JP6638958B2 - Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, method for producing the same, and antifouling method - Google Patents
Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, method for producing the same, and antifouling method Download PDFInfo
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- JP6638958B2 JP6638958B2 JP2018550200A JP2018550200A JP6638958B2 JP 6638958 B2 JP6638958 B2 JP 6638958B2 JP 2018550200 A JP2018550200 A JP 2018550200A JP 2018550200 A JP2018550200 A JP 2018550200A JP 6638958 B2 JP6638958 B2 JP 6638958B2
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- antifouling
- coating film
- antifouling coating
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical compound [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- WBPKUDYPHXKHJC-UHFFFAOYSA-L zinc 2-methylprop-2-enoic acid prop-2-enoate Chemical compound [Zn++].[O-]C(=O)C=C.[O-]C(=O)C=C.CC(=C)C(O)=O WBPKUDYPHXKHJC-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Description
本発明は、防汚塗料組成物、これを用いた、防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに防汚方法に関する。 The present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating film using the same, a method for producing the same, and an antifouling method.
現在、船舶等の水生生物による汚損を防ぐ方法として、水中において表面から塗膜が更新する特性を有する加水分解性重合体を用いる手法が広く利用されている。
このような加水分解性重合体をバインダーとする防汚塗膜は、水中において加水分解の進行とともに表面から親水化し、親水化した部分が水流により研掃して塗膜更新性を発揮するものであり、その代表的なものとしてシリルエステル系重合体が広く用いられている。
シリルエステル系重合体としては、加水分解性基であるトリアルキルシリルエステル基を含む単量体とその他の併用単量体とを重合させて得られる共重合体が用いられることが一般的であり、組み合わせる併用単量体の種類や量によって、重合体の塗膜更新速度や防汚性が大きく影響を受けるため、その研究が盛んに行われている。
このような併用単量体として近年、塗膜の防汚性を向上させる目的でオルガノポリシロキサン構造を有するものが検討されている。
例えば特許文献１には、シリコン含有重合性単量体から誘導される構成単位と、トリオルガノシリル（メタ）アクリレートから誘導される構成単位とを含む加水分解性樹脂を含有する防汚塗料組成物が開示されている。At present, as a method for preventing pollution by aquatic organisms such as ships, a method using a hydrolyzable polymer having a property of renewing a coating film from the surface in water is widely used.
The antifouling coating film using such a hydrolyzable polymer as a binder is hydrophilized from the surface with the progress of hydrolysis in water, and the hydrophilized portion is polished by a water flow to exhibit renewability of the coating film. As a typical example, a silyl ester polymer is widely used.
As the silyl ester polymer, a copolymer obtained by polymerizing a monomer containing a trialkylsilyl ester group, which is a hydrolyzable group, and another combined monomer is generally used. Since the renewal speed and antifouling property of the polymer are greatly affected by the kind and amount of the combined monomer used in combination, researches on the method are actively conducted.
In recent years, as such a combination monomer, a monomer having an organopolysiloxane structure has been studied for the purpose of improving the antifouling property of a coating film.
For example, Patent Document 1 discloses an antifouling paint composition containing a hydrolyzable resin containing a structural unit derived from a silicon-containing polymerizable monomer and a structural unit derived from triorganosilyl (meth) acrylate. Is disclosed.
しかし、上記特許文献１に開示された防汚塗料組成物は、水中での静置の浸漬状態では長期に良好な防汚性を発揮するものの、オルガノポリシロキサンの水透過性由来と推定される塗膜内部状態の変質のため、長期にわたり高速水流に曝されると、防汚性及び上塗り付着性（リコート性）が低下するという課題が判明した。
このような課題に鑑み、本発明は高速水流環境下においても長期に防汚性能を発揮することができ、乾湿交互部においても防汚性に優れ、更に、リコート性に優れる防汚塗膜が得られる防汚塗料組成物を提供することを目的とする。更に、本発明は、前記防汚塗料組成物を使用した防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに、防汚方法を提供することを目的とする。However, although the antifouling paint composition disclosed in Patent Document 1 exhibits good antifouling properties for a long period of time when left standing in water, it is presumed to be derived from the water permeability of organopolysiloxane. The subject that the antifouling property and the topcoat adhesion (recoating property) deteriorate when exposed to a high-speed water stream for a long period of time due to deterioration of the internal state of the coating film has been found.
In view of such problems, the present invention can exhibit antifouling performance for a long period of time even under a high-speed water flow environment, has excellent antifouling properties even in a dry / wet alternating portion, and further has an antifouling coating film having excellent recoating properties. It is an object to provide the obtained antifouling paint composition. Further, another object of the present invention is to provide an antifouling coating film, a substrate with an antifouling coating film, a method for producing the same, and an antifouling method using the antifouling coating composition.
本発明者らが鋭意検討した結果、以下に示す防汚塗料組成物を用いることで上記課題を解決できることを見出し、本発明を完成させるに至った。
本発明の要旨は以下のとおりである。As a result of intensive studies by the present inventors, they have found that the above problem can be solved by using the following antifouling paint composition, and have completed the present invention.
The gist of the present invention is as follows.
本発明は、以下の［１］〜［２５］に関する。
［１］ シリルエステル系共重合体（Ａ）を含有し、該シリルエステル系共重合体（Ａ）が、（ｉ）トリアルキルシリルメタクリレート（ａ１）に由来する構成単位、及び（ii）下記式（Ｉ）で表される化合物（ａ２）に由来する構成単位を有することを特徴とする、防汚塗料組成物。The present invention relates to the following [1] to [25].
[1] A silyl ester-based copolymer (A) is contained, wherein the silyl ester-based copolymer (A) is derived from (i) a trialkylsilyl methacrylate (a1) structural unit, and (ii) a compound represented by the following formula: An antifouling paint composition comprising a structural unit derived from the compound (a2) represented by (I).
（式（Ｉ）中、Ｒ１、Ｒ２及びＲ３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）
(In the formula (I), R 1 , R 2 and R 3 each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and m And n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)
［２］ 前記シリルエステル系共重合体（Ａ）が、トリアルキルシリルメタクリレート（ａ１）に由来する構成単位を２０〜８０質量％、好ましくは４０〜７０質量％含有する、［１］に記載の防汚塗料組成物。
［３］ 前記シリルエステル系共重合体（Ａ）が、化合物（ａ２）に由来する構成単位を１〜３０質量％、好ましくは１．５〜１５質量％含有する、［１］又は［２］に記載の防汚塗料組成物。
［４］ 前記トリアルキルシリルメタクリレート（ａ１）が、トリイソプロピルシリルメタクリレートである、［１］〜［３］のいずれかに記載の防汚塗料組成物。
［５］ 前記シリルエステル系共重合体（Ａ）が、式（Ｉ）中、ｎが０であり、ｐが１であり、ｑが０である化合物（ａ２１）、式（Ｉ）中、ｎが０であり、ｐ及びｑが１である化合物（ａ２２）、並びに式（Ｉ）中、ｎが１以上である化合物（ａ２３）よりなる群から選択される少なくとも１つの化合物に由来する構成単位を有する、［１］〜［４］のいずれかに記載の防汚塗料組成物。
［６］ 前記シリルエステル系共重合体（Ａ）が、更に１以上の（iii）その他の単量体（ａ３）に由来する構成単位を有する、［１］〜［５］のいずれか１つに記載の防汚塗料組成物。
［７］ 前記その他の単量体（ａ３）が、下記式（II）で表される単量体（ａ３１）を含有する、［６］に記載の防汚塗料組成物。[2] The method according to [1], wherein the silyl ester-based copolymer (A) contains 20 to 80% by mass, preferably 40 to 70% by mass of a structural unit derived from a trialkylsilyl methacrylate (a1). Antifouling paint composition.
