hexa(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol hepta(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol octa(ethylene oxide-modified (meth)acrylate), tri-pentaerythritol di(propylene oxide-modified (meth)acrylate), tri-pentaerythritol tri(propylene oxide-modified (meth)acrylate), tri-pentaerythritol tetra(propylene oxide-modified (meth)acrylate), tri-pentaerythritol penta(propylene oxide-modified (meth)acrylate), tri-pentaerythritol hexa(propylene oxide-modified (meth)acrylate), tri-pentaerythritol hepta(propylene oxide-modified (meth)acrylate), tri-pentaerythritol octa(propylene oxide-modified (meth)acrylate), and the like.

[0127] ((poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylates) "(Poly)trimethylolpropane poly(epoxyalkylene-modified or epoxy-modified) (meth)acrylate" means "at least one of the group consisting of trimethylolpropane poly(meth)acrylate, trimethylolpropane polyepoxyalkylene-modified (meth)acrylate, trimethylolpropane polyepoxy-modified (meth)acrylate, polytrimethylolpropane poly(meth)acrylate, polytrimethylolpropane polyepoxyalkylene-modified (meth)acrylate, and polytrimethylolpropane polyepoxy-modified (meth)acrylate."

[0128] Trimethylolpropane poly(meth)acrylates are exemplified by trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the like.

[0129] Trimethylolpropane polyepoxyalkylene-modified (meth)acrylates are exemplified by trimethylolpropane di(epoxyethane-modified (meth)acrylate), trimethylolpropane tri(epoxyethane-modified (meth)acrylate), trimethylolpropane di(epoxypropane-modified (meth)acrylate), trimethylolpropane tri(epoxypropane-modified (meth)acrylate), and the like.

[0130] Trimethylolpropane polyepoxy-modified (meth)acrylates are exemplified by trimethylolpropane diepoxy(meth)acrylate, trimethylolpropane trialkylene(meth)acrylate, and the like.

[0131] Polytrimethylolpropane poly(meth)acrylates are exemplified by di-trimethylolpropane di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like.

[0132] Polytrimethylolpropane polyepoxyalkylene-modified (meth)acrylates are exemplified by di-trimethylolpropane di(epoxyethane-modified (meth)acrylate), di-trimethylolpropane tri(epoxyethane-modified (meth)acrylate), ditrimethylolpropane tetra(epoxyethane-modified (meth)acrylate), di-trimethylolpropane di(epoxypropane-modified (meth)acrylate), di-trimethylolpropane tri(epoxypropane-modified (meth)acrylate), ditrimethylolpropane tetra(epoxypropane-modified (meth)acrylate), and the like.

[0133] Polytrimethylolpropane polyepoxy-modified (meth)acrylates are exemplified by di-trimethylolpropane diepoxy(meth)acrylate, di-trimethylolpropane triepoxy(meth)acrylate, ditrimethylolpropane tetraalkylene(meth)acrylate, and the like.

[0134] ((Poly)glycerol poly(epoxyalkylene-modified or epoxy-modified) (meth)acrylate) "(Poly)glycerol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one of the group consisting of glycerol poly(meth)acrylate, glycerol polyalkylene oxide-modified (meth)acrylate, glycerol polyepoxy-modified (meth)acrylate, polyglycerol poly(meth)acrylate, polyglycerol polyalkylene oxide-modified (meth)acrylate, and polyglycerol polyepoxy-modified (meth)acrylate".

[0135] Glycerol poly(meth)acrylates are exemplified by glycerol di(meth)acrylate, glycerol tri(meth)acrylate, and the like.

[0136] Glycerol polyalkylene oxide-modified (meth)acrylates are exemplified by glycerol di(ethylene oxide-modified (meth)acrylate), glycerol tri(ethylene oxide-modified (meth)acrylate), glycerol di(propylene oxide-modified (meth)acrylate), glycerol tri(epoxy (meth)acrylate), and the like.

[0137] Glycerol polyepoxy-modified (meth)acrylates are exemplified by glycerol diepoxy (meth)acrylate, glycerol trialkylene (meth)acrylate, and the like.

[0138] Polyglycerol poly(meth)acrylates are exemplified by diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, triglycerol di(meth)acrylate, triglycerol tri(meth)acrylate, triglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, and the like.

