WO2020235516A1 - Multilayer antifouling coating and coated object having said coating on surface - Google Patents

Multilayer antifouling coating and coated object having said coating on surface Download PDF

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Publication number
WO2020235516A1
WO2020235516A1 PCT/JP2020/019578 JP2020019578W WO2020235516A1 WO 2020235516 A1 WO2020235516 A1 WO 2020235516A1 JP 2020019578 W JP2020019578 W JP 2020019578W WO 2020235516 A1 WO2020235516 A1 WO 2020235516A1
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Prior art keywords
monomer
copolymer
coating film
mass
antifouling
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PCT/JP2020/019578
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French (fr)
Japanese (ja)
Inventor
拓也 安井
崇 松木
英典 和久
慧 小林
基道 伊藤
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日東化成株式会社
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Application filed by 日東化成株式会社 filed Critical 日東化成株式会社
Priority to KR1020217041925A priority Critical patent/KR20220012899A/en
Priority to CN202080037675.7A priority patent/CN113939565A/en
Publication of WO2020235516A1 publication Critical patent/WO2020235516A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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    • C09D5/1668—Vinyl-type polymers
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Abstract

Provided is a multilayer antifouling coating having excellent impact resistance and having early stage immersion antifouling properties and long-term antifouling properties that are both excellent.　The present invention provides a multilayer antifouling coating having a lower layer coating and an upper layer coating formed thereon. In the multilayer antifouling coat film, the upper layer coating contains a copolymer A, the lower layer coating contains a copolymer B, and the upper layer coating and the lower layer coating each contain an antifouling chemical agent. The copolymer A is a copolymer comprising a first monomer mixture, which contains a monomer (a) and a monomer (c), and may also contain a monomer (b). The copolymer B is a copolymer comprising a second monomer mixture containing at least one of the monomer (a) and the monomer (b). The monomers (a) to (c) are represented respectively by formulae (1) to (3). In the copolymer A, when the first monomer mixture is 100% by mass, the content of the monomer (a) is 10 to 45% by mass, the content of the monomer (b) is 0 to 15% by mass, the content of the monomer (c) is 20 to 50% by mass, and the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass. In the copolymer B, which is a copolymer that is different from the copolymer A, when the second monomer mixture represents 100% by mass, the total content of the monomer (a) and the monomer (b) is 46 to 65% by mass.

Description

複層防汚塗膜、該塗膜を表面に有する塗装物Multi-layer antifouling coating film, coating film having the coating film on the surface
　本発明は、複層防汚塗膜、該塗膜を表面に有する塗装物に関する。 The present invention relates to a multi-layer antifouling coating film and a coating material having the coating film on the surface.
　フジツボ、セルプラ、ムラサキイガイ、フサコケムシ、ホヤ、アオノリ、アオサ、スライム等の水棲汚損生物が、船舶（特に船底部分）や漁網類、漁網付属具等の漁業具や発電所導水管等の水中構造物に付着することにより、それら船舶等の機能が害される、外観が損なわれる等の問題がある。 Aquatic pollutants such as Fujitsubo, Serupura, Murasakiigai, Fusakokemushi, Hoya, Green laver, Sea lettuce, and slime are applied to underwater structures such as ships (especially the bottom of ships), fishing nets, fishing net accessories, and other fishing equipment and power plant water pipes. Adhesion causes problems such as impairing the functions of those ships and impairing their appearance.
　このような問題を防ぐために、船舶等に防汚塗料組成物を塗布して防汚塗膜を形成し、防汚塗膜から防汚薬剤を徐放させることによって、長期間に渡って防汚性能を発揮させる技術が知られている（特許文献１）。 In order to prevent such problems, an antifouling paint composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is gradually released from the antifouling coating film to prevent fouling over a long period of time. A technique for exerting performance is known (Patent Document 1).
特開２０００－１７２０３号公報Japanese Unexamined Patent Publication No. 2000-17203
　しかし、特許文献１のような、加水分解による塗膜更新性塗膜は、一般的に浸水初期の塗膜更新性が悪いと言われている。特に艤装期間は、船舶が静置した状態であるため、塗膜更新性は非常に劣る。そのため、浸水初期において、スライム等の付着が容易に起こり、その後フジツボやセルプラ等の付着が続いて引き起こされ、燃費の低下、外観が損なわれる等の問題があった。 However, it is generally said that the coating film renewability by hydrolysis as in Patent Document 1 has poor coating film renewability at the initial stage of flooding. Especially during the dressing period, since the ship is in a stationary state, the paint film renewability is very poor. Therefore, in the initial stage of flooding, slime or the like easily adheres, and then barnacles, cell plastics, or the like are subsequently adhered, resulting in problems such as deterioration of fuel efficiency and deterioration of appearance.
　本発明はこのような事情に鑑みてなされたものであり、耐衝撃性に優れ、かつ浸水初期の防汚性及び長期防汚性の両方に優れた複層防汚塗膜を提供するものである。 The present invention has been made in view of such circumstances, and provides a multi-layer antifouling coating film having excellent impact resistance and excellent both antifouling property at the initial stage of flooding and long-term antifouling property. is there.
　本発明によれば、下層塗膜と、その上に形成された上層塗膜を有する複層防汚塗膜であって、前記上層塗膜は、共重合体Ａを含み、前記下層塗膜は、共重合体Ｂを含み、前記上層塗膜及び下層塗膜は、それぞれ、防汚薬剤を含み、前記共重合体Ａは、単量体（ａ）と単量体（ｃ）を含み、且つ単量体（ｂ）を含んでもよい第１単量体混合物の共重合体であり、前記共重合体Ｂは、前記単量体（ａ）と単量体（ｂ）の少なくとも一方を含む第２単量体混合物の共重合体であり、前記単量体（ａ）～（ｃ）は、それぞれ、一般式（１）～（３）で表され、前記共重合体Ａは、第１単量体混合物を１００質量％とすると、前記単量体（ａ）の含有量が１０～４５質量％であり、前記単量体（ｂ）の含有量が０～１５質量％であり、前記単量体（ｃ）の含有量が２０～５０質量％であり、前記単量体（ａ）と前記単量体（ｂ）の合計含有量が１０～４５質量％であり、前記共重合体Ｂは、前記共重合体Ａ以外の共重合体であり、且つ第２単量体混合物を１００質量％とすると、前記単量体（ａ）と前記単量体（ｂ）の合計含有量が４６～６５質量％である、複層防汚塗膜が提供される。 According to the present invention, it is a multi-layer antifouling coating having a lower layer coating film and an upper layer coating film formed on the lower layer coating film, wherein the upper layer coating film contains a copolymer A, and the lower layer coating film is , The upper layer coating film and the lower layer coating film each contain an antifouling agent, and the copolymer A contains a monomer (a) and a monomer (c), respectively. It is a copolymer of a first monomer mixture which may contain a monomer (b), and the copolymer B contains at least one of the monomer (a) and the monomer (b). It is a copolymer of a two-monomer mixture, and the monomers (a) to (c) are represented by the general formulas (1) to (3), respectively, and the copolymer A is the first monomer. Assuming that the weight mixture is 100% by mass, the content of the monomer (a) is 10 to 45% by mass, the content of the monomer (b) is 0 to 15% by mass, and the simple The content of the weight (c) is 20 to 50% by mass, the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass, and the copolymer B is Is a copolymer other than the copolymer A, and the total content of the monomer (a) and the monomer (b) is 46, assuming that the second monomer mixture is 100% by mass. A multi-layer antifouling coating having a content of up to 65% by mass is provided.
　本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、上記構成の複層防汚塗膜が上記課題を解決できることを見出し、本発明の完成に到った。 As a result of intensive research to solve the above problems, the present inventor has found that the multi-layer antifouling coating film having the above structure can solve the above problems, and has reached the completion of the present invention.
以下、本発明について詳細を説明する。 Hereinafter, the present invention will be described in detail.