[3] [1] or [2], wherein the silyl ester-based copolymer (A) contains 1 to 30% by mass, preferably 1.5 to 15% by mass of a structural unit derived from the compound (a2). 3. The antifouling coating composition according to item 1.
[4] The antifouling coating composition according to any one of [1] to [3], wherein the trialkylsilyl methacrylate (a1) is triisopropylsilyl methacrylate.
[5] The compound (a21), wherein n is 0, p is 1 and q is 0 in the formula (I), wherein the silyl ester-based copolymer (A) is Is 0, and p and q are 1 and a structural unit derived from at least one compound selected from the group consisting of a compound (a23) in which n is 1 or more in the formula (I). The antifouling paint composition according to any one of [1] to [4], having:
[6] Any one of [1] to [5], wherein the silyl ester-based copolymer (A) further has one or more structural units derived from (iii) another monomer (a3). 3. The antifouling coating composition according to item 1.
[7] The antifouling coating composition according to [6], wherein the other monomer (a3) contains a monomer (a31) represented by the following formula (II).
（式（II）中、Ｒ４は水素原子又はメチル基を示し、Ｒ５は水素原子又は一価の炭化水素基を示し、Ｒ６は二価の炭化水素基を示し、ｓは１〜６の整数を示す。）
(In the formula (II), R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrogen atom or a monovalent hydrocarbon group, R 6 represents a divalent hydrocarbon group, and s represents 1 to 6 Represents an integer.)
［８］ 式（II）中、Ｒ４が水素原子である、［７］に記載の防汚塗料組成物。
［９］ 式（II）中、Ｒ５が一価の炭化水素基であり、好ましくは炭素数１〜６のアルキル基、より好ましくは炭素数１〜４のアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基）であり、更に好ましくはメチル基である、［７］又は［８］に記載の防汚塗料組成物。
［１０］ 式（II）中、Ｒ６が炭素数２〜６のアルキレン基であり、好ましくは炭素数２〜４のアルキレン基であり、更に好ましくはエチレン基又はプロピレン基である、［７］〜［９］のいずれか１つに記載の防汚塗料組成物。
［１１］ 式（II）中、ｓが１〜３の整数であり、好ましくは１である、［７］〜［１０］のいずれか１つに記載の防汚塗料組成物。
［１２］ 前記シリルエステル系共重合体（Ａ）が、式（II）で表される単量体（ａ３１）に由来する構成単位を１０〜３５質量％、好ましくは１５〜３０質量％含有する、［７］〜［１１］のいずれか１つに記載の防汚塗料組成物。
［１３］ 前記その他の単量体（ａ３）が、メチルメタクリレートを含有する、［７］〜［１２］のいずれか１つに記載の防汚塗料組成物。
［１４］ 前記シリルエステル系共重合体（Ａ）が、不飽和脂肪酸に由来する構成単位を１０質量％以下、好ましくは５質量％以下、更に好ましくは１質量％以下、より更に好ましくは０質量％含有する、［１］〜［１３］のいずれかに記載の防汚塗料組成物。
［１５］ 前記シリルエステル系共重合体（Ａ）の重量平均分子量が、３，０００〜７０，０００、好ましくは１０，０００〜５０，０００である、［１］〜［１４］のいずれかに記載の防汚塗料組成物。
［１６］ 防汚塗料組成物の固形分中、前記シリルエステル系共重合体（Ａ）を５〜５０質量％、好ましくは１０から３５質量％、より好ましくは１０〜２０質量％含有する、［１］〜［１５］のいずれか１つに記載の防汚塗料組成物。
［１７］ 更に、防汚剤（Ｂ）を含有する、［１］〜［１６］のいずれか１つに記載の防汚塗料組成物。
［１８］ 前記防汚剤（Ｂ）が亜酸化銅（Ｂ１）を含有する、［１７］に記載の防汚塗料組成物。
［１９］ 防汚塗料組成物の固形分中、前記亜酸化銅（Ｂ１）を２０〜８０質量％、好ましくは４０〜７０質量％、より好ましくは５０〜６５質量％含有する、［１８］に記載の防汚塗料組成物。
［２０］ 更に、モノカルボン酸化合物（Ｃ）を含有する、［１］〜［１９］のいずれか１つに記載の防汚塗料組成物。
［２１］ 更に、その他バインダー成分（Ｄ）、顔料（Ｅ）、有機溶剤（Ｆ）、タレ止め剤・沈降防止剤（Ｇ）、脱水剤（Ｈ）、及び可塑剤（Ｉ）よりなる群から選択される少なくとも１つを含有する、［１］〜［２０］のいずれか１つに記載の防汚塗料組成物。
［２２］ ［１］〜［２１］のいずれか１つに記載の防汚塗料組成物から形成された防汚塗膜。
［２３］ ［２２］に記載の防汚塗膜で被覆された防汚塗膜付き基材。
［２４］ ［１］〜［２１］のいずれか１つに記載の防汚塗料組成物を基材に塗布又は含浸し、塗布体又は含浸体を得る工程（１）、及び前記塗布体又は含浸体を乾燥する工程（２）を有する、防汚塗膜付き基材の製造方法。
［２５］ ［２２］に記載の防汚塗膜を使用する、防汚方法。[8] The antifouling coating composition according to [7], wherein in the formula (II), R 4 is a hydrogen atom.
[9] In the formula (II), R 5 is a monovalent hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group Group, propyl group, butyl group), and more preferably a methyl group, the antifouling coating composition according to [7] or [8].
[10] In the formula (II), R 6 is an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an ethylene group or a propylene group. -The antifouling coating composition according to any one of [9].
[11] The antifouling coating composition according to any one of [7] to [10], wherein in formula (II), s is an integer of 1 to 3, preferably 1.
[12] The silyl ester-based copolymer (A) contains 10 to 35% by mass, preferably 15 to 30% by mass of a structural unit derived from the monomer (a31) represented by the formula (II). , [7]-The antifouling coating composition according to any one of [11].
[13] The antifouling coating composition according to any one of [7] to [12], wherein the other monomer (a3) contains methyl methacrylate.
[14] The silyl ester copolymer (A) contains 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0% by mass of a structural unit derived from an unsaturated fatty acid. %. The antifouling coating composition according to any one of [1] to [13].
[15] Any of [1] to [14], wherein the weight average molecular weight of the silyl ester copolymer (A) is from 3,000 to 70,000, preferably from 10,000 to 50,000. The antifouling paint composition according to the above.
[16] The solid content of the antifouling coating composition contains 5 to 50% by mass, preferably 10 to 35% by mass, more preferably 10 to 20% by mass of the silyl ester-based copolymer (A). The antifouling coating composition according to any one of 1) to [15].