[0139] Polyglycerol polyalkylene oxide-modified (meth)acrylates are exemplified by diglycerol di(ethylene oxide-modified (meth)acrylate), diglycerol tri(ethylene oxide-modified (meth)acrylate), diglycerol tetra(ethylene oxide-modified (meth)acrylate), triglycerol di(ethylene oxide-modified (meth)acrylate), triglycerol tri(ethylene oxide-modified (meth)acrylate), triglycerol tetra(ethylene oxide-modified (meth)acrylate), triglycerol penta(ethylene oxide-modified (meth)acrylate) diglycerol di(propylene oxide-modified (meth)acrylate), diglycerol tri(propylene oxide-modified (meth)acrylate), diglycerol tetra(epoxy (meth)acrylate), triglycerol di(propylene oxide-modified (meth)acrylate), triglycerol tri(propylene oxide-modified (meth)acrylate), triglycerol tetra(propylene oxide-modified (meth)acrylate), triglycerol penta(epoxy (meth)acrylate), and the like.

[0140] Polyglycerol polyepoxy-modified (meth)acrylates include, for example, diglyceryl di(meth)acrylate, diglyceryl tri(meth)acrylate, diglyceryl tetraalkylene(meth)acrylate, triglyceryl di(meth)acrylate, triglyceryl tri(meth)acrylate, triglyceryl tetra(meth)acrylate, triglyceryl pentaalkylene(meth)acrylate, and the like.

[0141] Polyfunctional (meth)acrylamides include, for example, N,N'-bis(meth)acryloyl-4,7,10-trioxa-l,13-tridecanediamine, N,N',N"-tris(meth)acryloyldiethylenetriamine, 1,3,5-tris(meth)acryloylhexahydro-l,3,5-triazine, N,N'-{[(2-(meth)acrylamido-2-[(3-(meth)acrylamidopropoxy)methyl]propane-l,3-diyl)bis(oxy)]bis(propane-l,3-diyl)}di(meth)acrylamide, N,N',N",N"-tetra(meth)acryloyltrisethylenetetramine, and the like.

[0142] "Poly(meth)acrylate containing an oxygen-hydrogen bond" means a poly(meth)acrylate having an oxygen-hydrogen bond at a pH of 7 or less. The poly(meth)acrylate containing an oxygen-hydrogen bond can be a salt at a pH higher than 7.

[0143] Poly(meth)acrylates containing an oxygen-hydrogen bond include, for example, poly(meth)acrylates containing a hydroxyl group, poly(meth)acrylates containing a carboxyl group, and the like.

[0144] Poly(meth)acrylates containing a carboxyl group include, for example, reaction products of poly(meth)acrylates containing a hydroxyl group with carboxylic anhydrides, and the like.

[0145] As the poly(meth)acrylates containing a hydroxyl group, compounds having a hydroxyl group among the above poly(meth)acrylates can be mentioned.

[0146] Carboxylic anhydrides include, for example, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, itaconic anhydride, succinic anhydride, and the like.

[0147] Articles (poly(meth)acrylates containing a carboxyl group) include, for example, Aronix M510 (acid value: 80 mgKOH / g to 120 mgKOH / g), Aronix M520 (acid value: 20 mgKOH / g to 40 mgKOH / g), Aronix M521 (acid value: 65 mgKOH / g to 69 mgKOH / g) (all of which are manufactured by Toagosei Co., Ltd.), and the like.

[0148] In one embodiment, the carboxyl group-containing poly(meth)acrylate preferably elects a reaction product of a hydroxyl group-containing (poly)pentapolyol poly(meth)acrylate with a carboxylic anhydride, more preferably elects a reaction product of a hydroxyl group-containing (poly)pentapolyol poly(meth)acrylate with succinic anhydride.

[0149] The (meth)acryloyl number (not including poly(meth)acrylate in urethane bond) is exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, etc. In one embodiment, the (meth)acryloyl number is preferably elected from the range of 2 to 20.

[0150] The hydroxyl value (not including poly(meth)acrylate in urethane bond) is exemplified by 800 mgKOH / g, 700 mgKOH / g, 600 mgKOH / g, 500 mgKOH / g, 450 mgKOH / g, 400 mgKOH / g, 350 mgKOH / g, 300 mgKOH / g, 250 mgKOH / g, 200 mgKOH / g, 150 mgKOH / g, 100 mgKOH / g, 50 mgKOH / g, 25 mgKOH / g, 10 mgKOH / g, 0 mgKOH / g, etc. In one embodiment, the hydroxyl value is preferably elected from the range of 0 mgKOH / g to 800 mgKOH / g.