１．複層防汚塗膜
　本発明の一実施形態の複層防汚塗膜は、下層塗膜と、その上に形成された上層塗膜を有する。下層塗膜と上層塗膜は、どちらも加水分解型防汚塗膜である。 1. 1. Multi-layer antifouling coating film The multi-layer antifouling coating film according to the embodiment of the present invention has a lower layer coating film and an upper layer coating film formed on the lower layer coating film. Both the lower layer coating film and the upper layer coating film are hydrolysis type antifouling coating films.
１－１．上層塗膜
　上層塗膜は、共重合体Ａと、防汚薬剤を含む。上層塗膜は、上層塗膜に含まれる成分を溶媒に溶解又は分散させることによって得られる防汚塗料組成物を用いて形成することができる。 1-1. Upper coating film The upper coating film contains the copolymer A and an antifouling agent. The upper layer coating film can be formed by using an antifouling coating composition obtained by dissolving or dispersing the components contained in the upper layer coating film in a solvent.
＜共重合体Ａ＞
　共重合体Ａは、第１単量体混合物の共重合体である。第１単量体混合物は、単量体（ａ）と単量体（ｃ）を含み、且つ単量体（ｂ）を含んでもよく、単量体（ａ）～（ｃ）以外の単量体を含んでもよい。 <Copolymer A>
Copolymer A is a copolymer of the first monomer mixture. The first monomer mixture contains a monomer (a) and a monomer (c), and may contain a monomer (b), and is a single amount other than the monomers (a) to (c). It may include the body.
　共重合体Ａは、第１単量体混合物を１００質量％とすると、前記単量体（ａ）の含有量が１０～４５質量％であり、前記単量体（ｂ）の含有量が０～１５質量％であり、前記単量体（ｃ）の含有量が２０～５０質量％であり、前記単量体（ａ）と前記単量体（ｂ）の合計含有量が１０～４５質量％である。 Assuming that the first monomer mixture is 100% by mass, the copolymer A has a content of the monomer (a) of 10 to 45% by mass and a content of the monomer (b) of 0. The content of the monomer (c) is 20 to 50% by mass, and the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass. %.
　単量体（ａ）の含有量は、具体的には例えば、１０、１５、２０、２５、３０、３５、４０、４５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。単量体（ｂ）の含有量は、具体的には例えば、０、５、１０、１５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。単量体（ｃ）の含有量は、具体的には例えば、２０、２５、３０、３５、４０、４５、５０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。単量体（ａ）と単量体（ｂ）の合計含有量は、具体的には例えば、１０、１５、２０、２５、３０、３５、４０、４５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Specifically, the content of the monomer (a) is, for example, 10, 15, 20, 25, 30, 35, 40, 45% by mass, and is in the range between any two of the numerical values exemplified here. It may be inside. Specifically, the content of the monomer (b) is, for example, 0, 5, 10, 15% by mass, and may be in the range between any two of the numerical values exemplified here. Specifically, the content of the monomer (c) is, for example, 20, 25, 30, 35, 40, 45, 50% by mass, and is within the range between any two of the numerical values exemplified here. There may be. Specifically, the total content of the monomer (a) and the monomer (b) is, for example, 10, 15, 20, 25, 30, 35, 40, 45% by mass, and the numerical values exemplified here. It may be within the range between any two of.
　単量体（ａ）は、一般式（１）で表されるメタクリル酸トリオルガノシリル単量体である。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ１～Ｒ３はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基である。） The monomer (a) is a triorganosilyl methacrylate monomer represented by the general formula (1).
Figure JPOXMLDOC01-appb-C000004
 (In the formula, R 1 to R 3 are the same or different branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, respectively.)
　Ｒ１～Ｒ３はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基を示す。炭素数３～８の分岐アルキル基としては、例えば、イソプロピル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、１－エチルプロピル基、１－メチルブチル基、１－メチルペンチル基、１，１－ジメチルプロピル基、１，１－ジメチルブチル基、テキシル基、シクロヘキシル基、１，１－ジメチルペンチル基、１－メチルヘキシル基、１，１－ジメチルヘキシル基、１－メチルヘプチル基、２－メチルブチル基、２－エチルブチル基、２，２－ジメチルプロピル基、シクロヘキシルメチル基、２－エチルヘキシル基、２－プロピルペンチル基、３－メチルペンチル基等が挙げられる。Ｒ１～Ｒ３として好ましいものは、イソプロピル基、ｓ－ブチル基、ｔ－ブチル基、フェニル基、及び２－エチルヘキシル基である。特に好ましいものは、イソプロピル基である。 R 1 to R 3 represent branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, which are the same or different from each other. Examples of the branched alkyl group having 3 to 8 carbon atoms include an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, and 1,1. -Dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methylheptyl group, 2-methylbutyl group Examples thereof include a group, a 2-ethylbutyl group, a 2,2-dimethylpropyl group, a cyclohexylmethyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a 3-methylpentyl group and the like. Preferred as R 1 to R 3 are an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group. Particularly preferred are isopropyl groups.
　単量体（ａ）としては、例えば、メタクリル酸トリイソプロピルシリル、メタクリル酸トリイソブチルシリル、メタクリル酸トリｓ－ブチルシリル、メタクリル酸トリイソペンチルシリル、メタクリル酸トリフェニルシリル、メタクリル酸ジイソプロピルフェニルシリル、メタクリル酸ジイソプロピルイソブチルシリル、メタクリル酸ジイソプロピルｓ－ブチルシリル、メタクリル酸ジイソプロピルイソペンチルシリル、メタクリル酸イソプロピルジイソブチルシリル、メタクリル酸イソプロピルジｓ－ブチルシリル、メタクリル酸ｔ－ブチルジイソプチルシリル、メタクリル酸ｔ－ブチルジイソペンチルシリル、メタクリル酸ｔ－ブチルジフェニルシリル、メタクリル酸ジイソプロピルテキシルシリル、メタクリル酸ジイソプロピルシクロヘキシルシリル、メタクリル酸トリシクロヘキシルシリル、メタクリル酸トリ１，１－ジメチルペンチルシリル、メタクリル酸トリ２，２－ジメチルプロピルシリル、メタクリル酸トリシクロヘキシルメチルシリル、メタクリル酸ジイソプロピルシクロヘキシルメチルシリル、メタクリル酸トリ２－エチルヘキシルシリル、メタクリル酸トリ２－プロピルペンチルシリル等が挙げられる。好ましくは、メタクリル酸トリイソプロピルシリル、メタクリル酸トリｓ－ブチルシリル、メタクリル酸ｔ－ブチルジフェニルシリル、メタクリル酸トリ２－エチルヘキシルシリル等が挙げられる。これらの単量体（ａ）は、単独で又は２種以上を組み合わせて使用できる。 Examples of the monomer (a) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tris-butylsilyl methacrylate, triisopentylsilyl methacrylate, triphenylsilyl methacrylate, diisopropylphenylsilyl methacrylate, and methacrylic acid. Diisopropylisobutylsilylate acid, diisopropyls-butylsilylmethacrylate, diisopropylisopentylsilyl methacrylate, isopropyldiisobutylsilylacrylate, isopropyldis-butylsilylmethacrylate, t-butyldiisoputylsilylmethacrylate, t-butyldiisomethacrylate Pentylsilyl, t-butyldiphenylsilyl methacrylate, diisopropyltexylsilyl methacrylate, diisopropylcyclohexylsilyl methacrylate, tricyclohexylsilyl methacrylate, tri-1,1-dimethylpentylsilyl methacrylate, tri 2,2-dimethylpropyl methacrylate Examples thereof include silyl, tricyclohexylmethylsilyl methacrylate, diisopropylcyclohexylmethylsilyl methacrylate, tri2-ethylhexylsilyl methacrylate, tri2-propylpentylsilyl methacrylate and the like. Preferred examples thereof include triisopropylsilyl methacrylate, tris-butylsilyl methacrylate, t-butyldiphenylsilyl methacrylate, tri2-ethylhexylsilyl methacrylate and the like. These monomers (a) can be used alone or in combination of two or more.
　単量体（ｂ）は、一般式（２）で表されるアクリル酸トリオルガノシリル単量体である。
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ１～Ｒ３はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基である。） The monomer (b) is a triorganosilyl monomeric acid acrylate represented by the general formula (2).