[17] The antifouling coating composition according to any one of [1] to [16], further comprising an antifouling agent (B).
[18] The antifouling paint composition according to [17], wherein the antifouling agent (B) contains cuprous oxide (B1).
[19] The composition according to [18], wherein the solid content of the antifouling coating composition contains 20 to 80% by mass, preferably 40 to 70% by mass, more preferably 50 to 65% by mass of the cuprous oxide (B1). The antifouling paint composition according to the above.
[20] The antifouling coating composition according to any one of [1] to [19], further comprising a monocarboxylic acid compound (C).
[21] Further, from the group consisting of other binder components (D), pigments (E), organic solvents (F), anti-sagging agents and anti-settling agents (G), dehydrating agents (H), and plasticizers (I). The antifouling paint composition according to any one of [1] to [20], containing at least one selected from the group consisting of:
[22] An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [21].
[23] A substrate with an antifouling coating film coated with the antifouling coating film according to [22].
[24] A step (1) of coating or impregnating a substrate with the antifouling coating composition according to any one of [1] to [21] to obtain a coated body or impregnated body, and the coated body or impregnated body A method for producing a substrate with an antifouling coating film, comprising a step (2) of drying the body.
[25] An antifouling method using the antifouling coating film according to [22].
本発明によれば、高速水流環境下においても長期に防汚性能を発揮することができ、乾湿交互部においても防汚性に優れ、更に、リコート性に優れる防汚塗膜が得られる防汚塗料組成物を提供することができる。更に、本発明によれば、前記防汚塗料組成物を使用した防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに、防汚方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, antifouling performance can be exhibited for a long period of time even in a high-speed water flow environment, antifouling properties are excellent even in a dry / wet alternating portion, and further, an antifouling coating film having excellent recoating properties is obtained. A coating composition can be provided. Further, according to the present invention, an antifouling coating film, a substrate with an antifouling coating film using the antifouling coating composition, a method for producing the same, and an antifouling method can be provided.
以下、本発明に係る防汚塗料組成物、防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに防汚方法について詳細に説明する。
なお、以下の説明において、「（メタ）アクリロイル」、「（メタ）アクリル酸」及び「（メタ）アクリレート」は、それぞれ「アクリロイル又はメタクリロイル」、「アクリル酸又はメタクリル酸」、及び「アクリレート又はメタクリレート」を意味する。
［防汚塗料組成物］
本発明の防汚塗料組成物（以下、単に「塗料組成物」ともいう。）は、シリルエステル系共重合体（Ａ）を含有し、該シリルエステル系共重合体（Ａ）が、（ｉ）トリアルキルシリルメタクリレート（ａ１）に由来する構成単位、及び（ii）下記式（Ｉ）で表される化合物（ａ２）に由来する構成単位を有することを特徴とする。Hereinafter, the antifouling coating composition, the antifouling coating film, the substrate with the antifouling coating film, the production method thereof, and the antifouling method according to the present invention will be described in detail.
In the following description, “(meth) acryloyl”, “(meth) acrylic acid” and “(meth) acrylate” are “acryloyl or methacryloyl”, “acrylic acid or methacrylic acid”, and “acrylate or methacrylate”, respectively. Means.
[Antifouling paint composition]
The antifouling paint composition of the present invention (hereinafter, also simply referred to as “paint composition”) contains a silyl ester copolymer (A), and the silyl ester copolymer (A) contains (i) ) A structural unit derived from a trialkylsilyl methacrylate (a1) and (ii) a structural unit derived from a compound (a2) represented by the following formula (I).
（式（Ｉ）中、Ｒ１、Ｒ２及びＲ３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）
(In the formula (I), R 1 , R 2 and R 3 each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and m And n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)
本発明によれば、高速水流環境下においても長期に防汚性能を発揮することができ、乾湿交互部においても防汚性に優れ、更に、リコート性に優れる防汚塗膜が得られる防汚塗料組成物を提供することができる。
特許文献１に記載された防汚塗料組成物では、水中での静置の浸漬状態では長期に良好な防汚性を発揮するものの、オルガノポリシロキサンの水透過性由来と推定される塗膜内部状態の変質のため、長期にわたり高速水流に曝されると、防汚性及び上塗り付着性（リコート性）が低下するという問題があった。本発明は、特定のシリルエステル系共重合体（Ａ）を含有することにより、長期にわたって防汚性が維持され、リコート性にも優れた防汚塗膜を形成できる防汚塗料組成物が提供されることを見出したものである。更に、予測しがたい効果として、乾湿交互部においても防汚性に優れる防汚塗膜が得られた。ADVANTAGE OF THE INVENTION According to this invention, antifouling performance can be exhibited for a long period of time even in a high-speed water flow environment, antifouling properties are excellent even in a dry / wet alternating portion, and further, an antifouling coating film having excellent recoating properties is obtained. A coating composition can be provided.
The antifouling coating composition described in Patent Document 1 exhibits good antifouling properties for a long period of time in a immersion state of standing in water, but the inside of the coating film which is presumed to be derived from the water permeability of organopolysiloxane. When exposed to a high-speed water stream for a long period of time due to deterioration of the state, there is a problem that the antifouling property and the adhesion to the top coat (recoat property) are reduced. The present invention provides an antifouling paint composition which contains a specific silyl ester copolymer (A), thereby maintaining an antifouling property for a long time and forming an antifouling coating film having excellent recoating properties. It is found that it is done. Further, as an unpredictable effect, an antifouling coating film having excellent antifouling properties was obtained even in the dry / wet alternating portion.
なお、上記の効果が得られる詳細な作用機序は必ずしも明らかではないが、一部は以下のように推定される。すなわち、特定のシリルエステル系共重合体（Ａ）を含有することにより、防汚塗膜に適度な耐水性と水中での表面からの塗膜更新性が付与され、より長期にわたって防汚性が維持されるとともに、適度な耐水性により、塗膜内部状態の変質が抑制されて、リコート性に優れた防汚塗膜が得られたものと考えられる。
以下、本発明の防汚塗料組成物が含有する各成分について詳述する。Although the detailed mechanism of action for obtaining the above-mentioned effects is not necessarily clear, some of them are presumed as follows. That is, by containing the specific silyl ester-based copolymer (A), the antifouling coating film is provided with appropriate water resistance and renewability of the coating film from the surface in water, and the antifouling property is maintained for a longer period of time. It is considered that, while being maintained, due to appropriate water resistance, deterioration of the internal state of the coating film was suppressed, and an antifouling coating film having excellent recoating properties was obtained.
Hereinafter, each component contained in the antifouling coating composition of the present invention will be described in detail.