[0151] The acid value (not including poly(meth)acrylate in urethane bond) is exemplified by 300 mgKOH / g, 290 mgKOH / g, 280 mgKOH / g, 270 mgKOH / g, 260 mgKOH / g, 250 mgKOH / g, 240 mgKOH / g, 230 mgKOH / g, 220 mgKOH / g, 210 mgKOH / g, 200 mgKOH / g, 190 mgKOH / g, 180 mgKOH / g, 170 mgKOH / g, 160 mgKOH / g, 150 mgKOH / g, 140 mgKOH / g, 130 mgKOH / g, 120 mgKOH / g, 110 mgKOH / g, 100 mgKOH / g, 90 mgKOH / g, 80 mgKOH / g, 70 mgKOH / g, 60 mgKOH / g, 50 mgKOH / g, 40 mgKOH / g, 30 mgKOH / g, 20 mgKOH / g, 10 mgKOH / g, 0 mgKOH / g, etc. In one embodiment, the acid value is preferably elected from the range of 0 mgKOH / g to 300 mgKOH / g.

[0152] The content of the urethane bond (mass %) is, for example, 98 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0 mass %, or the like. In one embodiment, the content is preferably 0 mass % to 98 mass %.

[0153] <mono(meth)acrylate> In one embodiment, the antifouling coating agent can optionally contain a mono(meth)acrylate. The mono(meth)acrylate can be used alone or two or more kinds can be used.

[0154] The mono(meth)acrylate is, for example, a linear alkyl mono(meth)acrylate, a branched alkyl mono(meth)acrylate, a cyclic alkyl mono(meth)acrylate, or the like.

[0155] The linear alkyl mono(meth)acrylate is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, or the like.

[0156] The branched alkyl mono(meth)acrylate is, for example, isopropyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, diethyl (meth)acrylate, trimethyl (meth)acrylate, trimethyl (meth)acrylate, trimethyl (meth)acrylate, or the like.

[0157] The cyclic alkyl mono(meth)acrylate is, for example, cyclohexyl mono(meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, or the like.

[0158] The mass % content (mon(meth)acrylate / antifouling coating agent nonvolatile matter) is, for example, 98 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0 mass %, or the like. In one embodiment, the content is preferably 0 mass % to 98 mass %.

[0159] <Organically modified silicone> In one embodiment, the coating agent can optionally contain an organically modified silicone. The organically modified silicone can be used alone or two or more kinds can be used.

[0160] The silicone urethane poly(meth)acrylate is not an organically modified silicone.

[0161] "Organically modified silicone" refers to a compound in which an organic group is introduced into a silicone. The organically modified silicone is, for example, a side chain organically modified silicone, a full end group organically modified silicone, a partial end group organically modified silicone, a side chain full end group organically modified silicone, or the like.

[0162] The organically modified silicone is, for example, an acrylic-modified silicone, a polyester-modified silicone, a polyether-modified silicone, a carbinol-modified silicone, or the like.

[0163] The product (acrylic-modified silicone) is, for example, ZX-028-G (manufactured by T&K TOKA Co., Ltd.), BYK-3565, BYK-SILCLEAN 3700 (manufactured by BYK Chemie Japan Co., Ltd.), SYMACUS-270 (manufactured by Toagosei Co., Ltd.), or the like.

[0164] The product (polyester-modified silicone) is, for example, BYK-370 (manufactured by BYK), or the like.

[0165] The product (polyether-modified silicone) is, for example, BYK-348, BYK-375, BYK-377, BYK-SILCLEAN 3720 (manufactured by BYK Chemie Japan Co., Ltd.), X-22-4952, X-22-4272, KF-6123 (manufactured by Shin-Etsu Chemical Co., Ltd.), or the like.

[0166] The product (carbitol-modified silicone) is exemplified by X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003, KF-6123, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0425, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA26 (manufactured by JNC Corporation), and the like.

[0167] The content (silicone / antifouling coating agent nonvolatile matter) is exemplified by 20 mass%, 19 mass%, 17 mass%, 15 mass%, 13 mass%, 11 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.4 mass%, 0.3 mass%, 0.1 mass%, 0 mass%, and the like. In one embodiment, the content is preferably exemplified by 0 mass% to 20 mass%, more preferably by 0 mass% to 10 mass%.