Figure JPOXMLDOC01-appb-C000005
 (In the formula, R 1 to R 3 are the same or different branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, respectively.)
　一般式（２）のＲ１～Ｒ３の説明は、一般式（１）のＲ１～Ｒ３の説明と同じである。 The description of R 1 to R 3 of the general formula (2) is the same as the description of R 1 to R 3 of the general formula (1).
　単量体（ｂ）としては、単量体（ａ）として例示した化合物の名称の「メタクリル酸」を「アクリル酸」としたものが挙げられる。 Examples of the monomer (b) include those in which the name "methacrylic acid" of the compound exemplified as the monomer (a) is changed to "acrylic acid".
　単量体（ｃ）は、一般式（３）で表される（メタ）アクリル酸エステル単量体である。単量体（ｃ）は、アクリロイルオキシ基またはメタクリロイルオキシ基を有するとともに、アルコキシまたはアリーロキシポリエチレングリコール基を有するものである。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ４は、水素原子又はメチル基であり、Ｒ５は、アルキル基またはアリール基であり、ｎは１～２５である。） The monomer (c) is a (meth) acrylic acid ester monomer represented by the general formula (3). The monomer (c) has an acryloyloxy group or a methacryloyloxy group, and also has an alkoxy or allyloxypolyethylene glycol group.
Figure JPOXMLDOC01-appb-C000006
 (In the formula, R 4 is a hydrogen atom or a methyl group, R 5 is an alkyl group or an aryl group, and n is 1 to 25.)
　ポリエチレングリコールの重合度（ｎ）は１～２５であり、好ましくは１～５であり、具体的には例えば、１、２、３、４、５、１０、１５、２０、２５であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The degree of polymerization (n) of polyethylene glycol is 1 to 25, preferably 1 to 5, and specifically, for example, 1, 2, 3, 4, 5, 10, 15, 20, 25. It may be within the range between any two of the numerical values exemplified in 1.
　アルキル基としては、メチル、エチル、プロピル、ブチルなどの炭素数が１２以下の直鎖状または分岐状のアルキル基；シクロヘキシルや置換シクロヘキシルなどの環状アルキル基等が挙げられる。 Examples of the alkyl group include a linear or branched alkyl group having 12 or less carbon atoms such as methyl, ethyl, propyl and butyl; a cyclic alkyl group such as cyclohexyl and substituted cyclohexyl.
　アリール基としては、アリール基や置換アリールなどが挙げられる。置換アリール基としては、ハロゲン、炭素数１８程度までのアルキル基、アシル基、ニトロ基またはアミノ基などで置換されたアリ―ル基などがある。 Examples of the aryl group include an aryl group and a substituted aryl. Examples of the substituted aryl group include a halogen, an alkyl group having up to about 18 carbon atoms, an acyl group, an aryl group substituted with a nitro group, an amino group, and the like.
　単量体（ｃ）としては、分子内に（メタ）アクリロイルオキシ基を有するものとして、メトキシエチル（メタ）アクリレ―ト、エトキシエチル（メタ）アクリレ―ト、プロピオキシエチル（メタ）アクリレ―ト、ブトキシエチル（メタ）アクリレ―ト、ヘキサオキシエチル（メタ）アクリレ―ト、メトキシジエチレングリコ―ル（メタ）アクリレ―ト、メトキシトリエチレングリコ―ル（メタ）アクリレ―ト、エトキシジエチレングリコ―ル（メタ）アクリレ―ト、エトキシトリエチレングリコ―ル（メタ）アクリレ―トなどが挙げられる。 As the monomer (c), those having a (meth) acryloyloxy group in the molecule include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and propioxyethyl (meth) acrylate. , Butoxyethyl (meth) acrylic, hexaoxyethyl (meth) acrylic, methoxydiethyleneglycol (meth) acrylic, methoxytriethyleneglycol (meth) acrylic, ethoxydiethyleneglycol (meth) ) Acrylate, ethoxytriethyleneglycol (meth) acylate and the like.
　単量体（ａ）～（ｃ）以外の単量体としては、単量体（ａ）～（ｃ）と共重合可能なエチレン性不飽和単量体が挙げられる。このような単量体としては、一般式（３）以外の（メタ）アクリル酸エステル、ビニル化合物、芳香族化合物、二塩基酸のジアルキルエステル化合物等が挙げられる。なお、本明細書において、（メタ）アクリル酸エステルは、アクリル酸エステル、又はメタアクリル酸エステルを意味する。 Examples of the monomers other than the monomers (a) to (c) include ethylenically unsaturated monomers copolymerizable with the monomers (a) to (c). Examples of such a monomer include (meth) acrylic acid esters other than the general formula (3), vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, and the like. In the present specification, the (meth) acrylic acid ester means an acrylic acid ester or a metaacrylic acid ester.
　（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２一エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸ベンジル、及び（メタ）アクリル酸フェニル等が挙げられる。 Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth). ) 21-ethylhexyl acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) ) Glycidyl acrylate, flufuryl acrylate, tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic Examples include phenyl acid acid.
　ビニル化合物としては、例えば、塩化ビニル、塩化ビニリデン、アクリロニトリル、メタクリロニトリル、酢酸ビニル、安息香酸ビニル、ビニルブチレート、ブチルビニルエーテル、ラウリルビニルエーテル、Ｎ－ビニルピロリドン等の官能基を有するビニル化合物が挙げられる。 Examples of the vinyl compound include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone. Be done.
　芳香族化合物としては、例えば、スチレン、ビニルトルエン、α－メチルスチレン等が挙げられる。 Examples of the aromatic compound include styrene, vinyltoluene, α-methylstyrene and the like.
　二塩基酸のジアルキルエステル化合物としては、マレイン酸ジメチル、マレイン酸ジブチル、フマル酸ジメチル等が挙げられる。 Examples of the dialkyl ester compound of dibasic acid include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
＜共重合体Ａの合成＞
　共重合体Ａは、第１単量体混合物を共重合することにより得ることができる。前記共重合は、例えば、重合開始剤の存在下で行われる。 <Synthesis of copolymer A>
The copolymer A can be obtained by copolymerizing the first monomer mixture. The copolymerization is carried out, for example, in the presence of a polymerization initiator.
　共重合体Ａの重量平均分子量は、５０００～３０００００であることが望ましい。分子量が５０００未満であれば、防汚塗料の塗膜が脆弱となり、剥離やクラックを起こし易く、また、３０００００を超えると、共重合体溶液の粘度が上昇し、取扱いが困難となるからである。 It is desirable that the weight average molecular weight of the copolymer A is 5000 to 300,000. This is because if the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels or cracks, and if it exceeds 300,000, the viscosity of the copolymer solution increases and handling becomes difficult. ..
　前記重合反応において使用される重合開始剤としては、例えば、２，２′－アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２′－アゾビス－２－メチルブチロニトリル、ジメチル－２，２′－アゾビスイソブチレート等のアゾ化合物、ベンゾイルパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、ｔｅｒｔ－ブチルパーオクトエート、ｔｅｒｔ－ブチルパーオキシ２－エチルヘキサノエート、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエ－ト、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート等の過酸化物が挙げられる。これら重合開始剤は、単独又は２種以上を組み合わせて使用できる。重合開始剤としては、特に、ＡＩＢＮ、ｔｅｒｔ－ブチルパーオクトエート、及び、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエ－トが好ましい。
重合開始剤の使用量を適宜設定することにより、共重合体Ａの分子量を調整することができる。 Examples of the polymerization initiator used in the polymerization reaction include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, and dimethyl-2,2'. -Azo compounds such as azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, tert-butylperoctate, tert-butylperoxy Peroxide of 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, etc. Things can be mentioned. These polymerization initiators can be used alone or in combination of two or more. As the polymerization initiator, AIBN, tert-butylperoctate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferable.
The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
　重合方法としては、例えば、溶液重合、塊状重合、乳化重合、懸濁重合等が挙げられる。この中でも特に、簡便に、且つ、精度良く、共重合体Ａを得ることができる点で、溶液重合が好ましい。 Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like. Of these, solution polymerization is particularly preferable in that the copolymer A can be obtained easily and accurately.