＜シリルエステル系共重合体（Ａ）＞
本発明において、シリルエステル系共重合体（Ａ）は、（ｉ）トリアルキルシリルメタクリレート（ａ１）に由来する構成単位、及び（ii）上記式（Ｉ）で表される化合物（ａ２）に由来する構成単位を有する。また、シリルエステル系共重合体（Ａ）は、任意に（iii）その他の単量体（ａ３）に由来する構成単位を有し、（iii）その他の単量体（ａ３）に由来する構成単位を有することが好ましい。
なお、本発明において、「Ａに由来する構成単位を有する共重合体」とは、Ａが重合反応又は連鎖移動反応により導入された共重合体を意味する。従って、式（Ｉ）で表される化合物がメルカプトアルキル基を有する場合には、ラジカル重合末端が−ＳＨのＨを引き抜き、生成した−Ｓ・（Ｓラジカル）が重合を開始する形でシリルエステル系共重合体（Ａ）に導入されるが、このような場合にも、シリルエステル系共重合体（Ａ）は、式（Ｉ）で表される化合物に由来する構成単位を有するものである。
以下、各構成単位について説明する。<Silyl ester copolymer (A)>
In the present invention, the silyl ester-based copolymer (A) is derived from (i) a structural unit derived from a trialkylsilyl methacrylate (a1), and (ii) a compound derived from the compound (a2) represented by the above formula (I). Having the following structural unit. The silyl ester copolymer (A) optionally has a structural unit derived from (iii) another monomer (a3), and (iii) a structural unit derived from another monomer (a3). It preferably has units.
In the present invention, the “copolymer having a structural unit derived from A” means a copolymer in which A is introduced by a polymerization reaction or a chain transfer reaction. Therefore, when the compound represented by the formula (I) has a mercaptoalkyl group, the silyl ester is formed in such a form that the radical polymerization terminal extracts H of —SH and the generated —S · (S radical) initiates polymerization. The silyl ester copolymer (A) is introduced into the copolymer (A). In such a case, the silyl ester copolymer (A) has a structural unit derived from the compound represented by the formula (I). .
Hereinafter, each structural unit will be described.
〔（ｉ）トリアルキルシリルメタクリレート（ａ１）に由来する構成単位〕
トリアルキルシリルメタクリレート（ａ１）は、下記式（III）で表される単量体である。[(I) Structural unit derived from trialkylsilyl methacrylate (a1)]
Trialkylsilyl methacrylate (a1) is a monomer represented by the following formula (III).
（式（III）中、Ｒ７、Ｒ８、及びＲ９はそれぞれ独立に、一価の炭化水素基を示す。）
(In the formula (III), R 7 , R 8 , and R 9 each independently represent a monovalent hydrocarbon group.)
式（III）中、Ｒ７、Ｒ８及びＲ９は、それぞれ独立に一価の炭化水素基を表し、直鎖状、分岐鎖状、又は環状のアルキル基、及びアリール基等が挙げられ、前記アルキル基は、炭素数が好ましくは１〜１２、より好ましくは１〜８、更に好ましくは１〜４である。また、前記アリール基は、炭素数が好ましくは６〜１４、より好ましくは６〜１０である。
シリルエステル系共重合体（Ａ）が水中で適切な速度で加水分解する観点から、Ｒ７〜Ｒ９としては、メチル基、エチル基、イソプロピル基、ｎ−プロピル基、イソブチル基、ｓｅｃ−ブチル基、ｎ−ブチル基、２−エチルヘキシル基、フェニル基等が例示され、これらの中でも、イソプロピル基、ｎ−プロピル基、ｓｅｃ−ブチル基、ｎ−ブチル基、及びフェニル基よりなる群から選択されることが好ましく、Ｒ７〜Ｒ９の全てがイソプロピル基であることがより好ましい。In the formula (III), R 7 , R 8 and R 9 each independently represent a monovalent hydrocarbon group, and examples thereof include a linear, branched or cyclic alkyl group, and an aryl group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, and still more preferably 1 to 4. The aryl group preferably has 6 to 14, more preferably 6 to 10 carbon atoms.
From the viewpoint that the silyl ester-based copolymer (A) is hydrolyzed in water at an appropriate rate, R 7 to R 9 are methyl, ethyl, isopropyl, n-propyl, isobutyl, sec-butyl. Group, n-butyl group, 2-ethylhexyl group, phenyl group and the like, and among them, selected from the group consisting of isopropyl group, n-propyl group, sec-butyl group, n-butyl group, and phenyl group. It is more preferable that all of R 7 to R 9 are isopropyl groups.
シリルエステル系共重合体（Ａ）におけるトリアルキルシリルメタクリレート（ａ１）に由来する構成単位の含有量は、形成される防汚塗膜が適当な塗膜更新速度を有する点から全構成単位１００質量部に対して、好ましくは２０〜８０質量部、より好ましくは４０〜７０質量部である。
なお、本発明において、シリルエステル系共重合体（Ａ）中の各単量体等に由来する構成単位の各含有量（質量）の比率は、重合反応に用いる前記各単量体等（反応原料）の仕込み量（質量）の比率と同じものとしてみなすことができる。The content of the structural unit derived from the trialkylsilyl methacrylate (a1) in the silyl ester-based copolymer (A) is 100 parts by mass in view of the fact that the formed antifouling coating film has an appropriate coating film renewal speed. Parts by weight, preferably 20 to 80 parts by weight, more preferably 40 to 70 parts by weight.
In the present invention, the ratio of each content (mass) of the structural unit derived from each monomer or the like in the silyl ester copolymer (A) depends on the above-mentioned each monomer or the like used in the polymerization reaction. It can be regarded as the same as the ratio of the charged amount (mass) of the raw material).
本発明は、トリアルキルシリルアクリレートでなくトリアルキルシリルメタクリレートを用いる点に１つの特徴を有する。シリルエステル系共重合体（Ａ）の重合においては、式（Ｉ）で表される化合物（ａ２）の低溶解性等に起因すると考えられる均一な重合の困難さから、重合性の高いトリアルキルシリルアクリレートを用いることが一般的であった。本発明では、敢えて重合性の低いトリアルキルシリルメタクリレートを使用したことで、好適な塗膜物性と防汚性を発揮する防汚塗膜が得られるシリルエステル系共重合体（Ａ）を見出し、本発明を完成させた。 The present invention has one feature in using a trialkylsilyl methacrylate instead of a trialkylsilyl acrylate. In the polymerization of the silyl ester copolymer (A), a trialkyl having high polymerizability is considered due to the difficulty of uniform polymerization which is considered to be caused by the low solubility of the compound (a2) represented by the formula (I). It was common to use silyl acrylate. In the present invention, the use of trialkylsilyl methacrylate having low polymerizability darely finds a silyl ester copolymer (A) capable of obtaining an antifouling coating film exhibiting favorable coating film properties and antifouling properties, The present invention has been completed.
〔（ii）式（Ｉ）で表される化合物（ａ２）に由来する構成単位〕
本発明において、シリルエステル系共重合体（Ａ）は、下記式（Ｉ）で表される化合物（ａ２）に由来する構成単位を有する。[(Ii) Structural unit derived from compound (a2) represented by formula (I)]
In the present invention, the silyl ester copolymer (A) has a structural unit derived from a compound (a2) represented by the following formula (I).