[0168] <Diol containing acetylene structure> In one embodiment, the coating agent can optionally contain a diol containing an acetylene structure. The diol containing an acetylene structure can be used alone or two or more kinds thereof.

[0169] The "diol containing an acetylene structure" refers to a diol having a carbon-carbon triple bond.

[0170] In one embodiment, the diol containing an acetylene structure is represented by the following structural formula.

Chemical AG

[0171] The product (diol containing an ethynyl structure) is exemplified by SURFYNOL 61, 82, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, 465, 485, DF-110D, SE, SE-F; Dynol 604, 607; Olfine E1004, E1010, E1020, PD-001, PD-002W, PD-004, PD-005, EXP.4001, EXP.4200, EXP.4123, EXP.4300 (manufactured by Nippon Shokubai Co., Ltd.); Ethynyl alcohol E40, E60, E100, E130T, E200 (manufactured by Kawaken Fine Chemicals Co., Ltd.); and the like.

[0172] The content (diol containing an ethynyl structure / nonvolatile content of the antifouling coating agent) is exemplified by 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1.5 mass%, 1 mass%, 0.9 mass%, 0.8 mass%, 0.5 mass%, 0 mass%, and the like. In one embodiment, the content is preferably exemplified by 0 mass% to 10 mass%.

[0173] <Photopolymerization initiator> In one embodiment, the antifouling coating agent can optionally contain a photopolymerization initiator. The photopolymerization initiator can be used alone or two or more kinds can be used.

[0174] The photopolymerization initiator is exemplified by an α-hydroxydimethyl phenyl ketone group-containing photopolymerization initiator, α-hydroxy cycloalkyl phenyl ketone, α-amino alkyl phenyl ketone, benzyl dimethyl ketal, unsubstituted or substituted alkyl phenyl ketone, unsubstituted or substituted benzyl benzyl, unsubstituted or substituted benzophenone, acyl phosphine oxide, substituted thioxanthone, oxime ester, and the like.

[0175] The α-hydroxydimethyl phenyl ketone group-containing photopolymerization initiator is exemplified by 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropan-1-one, and the like.

[0176] The α-hydroxy cycloalkyl phenyl ketone is exemplified by 1-hydroxycyclohexyl phenyl ketone and the like.

[0177] The α-amino alkyl phenyl ketone is exemplified by 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and the like.

[0178] The benzyl dimethyl ketal is exemplified by 2,2-dimethoxy-1,2-diphenylethan-1-one and the like.

[0179] Unsubstituted or substituted benzyl ketones are exemplified by benzyl methyl ether, benzyl isopropyl ether, benzyl isobutyl ether, benzyl ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonipecotinyl phenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.

[0180] Unsubstituted or substituted benzyl ketones are exemplified by benzyl methyl ether, benzyl isopropyl ether, benzyl isobutyl ether, benzyl ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonipecotinyl phenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.

[0181] Unsubstituted or substituted benzyl ketones are exemplified by benzyl methyl ether, benzyl isopropyl ether, benzyl isobutyl ether, benzyl ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isonipecotinyl phenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.

[0182] Acyl phosphine oxides are exemplified by 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, and the like.

[0183] Substituted thioxanthones are exemplified by 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

[0184] Oxime esters are exemplified by 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyl oxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (i.e., 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidene)amino)oxy)ethan-1-one), and the like.

[0185] When electron beam curing is performed, a photopolymerization initiator is not required.

[0186] The mass % content (photopolymerization initiator / antifouling coating agent nonvolatile matter) is exemplified by 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass %, 0.9 mass %, 0.7 mass %, 0.5 mass %, 0 mass %, and the like. In one embodiment, the content is preferably exemplified by 0 mass % to 50 mass %.

[0187] <Water> Water can be used alone or two or more kinds can be used.

[0188] Water is exemplified by, for example, ultrapure water, pure water, distilled water, ion-exchanged water, tap water, and the like.

[0189] The mass % content (water / antifouling coating agent) is exemplified by, for example, 99 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass %, 0.9 mass %, 0.7 mass %, 0.5 mass %, and the like. In one embodiment, the content is preferably exemplified by 0.5 mass % to 99 mass %, and more preferably by 10 mass % to 60 mass %.

[0190] <Organic solvent> In one embodiment, the antifouling coating agent can optionally contain an organic solvent. The organic solvent can be used alone or two or more kinds can be used.