　前記重合反応においては、必要に応じて有機溶媒を用いてもよい。有機溶剤としては、例えば、キシレン、トルエン等の芳香族炭化水素系溶剤；ヘキサン、ヘプタン等の脂肪族炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸メトキシプロピル等のエステル系溶剤；イソプロピルアルコール、ブチルアルコール、プロピレングリコールモノメチルエーテル等のアルコール系溶剤；ジオキサン、ジエチルエーテル、ジブチルエーテル等のエーテル系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤等が挙げられる。この中でも特に、エステル系溶剤、アルコール系溶剤、芳香族炭化水素系溶剤が好ましく、酢酸ブチル、酢酸イソブチル、ブチルアルコール、プロピレングリコールモノメチルエーテル、トルエン、キシレンがより好ましい。これら溶媒については、単独あるいは２種以上を組み合わせて使用できる。 In the polymerization reaction, an organic solvent may be used if necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl. Alcohol-based solvents such as alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned. Of these, ester-based solvents, alcohol-based solvents, and aromatic hydrocarbon-based solvents are particularly preferable, and butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, toluene, and xylene are more preferable. These solvents can be used alone or in combination of two or more.
　重合反応における反応温度は、重合開始剤の種類等に応じて適宜設定すればよく、通常７０～１４０℃であり、好ましくは８０～１３０℃である。重合反応における反応時間は、反応温度等に応じて適宜設定すればよく、通常４～８時間程度である。
　重合反応は、窒素ガス、アルゴンガス等の不活性ガス雰囲気下で行われることが好ましい。 The reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 70 to 140 ° C., preferably 80 to 130 ° C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
＜防汚薬剤＞
　防汚薬剤としては、例えば無機薬剤及び有機薬剤が挙げられる。 <Anti-fouling agent>
Examples of antifouling agents include inorganic agents and organic agents.
　無機薬剤としては、例えば、亜酸化銅、チオシアン酸銅（一般名：ロダン銅）、銅粉等が挙げられる。この中でも特に、亜酸化銅とロダン銅が好ましく、亜酸化銅はグリセリン、ショ糖、ステアリン酸、ラウリン酸、リシチン、鉱物油などで表面処理されているものが、貯蔵時の長期安定性の点でより好ましい。 Examples of the inorganic drug include cuprous oxide, copper thiocyanate (generic name: copper rodan), copper powder and the like. Of these, cuprous oxide and copper rodane are particularly preferable, and copper braous oxide that has been surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc., has long-term stability during storage. Is more preferable.
　有機薬剤としては、例えば、２－メルカプトピリジン－Ｎ－オキシド銅（一般名：カッパーピリチオン）、２－メルカプトピリジン－Ｎ－オキシド亜鉛（一般名：ジンクピリチオン）、ジンクエチレンビスジチオカーバメート（一般名：ジネブ）、４，５－ジクロロ－２－ｎ－オクチル－３－イソチアゾロン（一般名：シーナイン２１１）、３，４－ジクロロフェニル－Ｎ－Ｎ－ジメチルウレア（一般名：ジウロン）、２－メチルチオ－４－ｔ－ブチルアミノ－６－シクロプロピルアミノ－ｓ－トリアジン（一般名：イルガロール１０５１）、２－（ｐ－クロロフェニル）－３－シアノ－４－ブロモ－５－トリフルオロメチルピロール（一般名：Ｅｃｏｎｅａ２８）、４－［１－（２，３－ジメチルフェニル）エチル］－１Ｈ－イミダゾール（一般名：メデトミジン）等が挙げられる。
これらの防汚薬剤は１種又は２種以上併用して使用できる。 Examples of organic agents include 2-mercaptopyridine-N-copperpyrrhion (generic name: copperpyrityon), 2-mercaptopyridine-N-zinc oxide (generic name: zincpyrityon), and zincethylenebisdithiocarbamate (generic name: geneb ), 4,5-Dichloro-2-n-octyl-3-isothiazolone (generic name: Seanine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: Irgalol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4- [1- (2,3-Dimethylphenyl) ethyl] -1H-imidazole (generic name: medetomidin) and the like.
These antifouling agents can be used alone or in combination of two or more.
　本発明の組成物中における防汚薬剤の含有量は特に制限されないが、固形分換算で、通常０．１～６０質量％であり、好ましくは１～５０質量％である。防汚薬剤の含有量は、具体的には例えば、０．１、１、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60% by mass, preferably 1 to 50% by mass in terms of solid content. Specifically, the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and here. It may be in the range between any two of the illustrated values.
＜その他の添加剤＞
　さらに本発明の上層塗膜には、必要に応じて溶出調整剤、可塑剤、顔料、染料、消泡剤、充填剤、脱水剤、揺変剤等を含有させることができる。 <Other additives>
Further, the upper coating film of the present invention may contain an elution adjuster, a plasticizer, a pigment, a dye, an antifoaming agent, a filler, a dehydrating agent, a shaking agent and the like, if necessary.
　溶出調整剤としては、例えば、ロジン、ロジン誘導体、ナフテン酸、シクロアルケニルカルボン酸、ビシクロアルケニルカルボン酸、バーサチック酸、トリメチルイソブテニルシクロヘキセンカルボン酸、及びこれらの金属塩等の、モノカルボン酸及びその塩、又は前記脂環式炭化水素樹脂が挙げられる。これらは単独又は２種以上で使用できる。 Examples of the dissolution modifier include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. Examples thereof include a salt or the alicyclic hydrocarbon resin. These can be used alone or in combination of two or more.
　前記ロジン誘導体としては、水添ロジン、不均化ロジン、マレイン化ロジン、ホルミル化ロジン、重合ロジン等を例示できる。前記脂環式炭化水素樹脂としては、市販品として、例えば、クイントン１５００、１５２５Ｌ、１７００（商品名、日本ゼオン社製）等が挙げられる。 Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. Examples of the commercially available alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Corporation) and the like.
　可塑剤としては、例えば、燐酸エステテル類、フタル酸エステル類、アジピン酸エステル類、セバシン酸エステル類、エポキシ化大豆油、アルキルビニルエーテル重合体、ポリアルキレングリコール類、ｔ－ノニルペンタスルフィド、ワセリン、ポリブテン、トリメリット酸トリス（２－エチルヘキシル）、シリコーンオイル、流動パラフィン、塩素化パラフィン等が挙げられる。これらは単独又は２種以上で使用できる。 Examples of the plasticizer include phosphoric acid ester, phthalate ester, adipate ester, sebacic acid ester, epoxidized soybean oil, alkyl vinyl ether polymer, polyalkylene glycol, t-nonyl pentasulfide, vaseline, and polybutene. , Trisyl trimellitic acid (2-ethylhexyl), silicone oil, liquid paraffin, chlorinated paraffin and the like. These can be used alone or in combination of two or more.
　充填剤としては、無機質充填剤及び／又は有機質充填剤が挙げられる。無機質充填剤としては例えば、炭酸カルシウム、重質炭酸カルシウム、軽質炭酸カルシウム、コロイド炭酸カルシウム、沈降性硫酸バリウム、バライト粉、酸化チタン、焼成カオリン、アミノシランで表面処理した焼成カオリン、けいそう土、水酸化アルミニウム、微粒状アルミナ、酸化マグネシウム、炭酸マグネシウム、酸化亜鉛、炭酸亜鉛、ベンガラ、酸化鉄、煙霧状金属酸化物、石英粉末、タルク、ゼオライト、ベントナイト、ガラス繊維、炭素繊維、微粉マイカ、溶融シリカ粉末、シリカ微粉末、煙霧状シリカ、沈降性シリカ、湿式シリカ、乾式シリカあるいはこれらをメチルトリクロロシラン、ジメチルジクロロシラン、ヘキサメチルジシラザン、ヘキサメチルシクロトリシロキサン、オクラメチルシクロテトラシロキサン等の有機ケイ素化合物で表面処理した疎水性フュームドシリカ、フタロシアニンブルー、カーボンブラック等が挙げられる。有機質充填剤としては例えば、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、アクリルシリコーンなどの合成樹脂粉末等が挙げられる。 Examples of the filler include an inorganic filler and / or an organic filler. Examples of the inorganic filler include calcium carbonate, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, precipitated barium sulfate, barite powder, titanium oxide, calcined kaolin, calcined kaolin surface-treated with aminosilane, silica soil, and water. Aluminum oxide, fine granular alumina, magnesium oxide, magnesium carbonate, zinc oxide, zinc carbonate, red iron oxide, fuming metal oxide, quartz powder, talc, zeolite, bentonite, glass fiber, carbon fiber, fine powder mica, molten silica Powder, silica fine powder, fuming silica, precipitated silica, wet silica, dry silica or organic silicon such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, oklamethylcyclotetrasiloxane. Examples thereof include hydrophobic fumed silica, phthalocyanine blue, and carbon black surface-treated with a compound. Examples of the organic filler include synthetic resin powders such as polypropylene, polyvinyl chloride, polystyrene, and acrylic silicone.