（式（Ｉ）中、Ｒ１、Ｒ２、及びＲ３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）
(In the formula (I), R 1 , R 2 , and R 3 each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, m and n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)
式（Ｉ）中、Ｒ１、Ｒ２、及びＲ３はそれぞれ独立に一価の炭化水素基を表し、例えばＲ７、Ｒ８、及びＲ９と同様の基が挙げられ、重合容易性の観点からアルキル基が好ましく、炭素数１〜６のアルキル基がより好ましく、炭素数１〜４のアルキル基、具体的には、メチル基、エチル基、プロピル基、ブチル基が更に好ましい。
式（Ｉ）中、Ｘはそれぞれ独立に（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を表し、均一な重合の進行の観点からは（メタ）アクリロイルオキシアルキル基が好ましく、形成する重合体の粘度を低減し、取り扱いを容易とする観点からはメルカプトアルキル基も好ましい。
前記（メタ）アクリロイルオキシアルキル基は、下記式（ＶＩ）で表される。In the formula (I), R 1 , R 2 , and R 3 each independently represent a monovalent hydrocarbon group, and examples thereof include groups similar to R 7 , R 8 , and R 9 . From the viewpoint, an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, and a butyl group is further preferable.
In the formula (I), Xs each independently represent a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and from the viewpoint of uniform polymerization progress, a (meth) acryloyloxyalkyl group is preferable, and the viscosity of the polymer to be formed is From the viewpoint of reducing the amount and facilitating handling, a mercaptoalkyl group is also preferable.
The (meth) acryloyloxyalkyl group is represented by the following formula (VI).
（式（ＶＩ）中、Ｒ１１は水素原子又はメチル基を示し、Ｒ１２はアルキレン基を示し、＊はＳｉとの結合位置を示す。）
(In the formula (VI), R 11 represents a hydrogen atom or a methyl group, R 12 represents an alkylene group, and * represents a bonding position to Si.)
Ｒ１２はアルキレン基を示し、反応性の観点から、炭素数が好ましくは１〜１２、より好ましくは２〜６、更に好ましくは２〜４である。R 12 represents an alkylene group, and preferably has 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4 carbon atoms from the viewpoint of reactivity.
前記メルカプトアルキル基は、下記式（ＶＩＩ）で表される。 The mercaptoalkyl group is represented by the following formula (VII).
（式(VII)中、Ｒ１３はアルキレン基を示し、＊はＳｉとの結合位置を示す。）
(In the formula (VII), R 13 represents an alkylene group, and * represents a bonding position to Si.)
Ｒ１３はアルキレン基を示し、反応性の観点から、炭素数が好ましくは１〜１２、より好ましくは２〜６、更に好ましくは２〜４である。R 13 represents an alkylene group, and preferably has 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4 carbon atoms from the viewpoint of reactivity.
このようなＸとしては（メタ）アクリロイルオキシエチル基、（メタ）アクリロイルオキシプロピル基、（メタ）アクリロイルオキシブチル基やメルカプトメチル基、メルカプトエチル基、メルカプトプロピル基、メルカプトブチル基等が挙げられる。 Examples of such X include a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, a (meth) acryloyloxybutyl group, a mercaptomethyl group, a mercaptoethyl group, a mercaptopropyl group, and a mercaptobutyl group.
式（Ｉ）中、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。
なお、ｍ及びｎは、それぞれ（ＳｉＲ２ ２Ｏ）、（ＳｉＸＲ３Ｏ）の平均付加モル数を意味する。
式（Ｉ）中、ｍ＋ｎは、２以上であることが好ましい。すなわち、式（Ｉ）で表される化合物は、ポリオルガノシロキサン部分を有することが好ましい。
なお、本明細書において、２以上の異なる繰り返し単位を［ ］間に並列記載している場合、それらの繰り返し単位が、それぞれランダム状、交互状又はブロック状のいずれの形及び順序で繰り返されていてもよいことを示す。つまり、例えば、式−［Ｙ３−Ｚ３］−（ここで、Ｙ、Ｚは繰り返し単位を示す）では、−ＹＹＺＹＺＺ−のようなランダム状でも、−ＹＺＹＺＹＺ−のような交互状でも、−ＹＹＹＺＺＺ−又は−ＺＺＺＹＹＹ−のようなブロック状でもよい。In the formula (I), m and n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.
Incidentally, m and n are each (SiR 2 2 O), which means an average addition mole number of (SiXR 3 O).
In the formula (I), m + n is preferably 2 or more. That is, the compound represented by the formula (I) preferably has a polyorganosiloxane moiety.
In addition, in this specification, when two or more different repeating units are described in parallel between [], those repeating units are repeated in any of random, alternating, and block shapes and orders. Indicates that you may. That is, for example, the formula - [Y 3 -Z 3] - ( wherein, Y, Z represents a repeating unit), the in random form, such as -YYZYZZ-, in alternate form, such as -YZYZYZ-, - It may be in a block shape such as YYZZZZ- or -ZZZYYY-.
ある一形態として、シリルエステル系共重合体（Ａ）が、式（Ｉ）中、ｎが０であり、ｐが１であり、ｑが０である化合物（ａ２１）に由来する構成単位を有することが好ましい。
このような化合物（ａ２１）に由来する構成単位を有するシリルエステル系共重合体（Ａ）を含有する防汚塗料組成物は、特に優れた防汚性を有する防汚塗膜を形成できる点で好ましい。
このような化合物（ａ２１）では、重合容易性等の観点からｍは３〜２００であることが好ましく、５〜７０であることがより好ましい。
このような化合物（ａ２１）としては市販のものを用いることができ、例えば、ＪＮＣ（株）製のＦＭ−０７１１（片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１，０００）、ＦＭ−０７２１（片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝５，０００）、ＦＭ−０７２５（片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１０，０００）、信越化学工業（株）製のＸ−２２−１７４ＡＳＸ（片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量９００ｇ／ｍｏｌ）、ＫＦ−２０１２（片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量４，６００ｇ／ｍｏｌ）、Ｘ−２２−２４２６（片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量１２，０００ｇ／ｍｏｌ）が挙げられる。In one embodiment, the silyl ester copolymer (A) has a structural unit derived from the compound (a21) in which n is 0, p is 1, and q is 0 in the formula (I). Is preferred.
The antifouling coating composition containing the silyl ester copolymer (A) having a structural unit derived from the compound (a21) is capable of forming an antifouling coating film having particularly excellent antifouling properties. preferable.
In such a compound (a21), m is preferably from 3 to 200, and more preferably from 5 to 70, from the viewpoint of easiness of polymerization and the like.
As such a compound (a21), commercially available ones can be used. For example, FM-0711 (methacryloyloxyalkyl-modified organopolysiloxane at one end, average molecular weight Mn = 1,000) manufactured by JNC Co., Ltd., FM -0721 (one-terminal methacryloyloxyalkyl-modified organopolysiloxane, average molecular weight Mn = 5,000), FM-0725 (one-terminal methacryloyloxyalkyl-modified organopolysiloxane, average molecular weight Mn = 10,000), Shin-Etsu Chemical Co., Ltd. X-22-174ASX (methacryloyloxyalkyl-modified organopolysiloxane at one end, functional group equivalent 900 g / mol), KF-2012 (methacryloyloxyalkyl-modified organopolysiloxane at one end, functional group equivalent 4,600 g / mol) , X 22-2426 (one terminal methacryloyloxy alkyl-modified organopolysiloxane, functional group equivalent 12,000 g / mol) and the like.