[0191] The organic solvent is exemplified by, for example, a ketone solvent, an aromatic solvent, an alcohol solvent, a glycol solvent, a glycol ether solvent, an ester solvent, a petroleum-based solvent, a halogenated alkane solvent, an amide solvent, and the like.

[0192] The ketone solvent is exemplified by, for example, methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and the like.

[0193] The aromatic solvent is exemplified by, for example, toluene, xylene, and the like.

[0194] The alcohol solvent is exemplified by, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, and the like.

[0195] The glycol solvent is exemplified by, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and the like.

[0196] The glycol ether solvent is exemplified by, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, ethylene glycol mono-t-butyl ether, and the like.

[0197] The ester solvent is exemplified by, for example, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and the like.

[0198] Petroleum-based solvents are exemplified by, for example, aromatic hydrocarbon oil (SOLVESSO) #100 (manufactured by Exxon), aromatic hydrocarbon oil (SOLVESSO) #150 (manufactured by Exxon), and the like.

[0199] Halogenated alkane solvents are exemplified by, for example, chloroform, and the like.

[0200] Amide solvents are exemplified by, for example, dimethylformamide, and the like.

[0201] The mass % content (organic solvent / antifouling coating agent) is exemplified by, for example, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, and the like. In one embodiment, the content is preferably exemplified by 0 mass % to 60 mass %.

[0202] <additives> The antifouling coating agent can optionally contain an agent (additive) that does not conform to any of the above.

[0203] Additives are exemplified by, for example, anti-slip agents, slip agents, preservatives, rust-preventive agents, pH adjustors, pigments, dyes, lubricants, leveling agents, catalysts, defoaming agents, photosensitizers, and the like.

[0204] In one embodiment, the mass part content (additive / antifouling coating agent) is preferably exemplified by less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, 0 mass %, and the like.

[0205] In one embodiment, the mass part content (additive / silicone urethane poly(meth)acrylate) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, and the like.

[0206] In one embodiment, the mass part content (additive / silicone urethane-free poly(meth)acrylate) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, and the like.

[0207] In one embodiment, the mass part content (additive / urethane bond-free poly(meth)acrylate) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, and the like.

[0208] In one embodiment, the mass part content (additive / mono(meth)acrylate) is preferably exemplified by less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, and the like.

[0209] In one embodiment, the form (antifouling coating agent) is preferably exemplified by an emulsified form.

[0210] The emulsification method includes, for example, a mechanical emulsification method, a physicochemical emulsification method, and the like.

[0211] The mechanical emulsification method includes, for example, a colloid mill emulsification method, a phase inversion emulsification method, a forced emulsification method, a reverse phase emulsification method, a high pressure emulsification method, and the like.

[0212] The emulsification device includes, for example, a propeller mixer, a turbine mixer, a homomixer, a dispersing mixer, a super mixer, a colloid mill, a high pressure homogenizer, and the like.

[0213] The physicochemical emulsification method includes, for example, a method of introducing a highly hydrophilic group into a molecular skeleton, and the like.

[0214] The method of introducing a highly hydrophilic group into a molecular skeleton includes, for example, a method of urethanizing an ester of polyalkyl glycol and polycarboxylic acid to obtain a urethane (meth)acrylate, and ionizing the urethane (meth)acrylate by an alkali to make it dispersible in water.

[0215] The salt base includes, for example, ammonia, caustic soda, and the like.

[0216] In one embodiment, the emulsification temperature is preferably selected from the range of 10°C to 70°C.

[0217] In one embodiment, the emulsification time is preferably selected from the range of 1 minute to 24 hours.

[0218] The kneading concentration includes, for example, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, and the like. In one embodiment, the kneading concentration is preferably selected from the range of 80 mass% to 90 mass%.

[0219] The viscosity (antifouling coating agent) includes, for example, 500000 mPa-s, 300000 mPa-s, 250000 mPa-s, 100000 mPa-s, 75000 mPa-s, 50000 mPa-s, 25000 mPa-s, 10000 mPa-s, 7500 mPa-s, 5000 mPa-s, 2000 mPa-s, 1000 mPa-s, 900 mPa-s, 700 mPa-s, 500 mPa-s, 300 mPa-s, 100 mPa-s, 90 mPa-s, 50 mPa-s, 30 mPa-s, 10 mPa-s, and the like. In one embodiment, the viscosity is preferably selected from the range of 10 mPa-s to 500000 mPa-s. The preferable reason includes, for example, improvement of curability, and the like.