　脱水剤としては、例えば、合成ゼオライト系吸着剤、オルソエステル類、テトラメトキシシラン、テトラエトキシシラン等のシリケート類やイソシアネート類、カルボジイミド類、カルボジイミダゾール類等が挙げられる。これらは単独または２種以上を組み合わせて使用することができる。 Examples of the dehydrating agent include synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.
＜防汚塗料組成物の製造方法＞
　上層塗膜用の防汚塗料組成物は、例えば、共重合体Ａ、防汚薬剤及び他の添加剤等を含有する混合液を、分散機を用いて混合分散することにより製造できる。
　前記混合液としては、共重合体及び防汚薬剤等の各種材料を溶媒に溶解または分散させたものであることが好ましい。
　前記分散機としては、例えば、微粉砕機として使用できるものを好適に用いることができる。例えば、市販のホモミキサー、サンドミル、ビーズミル等を使用することができる。また、撹拌機を備えた容器に混合分散用のガラスビーズ等を加えたものを用い、前記混合液を混合分散してもよい。 <Manufacturing method of antifouling paint composition>
The antifouling coating composition for the upper coating film can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer A, an antifouling agent, other additives and the like using a disperser.
As the mixed solution, it is preferable that various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent.
As the disperser, for example, one that can be used as a fine pulverizer can be preferably used. For example, a commercially available homomixer, sand mill, bead mill or the like can be used. Further, the mixed solution may be mixed and dispersed by using a container provided with a stirrer to which glass beads or the like for mixing and dispersing are added.
１－２．下層塗膜
　上層塗膜は、共重合体Ｂと、防汚薬剤を含む。下層塗膜は、下層塗膜に含まれる成分を溶媒に溶解又は分散させることによって得られる防汚塗料組成物を用いて形成することができる。 1-2. Lower coating film The upper coating film contains copolymer B and an antifouling agent. The underlayer coating film can be formed by using an antifouling coating composition obtained by dissolving or dispersing the components contained in the underlayer coating film in a solvent.
＜共重合体Ｂ＞
　共重合体Ｂは、第２単量体混合物の共重合体である。第２単量体混合物は、単量体（ａ）と単量体（ｂ）の少なくとも一方を含む。第２単量体混合物は、単量体（ａ）と（ｂ）のうちの一方のみを含んでもよく、両方を含んでもよい。第２単量体混合物は、単量体（ｃ）を含んでもよく、単量体（ａ）～（ｃ）以外の単量体を含んでもよい。単量体（ａ）～（ｃ）及びその他の単量体の説明は、共重合体Ａと同じである。 <Copolymer B>
Copolymer B is a copolymer of the second monomer mixture. The second monomer mixture contains at least one of the monomer (a) and the monomer (b). The second monomer mixture may contain only one of the monomers (a) and (b), or may contain both. The second monomer mixture may contain the monomer (c) or may contain a monomer other than the monomers (a) to (c). The description of the monomers (a) to (c) and other monomers is the same as that of the copolymer A.
　共重合体Ｂは、共重合体Ａ以外の共重合体であり、且つ第２単量体混合物を１００質量％とすると、単量体（ａ）と単量体（ｂ）の合計含有量が４６～６５質量％である。この合計含有量は、具体的には例えば、４６、５０、５５、６０、６５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。単量体（ａ）の含有量は、例えば、０～６５質量％であり、具体的には例えば、０、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。単量体（ｂ）の含有量は、例えば、０～６５質量％であり、具体的には例えば、０、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。単量体（ｃ）の含有量は、例えば０～５４質量％であり、具体的には例えば、０、５、１０、１５、２０、２５、３０、３５、４０、４５、５０、５４質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The copolymer B is a copolymer other than the copolymer A, and when the second monomer mixture is 100% by mass, the total content of the monomer (a) and the monomer (b) is It is 46 to 65% by mass. Specifically, the total content is, for example, 46, 50, 55, 60, 65% by mass, and may be in the range between any two of the numerical values exemplified here. The content of the monomer (a) is, for example, 0 to 65% by mass, and specifically, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55. , 60, 65% by mass, and may be within the range between any two of the numerical values exemplified here. The content of the monomer (b) is, for example, 0 to 65% by mass, and specifically, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55. , 60, 65% by mass, and may be within the range between any two of the numerical values exemplified here. The content of the monomer (c) is, for example, 0 to 54% by mass, and specifically, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 54 mass. %, Which may be within the range between any two of the numerical values exemplified here.
　単量体（ａ）～（ｃ）の説明は、共重合体Ａと同じである。 The description of the monomers (a) to (c) is the same as that of the copolymer A.
＜共重合体Ｂの合成＞
　共重合体Ｂは、第２単量体混合物を共重合することにより得ることができる。共重合体Ｂの物性や製造方法の説明は、共重合体Ａと同じである。 <Synthesis of copolymer B>
The copolymer B can be obtained by copolymerizing the second monomer mixture. The explanation of the physical properties of the copolymer B and the production method is the same as that of the copolymer A.
＜防汚薬剤＞
　防汚薬剤の説明は、上層塗膜と同じである。上層塗膜と下層塗膜の防汚薬剤は、同じであっても異なっていてもよい。 <Anti-fouling agent>
The description of the antifouling agent is the same as that of the upper coating film. The antifouling agent for the upper coating film and the lower coating film may be the same or different.
＜その他の添加剤＞
　さらに本発明の下層塗膜には、必要に応じて溶出調整剤、可塑剤、顔料、染料、消泡剤、充填剤、脱水剤、揺変剤等を含有させることができる。これらの説明は、上層塗膜と同じである。 <Other additives>
Further, the lower coating film of the present invention may contain an elution adjuster, a plasticizer, a pigment, a dye, an antifoaming agent, a filler, a dehydrating agent, a shaking agent and the like, if necessary. These explanations are the same as those of the upper coating film.
＜防汚塗料組成物の製造方法＞
　下層塗膜用の防汚塗料組成物は、例えば、共重合体Ｂ、防汚薬剤及び他の添加剤等を含有する混合液を、分散機を用いて混合分散することにより製造できる。その他の説明は、上層塗膜と同じである。 <Manufacturing method of antifouling paint composition>
The antifouling coating composition for the underlayer coating film can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer B, an antifouling agent, other additives and the like using a disperser. Other explanations are the same as those of the upper coating film.
２．複層防汚塗膜の形成方法
　本発明の複層防汚塗膜は、下層塗膜の上に、上層塗膜を形成することにより得られる。
　下層塗膜及び上層塗膜は、それぞれ、上記防汚塗料組成物を被塗膜形成物の表面（全体又は一部）に塗布することにより形成できる。塗布方法としては、例えば、ハケ塗り法、スプレー法、ディッピング法、フローコート法、スピンコート法等が挙げられる。これらは、１種又は２種以上を併用して行ってもよい。塗布後、乾燥させる。乾燥温度は、室温でよい。乾燥時間は、塗膜の厚み等に応じて適宜設定すればよい。 2. 2. Method for Forming Multi-Layer Antifouling Coating Film The multi-layer antifouling coating film of the present invention can be obtained by forming an upper layer coating film on a lower layer coating film.