また、ある一形態として、シリルエステル系共重合体（Ａ）が、式（Ｉ）中、ｎが０であり、ｐ及びｑが１である化合物（ａ２２）に由来する構成単位を有することも好ましい。
このような化合物（ａ２２）に由来する構成単位を有するシリルエステル系共重合体（Ａ）を含有する防汚塗料組成物は、形成される塗膜の上塗り付着性が良好となる点で好ましい。
このような化合物（ａ２２）では、重合容易性等の観点からｍは３〜２００であることが好ましく、５〜７０であることがより好ましい。
このような化合物（ａ２２）としては市販のものを用いることができ、例えば、ＪＮＣ（株）製のＦＭ−７７１１（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１，０００）、ＦＭ−７７２１（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝５，０００）、ＦＭ−７７２５（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１０，０００）、信越化学工業（株）製のＸ−２２−１６４（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量１９０ｇ／ｍｏｌ）、Ｘ−２２−１６４ＡＳ（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量４５０ｇ／ｍｏｌ）、Ｘ−２２−１６４Ａ（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量８６０ｇ／ｍｏｌ）、Ｘ−２２−１６４Ｂ（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量１６３０ｇ／ｍｏｌ）、Ｘ−２２−１６４Ｃ（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量２，３７０ｇ／ｍｏｌ）、Ｘ−２２−１６４Ｅ（両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、官能基当量３，９００ｇ／ｍｏｌ）、Ｘ−２２−１６７Ｂ（両末端メルカプトアルキル変性オルガノポリシロキサン、官能基当量１，６７０ｇ／ｍｏｌ）が挙げられる。In one embodiment, the silyl ester-based copolymer (A) may have a structural unit derived from the compound (a22) in which n is 0 and p and q are 1 in the formula (I). preferable.
The antifouling coating composition containing the silyl ester-based copolymer (A) having the structural unit derived from the compound (a22) is preferable in that the formed coating film has good overcoat adhesion.
In such a compound (a22), m is preferably from 3 to 200, and more preferably from 5 to 70, from the viewpoint of easiness of polymerization and the like.
As such a compound (a22), commercially available ones can be used. For example, FM-7711 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 1,000) manufactured by JNC Co., Ltd., FM -7721 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 5,000), FM-7725 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 10,000), Shin-Etsu Chemical Co., Ltd. X-22-164 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 190 g / mol) and X-22-164AS (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 450 g / mol) , X-2 X-164A (methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 860 g / mol), X-22-164B (methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 1630 g / mol), X-22-164C (Methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 2,370 g / mol), X-22-164E (methacryloyloxyalkyl-modified organopolysiloxane at both terminals, functional group equivalent 3,900 g / mol), X-22 -167B (mercaptoalkyl-modified organopolysiloxane at both ends, functional group equivalent: 1,670 g / mol).
更に、ある一形態として、シリルエステル系共重合体（Ａ）が、式（Ｉ）中、ｎが１以上である化合物（ａ２３）に由来する構成単位を有することも好ましい。
シリルエステル系共重合体（Ａ）がこのような化合物（ａ２３）に由来する構成単位を有すると、粘度が低く取扱いが容易である点で好ましい。
このような化合物（ａ２３）においては、ｍは、好ましくは５０〜１，０００であり、ｎは、好ましくは１〜３０である。
このような化合物（ａ２３）としては市販のものを用いることができ、例えば、信越化学工業（株）製のＫＦ−２００１（側鎖メルカプトアルキル変性オルガノポリシロキサン、官能基当量１，９００ｇ／ｍｏｌ）、ＫＦ−２００４（側鎖メルカプトアルキル変性オルガノポリシロキサン、官能基当量３０，０００ｇ／ｍｏｌ）が挙げられる。Further, as one embodiment, it is preferable that the silyl ester copolymer (A) has a structural unit derived from the compound (a23) in which n is 1 or more in the formula (I).
It is preferable that the silyl ester-based copolymer (A) has a structural unit derived from such a compound (a23) because the viscosity is low and the handling is easy.
In such a compound (a23), m is preferably from 50 to 1,000, and n is preferably from 1 to 30.
As such a compound (a23), a commercially available compound can be used. For example, KF-2001 (side-chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent: 1,900 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. , KF-2004 (side-chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent 30,000 g / mol).
シリルエステル系共重合体（Ａ）における化合物（ａ２）に由来する構成単位の含有量は、防汚塗膜の乾湿交互条件での防汚性能や耐水性、下地付着性の観点から、全構成単位１００質量部に対して、好ましくは０．５〜５０質量部、より好ましくは１〜３０質量部、更に好ましくは１．５〜１５質量部である。 The content of the structural unit derived from the compound (a2) in the silyl ester-based copolymer (A) depends on the antifouling performance of the antifouling coating film under alternate dry and wet conditions, water resistance, and substrate adhesion. The amount is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 1.5 to 15 parts by mass with respect to 100 parts by mass.
〔（iii）その他の単量体（ａ３）に由来する構成単位〕
本発明において、シリルエステル系共重合体（Ａ）は、その他の単量体（ａ３）に由来する構成単位を有することが好ましい。
前記その他の単量体（ａ３）としては、前記単量体（ａ１）及び化合物（ａ２）と共重合可能な単量体を制限なく用いることができる。これらの中でも、その他の単量体（ａ３）は、エチレン性不飽和化合物であることが好ましい。
前記その他の単量体（ａ３）としては例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、３，５，５−トリメチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等のアルキル（メタ）アクリレート類又はアリール（メタ）アクリレート類；
２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、４−メトキシブチル（メタ）アクリレート、３−メトキシ−ｎ−プロピル（メタ）アクリレート、２−プロポキシエチル（メタ）アクリレート、２−ブトキシエチル（メタ）アクリレート、イソブトキシブチルジグリコール（メタ）アクリレート、２−フェノキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、ブトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート類又はアリーロキシアルキル（メタ）アクリレート類；
ヒドロキシメチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、及び２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；
グリシジル（メタ）アクリレート類；
後述する金属エステル基含有不飽和単量体（ａ３２）；
スチレン、α−メチルスチレン、酢酸ビニル、安息香酸ビニル、ビニルトルエン、アクリロニトリル、ビニルピリジン、ビニルピロリドン、塩化ビニルなどのビニル化合物等が挙げられる。これらの単量体は、１種単独で使用してもよく、２種以上を併用してもよい。[(Iii) Structural unit derived from other monomer (a3)]
In the present invention, the silyl ester copolymer (A) preferably has a structural unit derived from another monomer (a3).
As the other monomer (a3), a monomer copolymerizable with the monomer (a1) and the compound (a2) can be used without limitation. Among these, the other monomer (a3) is preferably an ethylenically unsaturated compound.
Examples of the other monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). A) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) Acrylate, alkyl (meth) acrylates such as benzyl (meth) acrylate or aryl (meth) acrylates;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 3-methoxy-n-propyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2- Butoxyethyl (meth) acrylate, isobutoxybutyldiglycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, Alkoxyalkyl (meth) acrylates such as phenoxy polyethylene glycol (meth) acrylate or aryloxyalkyl (meth) acrylates;
Hydroxy such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate Alkyl (meth) acrylates;
Glycidyl (meth) acrylates;
A metal ester group-containing unsaturated monomer (a32) described below;
Examples include vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl benzoate, vinyl toluene, acrylonitrile, vinyl pyridine, vinyl pyrrolidone, and vinyl chloride. These monomers may be used alone or in combination of two or more.