[0220] The viscosity can be measured according to the following conditions. Measuring machine: VISCOMETER TVK-10, (stock) East Machine Industry Co. Non-volatile matter concentration: 15 mass% Measuring temperature: 25°C

[0221] [Cured product] The present disclosure relates to a cured product of the antifouling coating agent.

[0222] The curing conditions are, for example, the following conditions.

[0223] [Laminated product]

[0224] The present disclosure relates to a laminated product comprising the cured product. The production method (laminated product) is, for example, the following production method. Coating step: a step of coating the composition on at least one side of a substrate Active energy ray curing step: a step of forming a cured product layer by irradiating an active energy ray

[0225] The substrate is, for example, a polycarbonate film, an acrylic film (polymethyl methacrylate film, etc.), a polystyrene film, a polyester film, a polyolefin film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS film, an AS film, a norbornene-based resin film, a cyclic olefin film, a polyvinyl alcohol film, etc.

[0226] In one embodiment, the thickness (substrate) is preferably 10 μm to 2000 μm.

[0227] In one embodiment, the thickness (cured product layer) is preferably 0.1 μm to 20 μm.

[0228] [Coating step] The coating method is, for example, bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coater coating, offset printing, flexographic printing, screen printing, etc.

[0229] [Active energy ray irradiation step] The active energy ray is, for example, ultraviolet rays, electron beams, etc.

[0230] The ultraviolet light source is, for example, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, etc.

[0231] In the case of using a high-pressure mercury lamp, the curing conditions are preferably the following conditions. Lamp output: 25 W / cm to 160 W / cm UV irradiance: 10 mW / cm 2 to 800 mW / cm 2 Cumulative light amount: 25 mJ / cm 2 ~2000 mJ / cm 2 Conveying speed: 1 m / min ~ 50 m / min

[0232] In the case of using an electron beam, the curing conditions are preferably selected from the following conditions, etc. Accelerating voltage: 10 kV ~ 300 kV Conveying speed: 5 m / min ~ 50 m / min [Examples]

[0233] Hereinafter, the present application will be specifically described by examples and comparative examples. However, the above description and the following examples are not described with the purpose of limiting the present application. The present application is limited only by the scope of the claims. Hereinafter, the values of parts, %, etc. are mass-based unless otherwise specified.

[0234] Production Example 1-1: Silicone urethane poly(meth)acrylate Into a reaction vessel equipped with a stirrer and a cooling tube, a polyisocyanate (see the following table), a mono-terminated hydroxyl group-containing polysiloxane (see the following table), a mono-terminated hydroxyl group-containing polyalkylene glycol (see the following table), 0.04 parts of 4-methoxyphenol, 161.9 parts of isobornyl acrylate, and 0.25 parts of tin octoate were added, and then the temperature in the system was raised to 70°C over about 15 minutes. Then, the reaction system was maintained at the same temperature for 1.5 hours, and then cooled to 60°C. Then, after adding a hydroxyl group-containing (poly) (meth) acrylate (see the following table) and 0.13 parts of tin octoate, the temperature in the system was raised to 75°C over about 15 minutes. Next, after maintaining the reaction system at the same temperature for 1 hour, 0.02 parts of 4-methoxyphenol was added, and then cooled to obtain an ester silicone urethane poly(meth) acrylate.

[0235] As long as not particularly mentioned, he was changed, for example, as in the following table, and otherwise the same as described.

[0236] [Table 1] HXR FM0411 M400 M1000 M305 Production Example 1-1 100 10 50 40 240 Production Example 1-2 100 15 50 40 240 Production Example 1-3 100 20 50 40 240 Production Example 1-4 100 30 50 40 240 Production Example 1-5 100 30 50 40 40 HXR: Isocyanurate of hexamethylene diisocyanate, Coronate HXR, manufactured by Dow Corning (Co.) FM0411: Mono-terminated hydroxyl group-containing polydimethylsiloxane, Silaplane FM-0411, manufactured by JNC (Co.) M400: Polyethylene glycol monomethyl ether, Uniox-400, manufactured by Nippon Oil (Co.) M1000: Polyethylene glycol monomethyl ether, Uniox M-1000, Nippon Oil Mills Co., Ltd. M305: Pentaerythritol polyacrylate, Aronix M-305, Toagosei Co., Ltd.