The lower coating film and the upper coating film can be formed by applying the antifouling coating composition to the surface (whole or part) of the coating film to be formed, respectively. Examples of the coating method include a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method and the like. These may be performed alone or in combination of two or more. After application, dry. The drying temperature may be room temperature. The drying time may be appropriately set according to the thickness of the coating film and the like.
　下層塗膜の厚さは、被塗膜形成物の種類等に応じて適宜設定すればよく、通常５０～５００μｍ、好ましくは１００～２００μｍである。上層塗膜の厚さは、船舶の航行速度、海水温度等に応じて適宜設定すればよく、通常５０～５００μｍ、好ましくは１００～２００μｍである。 The thickness of the undercoat film may be appropriately set according to the type of the coating film to be formed and the like, and is usually 50 to 500 μm, preferably 100 to 200 μm. The thickness of the upper coating film may be appropriately set according to the navigation speed of the ship, the seawater temperature, etc., and is usually 50 to 500 μm, preferably 100 to 200 μm.
　被塗膜形成物としては、例えば、船舶（特に船底）、漁業具または水中構造物等の表面に施された防汚塗膜であって、一定期間海水中で使用された後の旧塗膜が挙げられる。 The coating film formed product is, for example, an antifouling coating film applied to the surface of a ship (particularly the bottom of a ship), a fishing tool, an underwater structure, or the like, and is an old coating film after being used in seawater for a certain period of time. Can be mentioned.
　以下に、実施例等を示し本発明の特徴とするところをより一層明確にする。ただし、本発明は実施例等に限定されるものではない。
各製造例、実施例及び比較例中の％は重量％を示す。粘度は、２５℃での測定値であり、Ｂ形粘度計により求めた値である。重量平均分子量（Ｍｗ）は、ＧＰＣにより求めた値（ポリスチレン換算値）である。ＧＰＣの条件は下記の通りである。
装置・・・　東ソー株式会社製　ＨＬＣ－８２２０ＧＰＣ
カラム・・・　ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ　　２本
流量・・・　０．３５　ｍＬ／ｍｉｎ
検出器・・・　ＲＩ
カラム恒温槽温度・・・　４０℃
溶離液・・・　ＴＨＦ
加熱残分は、ＪＩＳ　Ｋ　５６０１－１－２：１９９９（ＩＳＯ　３２５１：１９９３）「塗料成分試験方法－加熱残分」に準拠して測定した値である。
また、表中の各成分の配合量の単位はｇである。 Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to the examples and the like.
% In each production example, example and comparative example indicates weight%. The viscosity is a value measured at 25 ° C. and is a value obtained by a B-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC. The conditions of GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column ・ ・ ・ TSKgel SuperHZM-M 2 flow rate ・ ・ ・ 0.35 mL / min
Detector ・ ・ ・ RI
Column constant temperature bath temperature ・ ・ ・ 40 ℃
Eluent ・ ・ ・ THF
The heating residue is a value measured in accordance with JIS K 5601-1-2: 1999 (ISO 3251: 1993) "Paint component test method-heating residue".
The unit of the blending amount of each component in the table is g.
１．共重合体溶液の製造例
＜製造例１（共重合体溶液Ａ１の製造）＞
　温度計、還流冷却器、撹拌機及び滴下ロートを備えたフラスコに、キシレン２６０ｇを仕込み、窒素雰囲気下、８５±５℃で攪拌しながら、メタクリル酸トリイソプロピルシリル２１５ｇ、メタクリル酸メチル１３５ｇ、アクリル酸２－メトキシエチル１５０ｇ、及び重合開始剤である１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート３ｇの混合液を２時間かけて滴下した。その後同温度で１時間攪拌を行った後、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート０．５ｇを１時間毎に５回添加して重合反応を完結した後、加熱残分が５０％になるようにキシレンを添加し溶解させることにより、共重合体溶液Ａ１を得た。得られた共重合体溶液の粘度は３２０ｍＰａ・ｓ（２５℃）、加熱残分は５０．７％、Ｍｗは４５，０００であった。 1. 1. Production Example of Copolymer Solution <Production Example 1 (Production of Copolymer Solution A1)>
260 g of xylene was placed in a flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, and while stirring at 85 ± 5 ° C. under a nitrogen atmosphere, 215 g of triisopropylsilyl methacrylate, 135 g of methyl methacrylate, and acrylic acid. A mixed solution of 150 g of 2-methoxyethyl and 3 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator was added dropwise over 2 hours. Then, after stirring at the same temperature for 1 hour, 0.5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 5 times every hour to complete the polymerization reaction. After that, xylene was added and dissolved so that the heating residue became 50% to obtain a copolymer solution A1. The viscosity of the obtained copolymer solution was 320 mPa · s (25 ° C.), the heating residue was 50.7%, and Mw was 45,000.
＜製造例２～１４（共重合体溶液Ａ２～Ａ６、Ｂ１～Ｂ３、Ｃ１～Ｃ５の製造）＞
　表１に示す単量体の混合物を用いて、製造例１と同様の操作で重合を行い、共重合体溶液Ａ２～Ａ６、Ｂ１～Ｂ３、Ｃ１～Ｃ５を得た。得られた各共重合体溶液の加熱残分、粘度、及び重量平均分子量を測定した。結果を表１に示す。 <Production Examples 2 to 14 (Production of Copolymer Solutions A2 to A6, B1 to B3, C1 to C5)>
Polymerization was carried out in the same manner as in Production Example 1 using the mixture of monomers shown in Table 1 to obtain copolymer solutions A2 to A6, B1 to B3, and C1 to C5. The heating residue, viscosity, and weight average molecular weight of each of the obtained copolymer solutions were measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
２．塗料組成物の製造例
　表２に示す成分を当該表に示す割合（質量％）で配合し、直径１．５～２．５ｍｍのガラスビーズと混合分散することにより塗料組成物Ｘ１～Ｘ８、Ｙ１～Ｙ３、Ｚ１～Ｚ５を製造した。 2. 2. Production Example of Paint Composition The components shown in Table 2 are blended in the proportion (mass%) shown in the table, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to form a paint composition X1 to X8, Y1. -Y3 and Z1 to Z5 were manufactured.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表２中の各成分の詳細は以下の通りである。 Details of each component in Table 2 are as follows.
＜溶出調整剤＞
　ロジン溶液：中国産ガムロジン（ＷＷ）の固形分５０％キシレン溶液
　ロジン亜鉛塩溶液：商品名「Ｂｒｅｍａｚｉｔ　３０５０」（Ｋｒａｅｍｅｒ社製）の固形分５０％キシレン溶液
　水添ロジン溶液：商品名「ハイペールＣＨ」（荒川化学工業（株）製）の固形分５０％キシレン溶液 <Elution adjuster>
Rosin solution: Chinese gum rosin (WW) solid content 50% xylene solution Rosin zinc salt solution: trade name "Bremazit 3050" (manufactured by Kraemer) solid content 50% xylene solution Hydrogenated rosin solution: trade name "Hyper CH" (Arakawa Chemical Industry Co., Ltd.) solid content 50% xylene solution
＜可塑剤＞
　塩素化パラフィン：商品名「Ｐａｒａｆｆｉｎ　Ｃｈｌｏｒｉｎａｔｅｄ　（Ｃｌ：４０％）」（和光純薬工業（株）製）
　Ｅ－２０００Ｈ：エポキシ化大豆油：商品名「サンソサイザー　Ｅ－２０００Ｈ」（新日本理化（株）製）
　ＤＩＮＣＨ：１，２－シクロヘキサンジカルボン酸ジイソノニル：商品名「ＨＥＸＡＭＯＬＬ（登録商標）　ＤＩＮＣＨ（登録商標）」（ＢＡＳＦ社製）
　ＴＯＴＭ：トリメリット酸トリ２－エチルヘキシル：商品名「Ｔｒｉｓ（２－ｅｔｈｙｌｈｅｘｙｌ）　Ｔｒｉｍｅｌｌｉｔａｔｅ」（東京化成（株）製） <Plasticizer>
Chlorinated paraffin: Product name "Paraffin Chlorinated (Cl: 40%)" (manufactured by Wako Pure Chemical Industries, Ltd.)