前記その他の単量体（ａ３）としては、下記式（II）で表される単量体（ａ３１）を含むことが好ましい。 The other monomer (a3) preferably includes a monomer (a31) represented by the following formula (II).
（式（II）中、Ｒ４は水素原子又はメチル基を示し、Ｒ５は水素原子又は一価の炭化水素基を示し、Ｒ６は二価の炭化水素基を示し、ｓは１〜６の整数を示す。）
(In the formula (II), R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrogen atom or a monovalent hydrocarbon group, R 6 represents a divalent hydrocarbon group, and s represents 1 to 6 Represents an integer.)
式（II）中、Ｒ４は水素原子又はメチル基を示し、重合容易性の観点から、水素原子であることが好ましく、形成される塗膜の耐水性の観点から、メチル基であることが好ましい。
式（II）中、Ｒ５は水素原子又は一価の炭化水素基を示し、防汚塗料組成物の安定性、及び形成される塗膜の物性の観点から、炭素数１〜６のアルキル基であることが好ましく、より好ましくは炭素数１〜４のアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基）であり、更に好ましくはメチル基である。
式（II）中、Ｒ６は二価の炭化水素基を示し、炭素数２〜６のアルキレン基であることが好ましく、より好ましくは炭素数２〜４のアルキレン基であり、更に好ましくはエチレン基又はプロピレン基である。
式（II）中、ｓは１〜６の整数を表し、好ましくは１〜３の整数、より好ましくは１である。ｓが１〜６の整数であると、シリルエステル系共重合体（Ａ）を含有する防汚塗料組成物により形成された塗膜に適度な親水性が付与され、耐水性に優れた防汚塗膜が得られるので好ましい。In the formula (II), R 4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of ease of polymerization, and is preferably a methyl group from the viewpoint of water resistance of a formed coating film. preferable.
In the formula (II), R 5 represents a hydrogen atom or a monovalent hydrocarbon group, and from the viewpoints of stability of the antifouling coating composition and physical properties of the formed coating film, an alkyl group having 1 to 6 carbon atoms. And more preferably an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, and a butyl group), and further preferably a methyl group.
In the formula (II), R 6 represents a divalent hydrocarbon group, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably ethylene. Or a propylene group.
In the formula (II), s represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1. When s is an integer of 1 to 6, appropriate hydrophilicity is imparted to the coating film formed by the antifouling coating composition containing the silyl ester copolymer (A), and the antifouling agent has excellent water resistance. It is preferable because a coating film can be obtained.
このような単量体（ａ３１）としては、前記のアルコキシアルキル（メタ）アクリレートが挙げられ、好ましくは２−メトキシエチル（メタ）アクリレートであり、より好ましくは２−メトキシエチルメタクリレートである。
シリルエステル系共重合体（Ａ）が、このような単量体（ａ３１）に由来する構成単位を有する場合、防汚塗膜の防汚性能や耐水性、硬度の観点から、単量体（ａ３１）に由来する構成単位の含有量は、シリルエステル系共重合体（Ａ）の全構成単位１００質量部に対して、好ましくは５〜４０質量部、より好ましくは１０〜３５質量部、更に好ましくは１５〜３０質量部である。Examples of such a monomer (a31) include the above-mentioned alkoxyalkyl (meth) acrylate, preferably 2-methoxyethyl (meth) acrylate, and more preferably 2-methoxyethyl methacrylate.
When the silyl ester-based copolymer (A) has a structural unit derived from such a monomer (a31), the monomer (a31) is preferred in view of the antifouling performance, water resistance, and hardness of the antifouling coating film. The content of the structural unit derived from a31) is preferably 5 to 40 parts by mass, more preferably 10 to 35 parts by mass, and more preferably 100 parts by mass of all the structural units of the silyl ester copolymer (A). Preferably it is 15 to 30 parts by mass.
本発明において、その他の単量体（ａ３）に由来する構成単位として、メチルメタクリレートに由来する構成単位を有することが好ましい。特に、シリルエステル系共重合体（Ａ）が、単量体（ａ３１）に由来する構成単位を有する場合、メチルメタクリレートに由来する構成単位を有することが好ましい。
メチルメタクリレートに由来する構成単位の含有量は、シリルエステル系共重合体（Ａ）の全構成単位１００質量部に対して、好ましくは０．５〜４０質量部、より好ましくは１〜３５質量部、更に好ましくは３〜３０質量部である。メチルメタクリレートに由来する構成単位の含有量が上記範囲内であると、塗膜強度に優れ、ひいては防汚性能に優れる防汚塗膜が得られる。In the present invention, it is preferable to have a structural unit derived from methyl methacrylate as a structural unit derived from the other monomer (a3). In particular, when the silyl ester-based copolymer (A) has a structural unit derived from the monomer (a31), it preferably has a structural unit derived from methyl methacrylate.
The content of the structural unit derived from methyl methacrylate is preferably 0.5 to 40 parts by mass, more preferably 1 to 35 parts by mass, based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). And more preferably 3 to 30 parts by mass. When the content of the structural unit derived from methyl methacrylate is within the above range, an antifouling coating film having excellent coating film strength and thus excellent antifouling performance can be obtained.
また、本発明において、その他の単量体（ａ３）として、不飽和脂肪酸、すなわち、エチレン性不飽和基と、カルボキシ基とを有する単量体の含有量が、少ないことが好ましい。具体的には、不飽和脂肪酸としては、メタクリル酸、アクリル酸が例示される。
これらの不飽和脂肪酸の含有量は、シリルエステル系共重合体（Ａ）の全構成単位１００質量部に対して、好ましくは１０質量部以下、より好ましくは５質量部以下、更に好ましくは１質量部以下、より更に好ましくは０質量部、すなわち含有しないことである。
不飽和脂肪酸の含有量が上記範囲内であると、塗装作業性及び貯蔵安定性に優れる傾向にある。In the present invention, as the other monomer (a3), the content of the unsaturated fatty acid, that is, the monomer having an ethylenically unsaturated group and a carboxy group is preferably small. Specifically, examples of unsaturated fatty acids include methacrylic acid and acrylic acid.
The content of these unsaturated fatty acids is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass, based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). Parts by mass, more preferably 0 parts by mass, that is, do not contain.
When the content of the unsaturated fatty acid is within the above range, coating workability and storage stability tend to be excellent.
シリルエステル系共重合体（Ａ）は、例えば、以下の手順で製造することができる。
撹拌機、コンデンサー、温度計、滴下装置、窒素導入管及び加熱冷却ジャケットを備えた反応容器に溶剤を仕込み、窒素気流下で８０〜９０℃の温度条件下に加熱撹拌を行う。同温度を保持しつつ滴下装置より、前記反応容器内に前記単量体（ａ１）、化合物（ａ２）、及び任意に単量体（ａ３）、並びに重合開始剤、連鎖移動剤、及び溶剤等の混合液を滴下し、重合反応を行うことによりシリルエステル系共重合体（Ａ）を得ることができる。The silyl ester copolymer (A) can be produced, for example, by the following procedure.