[0237] Production Example 2: Silicone-free urethane-free poly(meth)acrylate After adding isocyanurate-modified hexamethylene diisocyanate (product name "CORONATE HXR", manufactured by DKS Co., Ltd.) 42.9 parts, polyethylene glycol monomethyl ether (product name "Uniox M-1000", manufactured by Nippon Oil Mills Co., Ltd.) 50.7 parts, pentaerythritol polyacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.) 66.3 parts, stannous octoate 0.04 parts, and 4-methoxyphenol 0.09 parts to a reaction vessel equipped with a stirring device and a cooling tube, the temperature in the system was raised to 70°C over a period of about 15 minutes. Subsequently, after keeping the reaction system at this temperature for 1.5 hours, it was cooled to 60°C. Then, after adding pentaerythritol polyacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.) 28.8 parts and stannous octoate 0.08 parts, the temperature in the system was raised to 75°C over a period of about 15 minutes. Subsequently, after keeping the reaction system at this temperature for 1 hour, 4-methoxyphenol 0.09 parts was added, and after cooling, silicone-free urethane poly(meth)acrylate (non-volatile content 100%) was obtained.

[0238] Example: Antifouling coating agent The substances shown in the following table were mixed as non-volatile components, and then diluted (dilution solvent: water, non-volatile components 40%).

[0239] [Table 2] DPHA-40H: Urethane acrylate, KAYARAD DPHA-40H, Nippon Shokubai Co., Ltd. A-9550: Dipentaerythritol polyacrylate, NK Ester A-9550, Shin-Nakamura Chemical Co., Ltd. A-DPH-12E: Oxirane-modified dipentaerythritol polyacrylate, NK Ester A-DPH-12E, Shin-Nakamura Chemical Co., Ltd. M-305: Pentaerythritol polyacrylate, Aronix M-305, Toagosei Co., Ltd. M-933: Pentaerythritol polyacrylate, Aronix M-933, Toagosei Co., Ltd. M-408: ditrimethylolpropane tetraacrylate, Aronix M-408, manufactured by Toagosei (K.K.) M-510: polyacid-modified acrylic oligomer having three or more acrylate groups, Aronix M-510, manufactured by Toagosei (K.K.) BYK-348: polyether-modified silicone resin, manufactured by BYK Chemie Japan (K.K.) BYK-3565: acrylic-modified silicone resin, manufactured by BYK Chemie Japan (K.K.) Olfine EXP4300: acetylene glycol-based surfactant, manufactured by Nippon Shokubai (K.K.) DYNOL 607: acetylene glycol-based leveling agent, manufactured by Evonik Industries

[0240] Laminate A laminate was produced using the coating agent of the example under the following conditions. Substrate: PC plate Coating means: #28 bar coater Cured product stack thickness: 20 μm Drying conditions: 80°C, 5 minutes Curing device: ultraviolet curing device (product name "UBT-080-7A / BM", manufactured by Multi-PT, high-pressure mercury lamp 600 mJ / cm 2 )) Curing conditions: 520 mw / cm 2

[0241] Water contact angle The cured layer was measured under the following conditions. Water droplet amount: 2.0 μL Measurement device: contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., Drop Master DM-300) Analysis method: θ / 2 method Measurement time: 1 second after the water droplet was dropped Measurement temperature: 23°C Relative humidity: 50%

[0242] Marker erasability A mark was written on the cured product layer using a magic marker No. 700 (manufactured by Terukishi Chemical Industry Co., Ltd.), and the mark was wiped off with a cloth 1 minute later. The number in the table indicates the number of times of wiping required to remove the marker. "x" indicates that the marker could not be wiped off even if wiping was performed 5 times.

[0243] Steel wool resistance The cured layer was measured under the following conditions. Steel wool (#0000) Number of passes: 10 Load: 100 g Sliding distance: 4 cm O: No scratches X: Scratches.

Claims

1. An antifouling coating agent, the antifouling coating agent comprising: a silicone urethane poly(meth)acrylate, the silicone urethane poly(meth)acrylate comprising a hydroxyl group-containing polysiloxane unit, a hydroxyl group-containing (poly)(meth)acrylate unit, a single- terminal hydroxyl group-containing polyalkylene glycol unit, and a polyisocyanate unit.

2. The antifouling coating agent according to claim 1, comprising a diol containing an ethynyl structure.

3. A cured product of the antifouling coating agent according to claim 1 or 2.

4. A laminate comprising the cured product according to claim 3.

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