E-2000H: Epoxy soybean oil: Product name "Sun Sosizer E-2000H" (manufactured by New Japan Chemical Co., Ltd.)
DINCH: Diisononyl 1,2-cyclohexanedicarboxylic acid: Trade name "HEXAMOL® (registered trademark) DINCH (registered trademark)" (manufactured by BASF)
TOTM: Tri2-ethylhexyl trimellitic acid: Product name "Tris (2-ethylhexyl) Trimellitic" (manufactured by Tokyo Kasei Co., Ltd.)
＜防汚薬剤＞
　亜酸化銅：商品名「ＮＣ－３０１」（日進ケムコ（株）製）
　銅ピリチオン：商品名「カッパーオマジン」（アーチケミカル（株）製）
　エコニア：商品名「Ｅｃｏｎｅａ　０２８」...２－（ｐ－クロロフェニル）－３－シアノ－４－ブロモ－５－トリフルオロメチルピロール（ヤンセンＰＭＰ製）
　メデトミジン：商品名「４－（１－（２，３－Ｄｉｍｅｔｈｙｌｐｈｅｎｙｌ）ｅｔｈｙｌ）－１Ｈ－ｉｍｉｄａｚｏｌｅ」（和光純薬工業（株）　製） <Anti-fouling agent>
Copper oxide: Product name "NC-301" (manufactured by Nissin Chemco Co., Ltd.)
Copper pyrithion: Product name "Copper Omagin" (manufactured by Arch Chemical Co., Ltd.)
Econia: Product name "Econea 028" ... 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Medetomidine: Product name "4- (1- (2,3-Dimethylphenyl) ethyl) -1H-imidazole" (manufactured by Wako Pure Chemical Industries, Ltd.)
＜無機質充填剤＞
　タルク：商品名「クラウンタルク３Ｓ」（松村産業（株）製）
　酸化亜鉛：商品名「酸化亜鉛２」（正同化学（株）製）
　ベンガラ：商品名「ＴＯＤＡ　ＣＯＬＯＲ　ＥＰ－１３Ｄ」（戸田ピグメント（株）製）
　酸化チタン：商品名「ＦＲ－４１」（古河機械金属（株）製） <Inorganic filler>
Talc: Product name "Crown Talc 3S" (manufactured by Matsumura Sangyo Co., Ltd.)
Zinc oxide: Product name "Zinc oxide 2" (manufactured by Shodo Kagaku Co., Ltd.)
Bengala: Product name "TODA COLOR EP-13D" (manufactured by Toda Pigment Co., Ltd.)
Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.)
＜脱水剤＞
　テトラエトキシシラン：商品名「Ｔｅｔｒａｅｔｈｙｌ　Ｏｒｔｈｏｓｉｌｉｃａｔｅ」（東京化成（株）製） <Dehydrating agent>
Tetraethoxysilane: trade name "Tetraethyl Orthosilicate" (manufactured by Tokyo Kasei Co., Ltd.)
＜揺変剤＞
　脂肪族アマイド系揺変剤：商品名「ディスパロンＡ６０３－２０Ｘ」（楠本化成（株）製） <Shaking agent>
Aliphatic amide-based shaker: Brand name "Disparon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)
＜有機溶剤＞
　キシレン：（試薬、東京化成工業社製）、エチルベンゼン含有 <Organic solvent>
Xylene: (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), containing ethylbenzene
３．試験
　表２に示す塗料組成物Ｘ１～Ｘ８、Ｙ１～Ｙ３、Ｚ１～Ｚ５を、表３に示す組み合わせで用いることによって、下層塗膜及び上層塗膜を形成した。これによって、実施例・比較例の複層防汚塗膜を得た。得られた複層防汚塗膜について、以下に示すように、耐衝撃性試験及び防汚試験を行った。その結果を表３に示す。 3. 3. Tests The coating compositions X1 to X8, Y1 to Y3, and Z1 to Z5 shown in Table 2 were used in the combinations shown in Table 3 to form a lower layer coating film and an upper layer coating film. As a result, a multi-layer antifouling coating film of Examples and Comparative Examples was obtained. The obtained multi-layer antifouling coating film was subjected to an impact resistance test and an antifouling test as shown below. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
＜＜試験例１（耐衝撃性試験）＞＞
　水槽の中央に直径５１５ｍｍ及び高さ４４０ｍｍの回転ドラムを取付け、これをモーターで回転できるようにした。また、海水の温度を一定に保つための冷却装置、及び海水のｐＨを一定に保つためのｐＨ自動コントローラーを取付けた。試験板を下記の方法に従って作製した。 << Test Example 1 (Impact resistance test) >>
A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of seawater constant and an automatic pH controller for keeping the pH of seawater constant were installed. A test plate was prepared according to the following method.
　まず、鋼板（７５×１５０×１ｍｍ）上に、防錆塗料（ビニル系Ａ／Ｃ）を乾燥後の厚みが約５０μｍとなるよう塗布し乾燥させることにより防錆塗膜を形成した。その後、前記防錆塗膜の上に下層塗膜用の塗料組成物を乾燥後の厚みが約１５０μｍとなるよう塗布した。得られた塗布物を室温で２４時間乾燥させ、その後上層塗膜用の塗料組成物を乾燥後の厚みが１５０μｍとなるように塗布した。得られた複層塗膜を４０℃で３日間乾燥させることにより、厚みが約３００μｍの乾燥複層塗膜を有する試験板を作製した。 First, a rust-preventive coating (vinyl-based A / C) was applied onto a steel plate (75 × 150 × 1 mm) so that the thickness after drying was about 50 μm, and dried to form a rust-preventive coating. Then, a coating composition for a lower layer coating film was applied onto the rust preventive coating film so that the thickness after drying was about 150 μm. The obtained coating material was dried at room temperature for 24 hours, and then the coating composition for the upper coating film was applied so that the thickness after drying was 150 μm. The obtained multi-layer coating film was dried at 40 ° C. for 3 days to prepare a test plate having a dry multi-layer coating film having a thickness of about 300 μm.
　作製した試験板を上記回転装置の回転ドラムに海水と接触するように固定して、２０ノットの速度で回転ドラムを回転させた。その間、海水の温度を２５℃、ｐＨを８．０～８．２に保ち、一週間毎に海水を入れ換えた。ロータリー試験開始から３６ヶ月後の試験板を水洗乾燥後、耐衝撃性試験を行った。ＪＩＳ　Ｋ５６００－５－３：１９９９「塗料一般試験方法－塗膜の機械的性質－耐おもり落下性」に準じて落球式の条件を用いて測定を行った。
　結果は、おもりの先端の衝撃による塗膜の状態を以下の基準で判断した。
◎：塗膜の割れ、剥がれがない
〇：軽度の割れ、剥がれが観測される
△：中度の割れ、剥がれが観測される
×：重度の割れ、剥がれが観測される The prepared test plate was fixed to the rotating drum of the rotating device so as to come into contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During that time, the temperature of the seawater was maintained at 25 ° C. and the pH was maintained at 8.0 to 8.2, and the seawater was replaced every week. After 36 months from the start of the rotary test, the test plate was washed and dried with water, and then an impact resistance test was performed. Measurements were carried out using falling ball conditions in accordance with JIS K5600-5-3: 1999 "General paint test method-Mechanical properties of coating film-Weight drop resistance".
As a result, the state of the coating film due to the impact of the tip of the weight was judged according to the following criteria.
◎: No cracking or peeling of the coating film 〇: Mild cracking or peeling is observed △: Moderate cracking or peeling is observed ×: Severe cracking or peeling is observed
＜＜試験例２（防汚試験）＞＞
　硬質塩ビ板（１００×２００×２ｍｍ）の両面に乾燥塗膜としての厚みが約１００μｍとなるよう下層塗膜用の塗料組成物を塗布した。得られた塗布物を室温で２４時間乾燥させ、その上に、乾燥塗膜として厚みが約１００μｍとなるように上層塗膜用の塗料組成物を塗布した。得られた複層塗布物を室温（２５℃）で３日間乾燥させることにより、厚みが約２００μｍの乾燥複層塗膜を有する試験板を作製した。この試験板を三重県尾鷲市の海面下１．５ｍに浸漬して付着物による試験板の汚損を２４ヶ月観察した。 << Test Example 2 (Anti-fouling test) >>
A coating composition for a lower coating film was applied to both sides of a hard vinyl chloride plate (100 × 200 × 2 mm) so that the thickness of the dry coating film was about 100 μm. The obtained coating film was dried at room temperature for 24 hours, and a coating composition for an upper coating film was applied onto the dried coating film so as to have a thickness of about 100 μm. The obtained multi-layer coating material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry multi-layer coating film having a thickness of about 200 μm. This test plate was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and the stain on the test plate due to deposits was observed for 24 months.
　評価は、塗膜表面の状態を目視観察することにより行い、以下の基準で判断した。
◎：貝類や藻類などの汚損生物の付着がなく、かつ、スライムも殆ど付着していないレベル
○：貝類や藻類などの汚損生物の付着がなく、かつ、スライムが薄く（塗膜面が見える程度）付着して
いるものの刷毛で軽く拭いて取れるレベル
△：貝類や藻類などの汚損生物の付着はないが、スライムが薄く（塗膜面が見える程度）付着しており
刷毛で強く拭いて取れないレベル
×：貝類や藻類などの汚損生物の付着はないが、スライムが塗膜面が見えない程度に厚く付着して
おり刷毛で強く拭いても取れないレベル
××：貝類や藻類などの汚損生物が付着しているレベル The evaluation was performed by visually observing the state of the coating film surface, and judged according to the following criteria.
⊚: Level where no polluted organisms such as shellfish and algae adhere and almost no slime adheres ○: No adherence of polluted organisms such as shellfish and algae, and slime is thin (to the extent that the coating surface can be seen) ) Level that can be wiped off lightly with a brush even though it is attached △: There is no adhesion of polluted organisms such as shellfish and algae, but slime is thinly attached (to the extent that the coated surface can be seen) and cannot be wiped off strongly with a brush. Level ×: There is no adhesion of polluted organisms such as shellfish and algae, but slime is adhered so thick that the coated surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush. Level of algae
４．考察
　上記結果より、全ての実施例の複層防汚塗膜は、耐衝撃性及び防汚性が非常に優れていた。一方、全ての比較例の複層防汚塗膜は、耐衝撃性又は防汚性の何れかが良好でなかった。 4. Discussion From the above results, the multi-layer antifouling coating film of all the examples was very excellent in impact resistance and antifouling property. On the other hand, the multi-layer antifouling coating film of all the comparative examples did not have good impact resistance or antifouling property.
　比較例１では、下層塗膜中のシリルエステル含有量が低く、後半の塗膜更新がやや低下するとともにスケルトン層が生成し、塗膜が脆弱であった。
　比較例２では、上層塗膜の疎水性が高く、初期の塗膜溶解が小さいため、初期の防汚性が悪かった。
　比較例３は、上層塗膜中の共重合体を構成する単量体（ｃ）成分が少ないため、初期の塗膜溶解が小さく、初期の防汚性が悪かった。
　比較例４は、上層がアクリル酸トリイソプロピルシリルの共重合体からなる塗膜であり、後半にクラックが起こることで防汚性が悪化し、塗膜強度も落ちた。
　比較例５は、上層塗膜中のシリルエステル含有量が低く、初期から適正な塗膜更新が得られず、防汚性が劣るとともに塗膜も脆弱であった。
　比較例６は、単量体（ａ）～（ｃ）の何れも含まない共重合体からなる塗膜であり初期防汚性および塗膜強度が劣っていた。
　比較例７は、下層塗膜中のシリルエステル含有量が高すぎることにより、後半の塗膜更新が遅く、防汚性が一気に悪化した。 In Comparative Example 1, the silyl ester content in the lower coating film was low, the coating film renewal in the latter half was slightly reduced, a skeleton layer was formed, and the coating film was fragile.
In Comparative Example 2, the hydrophobicity of the upper coating film was high and the initial coating film dissolution was small, so that the initial antifouling property was poor.
In Comparative Example 3, since the monomer (c) component constituting the copolymer in the upper coating film was small, the initial coating film dissolution was small and the initial antifouling property was poor.
In Comparative Example 4, the upper layer was a coating film made of a copolymer of triisopropylsilyl acrylate, and cracks occurred in the latter half, so that the antifouling property was deteriorated and the coating film strength was also lowered.
In Comparative Example 5, the silyl ester content in the upper coating film was low, proper coating film renewal could not be obtained from the initial stage, the antifouling property was inferior, and the coating film was also fragile.
Comparative Example 6 was a coating film made of a copolymer containing none of the monomers (a) to (c), and was inferior in initial antifouling property and coating film strength.
In Comparative Example 7, since the silyl ester content in the lower coating film was too high, the coating film was renewed slowly in the latter half, and the antifouling property deteriorated at once.

Claims (2)

  1. 　下層塗膜と、その上に形成された上層塗膜を有する複層防汚塗膜であって、
    　前記上層塗膜は、共重合体Ａを含み、
    　前記下層塗膜は、共重合体Ｂを含み、
    　前記上層塗膜及び下層塗膜は、それぞれ、防汚薬剤を含み、
    　前記共重合体Ａは、単量体（ａ）と単量体（ｃ）を含み、且つ単量体（ｂ）を含んでもよい第１単量体混合物の共重合体であり、
    　前記共重合体Ｂは、前記単量体（ａ）と単量体（ｂ）の少なくとも一方を含む第２単量体混合物の共重合体であり、
    　前記単量体（ａ）～（ｃ）は、それぞれ、一般式（１）～（３）で表され、
    　前記共重合体Ａは、第１単量体混合物を１００質量％とすると、前記単量体（ａ）の含有量が１０～４５質量％であり、前記単量体（ｂ）の含有量が０～１５質量％であり、前記単量体（ｃ）の含有量が２０～５０質量％であり、前記単量体（ａ）と前記単量体（ｂ）の合計含有量が１０～４５質量％であり、
    　前記共重合体Ｂは、前記共重合体Ａ以外の共重合体であり、且つ第２単量体混合物を１００質量％とすると、前記単量体（ａ）と前記単量体（ｂ）の合計含有量が４６～６５質量％である、複層防汚塗膜。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１～Ｒ３はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基である。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ１～Ｒ３はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基である。）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ４は、水素原子又はメチル基であり、Ｒ５は、アルキル基またはアリール基であり、ｎは１～２５である。）     A multi-layer antifouling coating film having a lower layer coating film and an upper layer coating film formed on the lower layer coating film.
    The upper coating film contains the copolymer A and contains
    The underlayer coating film contains copolymer B and contains
    The upper coating film and the lower coating film each contain an antifouling agent and contain an antifouling agent.
    The copolymer A is a copolymer of a first monomer mixture containing the monomer (a) and the monomer (c) and may contain the monomer (b).
    The copolymer B is a copolymer of a second monomer mixture containing at least one of the monomer (a) and the monomer (b).
    The monomers (a) to (c) are represented by the general formulas (1) to (3), respectively.
    Assuming that the first monomer mixture is 100% by mass, the copolymer A has a content of the monomer (a) of 10 to 45% by mass and a content of the monomer (b). The content is 0 to 15% by mass, the content of the monomer (c) is 20 to 50% by mass, and the total content of the monomer (a) and the monomer (b) is 10 to 45. By mass%
    Assuming that the copolymer B is a copolymer other than the copolymer A and the second monomer mixture is 100% by mass, the monomer (a) and the monomer (b) A multi-layer antifouling coating having a total content of 46 to 65% by mass.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 to R 3 are the same or different branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, respectively.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 1 to R 3 are the same or different branched alkyl groups or phenyl groups having 3 to 8 carbon atoms, respectively.)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 4 is a hydrogen atom or a methyl group, R 5 is an alkyl group or an aryl group, and n is 1 to 25.)
  2. 　請求項１に記載の複層防汚塗膜を表面に有する塗装物。 A coated product having the multi-layer antifouling coating film according to claim 1 on the surface.
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