A solvent is charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating / cooling jacket, and is heated and stirred under a nitrogen stream at a temperature of 80 to 90 ° C. While maintaining the same temperature, the monomer (a1), the compound (a2), and optionally the monomer (a3), a polymerization initiator, a chain transfer agent, a solvent, etc. The silyl ester copolymer (A) can be obtained by dropping a mixed solution of the above and performing a polymerization reaction.
シリルエステル系共重合体（Ａ）の製造に用いることができる重合開始剤としては、特に制限はなく、各種ラジカル重合開始剤を用いることができる。具体的には、過酸化ベンゾイル、過酸化水素、クメンハイドロペルオキシド、ｔｅｒｔ−ブチルハイドロペルオキシド、過硫酸カリウム、過硫酸ナトリウム、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）〔ＡＭＢＮ〕、２，２’−アゾビス（２，４−ジメチルバレロニトリル）〔ＡＤＶＮ〕、及びｔｅｒｔ−ブチルパーオクトエート〔ＴＢＰＯ〕等が挙げられる。これらの重合開始剤は、１種単独で使用してもよく、２種以上を併用してもよい。なお、これらのラジカル重合開始剤は、反応開始時にのみ反応系内に添加してもよく、また反応開始時と反応途中との両方で反応系内に添加してもよい。
シリルエステル系共重合体（Ａ）の製造における重合開始剤の使用量は、前記各単量体等（反応原料）の合計１００質量部に対して０．１〜２０質量部が好ましい。The polymerization initiator that can be used for the production of the silyl ester copolymer (A) is not particularly limited, and various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2′-azobis (isobutyronitrile) [AIBN], 2,2 '-Azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], tert-butyl peroctoate [TBPO] and the like. These polymerization initiators may be used alone or in combination of two or more. These radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added to the reaction system both at the start of the reaction and during the reaction.
The amount of the polymerization initiator used in the production of the silyl ester copolymer (A) is preferably from 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the above-mentioned monomers and the like (reaction raw materials).
シリルエステル系共重合体（Ａ）の製造に用いることができる連鎖移動剤としては、特に制限はなく、例えば、α−メチルスチレンダイマー、チオグリコール酸、ジテルペン、ターピノーレン、γ−テルピネン；ｔｅｒｔ−ドデシルメルカプタン、及びｎ−ドデシルメルカプタン等のメルカプタン類；四塩化炭素、塩化メチレン、ブロモホルム、及びブロモトリクロロエタン等のハロゲン化物；イソプロパノール、グリセリン等の第２級アルコール；等が挙げられる。これらの連鎖移動剤は、１種単独で使用してもよく、２種以上を併用してもよい。
シリルエステル系共重合体（Ａ）の製造において連鎖移動剤を用いる場合、その使用量は、前記各単量体等（反応原料）の合計１００質量部に対して０．１〜５質量部が好ましい。The chain transfer agent that can be used in the production of the silyl ester copolymer (A) is not particularly limited, and includes, for example, α-methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, γ-terpinene; tert-dodecyl Mercaptans such as mercaptan and n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform and bromotrichloroethane; and secondary alcohols such as isopropanol and glycerin. These chain transfer agents may be used alone or in combination of two or more.
When a chain transfer agent is used in the production of the silyl ester-based copolymer (A), the amount of the chain transfer agent used is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of each monomer and the like (reaction raw materials). preferable.
シリルエステル系共重合体（Ａ）の製造に用いることができる溶剤としては、例えば、トルエン、キシレン、及びメシチレン等の芳香族系溶剤；プロパノール、ブタノール、プロピレングリコールモノメチルエーテル、ジ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；メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン等のケトン；酢酸エチル、酢酸ブチル等のエステル；水等が挙げられる。 Examples of the solvent that can be used for producing the silyl ester copolymer (A) include aromatic solvents such as toluene, xylene, and mesitylene; propanol, butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like. Alcohols; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as ethyl acetate and butyl acetate; and water.
シリルエステル系共重合体（Ａ）の重量平均分子量（Ｍｗ）は、塗料組成物の塗装作業性や防汚塗膜の強度などの観点から、３，０００〜７０，０００であることが好ましく、１０，０００〜５０，０００であることがより好ましい。
なお、シリルエステル系共重合体（Ａ）の重量平均分子量（Ｍｗ）は、実施例に記載の方法により測定したゲルパーミエーションクロマトグラフィー（ＧＰＣ）の値を指す。
また、シリルエステル系共重合体（Ａ）の多分散度（Ｍｗ／Ｍｎ）は特に限定されないが、均一な塗料組成物を得る観点から、好ましくは２０以下、より好ましくは１０以下である。The weight average molecular weight (Mw) of the silyl ester copolymer (A) is preferably from 3,000 to 70,000 from the viewpoint of coating workability of the coating composition, strength of the antifouling coating film, and the like, More preferably, it is 10,000 to 50,000.
The weight average molecular weight (Mw) of the silyl ester copolymer (A) refers to the value of gel permeation chromatography (GPC) measured by the method described in Examples.
The polydispersity (Mw / Mn) of the silyl ester-based copolymer (A) is not particularly limited, but is preferably 20 or less, more preferably 10 or less, from the viewpoint of obtaining a uniform coating composition.
本発明の防汚塗料組成物におけるシリルエステル系共重合体（Ａ）の含有量は、塗料組成物の固形分中、好ましくは５〜５０質量％、より好ましくは１０〜３５質量％、更に好ましくは１０〜２０質量％である。
なお、本発明において、防汚塗料組成物がシリルエステル系共重合体（Ａ）を２種以上含有する場合、上記の含有量はシリルエステル系共重合体（Ａ）の総含有量としての好ましい範囲であり、後述する各成分についても同様である。The content of the silyl ester copolymer (A) in the antifouling coating composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and still more preferably the solid content of the coating composition. Is 10 to 20% by mass.
In the present invention, when the antifouling coating composition contains two or more silyl ester copolymers (A), the above content is preferable as the total content of the silyl ester copolymer (A). And the same applies to each component described later.
＜任意成分＞
本発明の防汚塗料組成物は必要に応じて防汚剤（Ｂ）、モノカルボン酸化合物（Ｃ）、その他バインダー成分（Ｄ）、顔料（Ｅ）、有機溶剤（Ｆ）、タレ止め剤・沈降防止剤（Ｇ）、脱水剤（Ｈ）、可塑剤（Ｉ）等を含有していてもよい。<Optional components>
The antifouling paint composition of the present invention may contain, if necessary, an antifouling agent (B), a monocarboxylic acid compound (C), other binder components (D), a pigment (E), an organic solvent (F), an anti-sagging agent. It may contain an antisettling agent (G), a dehydrating agent (H), a plasticizer (I) and the like.
〔防汚剤（Ｂ）〕
本発明において、防汚塗膜に防汚性を付与する目的から、本発明の防汚塗料組成物は防汚剤（Ｂ）を含んでいてもよい。
防汚剤（Ｂ）としては、例えば、亜酸化銅、銅ピリチオン、亜鉛ピリチオン、チオシアン酸銅（ロダン銅）、銅（金属銅）、４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン（別名：ＤＣＯＩＴ）、４−ブロモ−２−（４−クロロフェニル）−５−（トリフルオロメチル）−１Ｈ−ピロール−３−カルボニトリル（別名：トラロピリル）、ボラン−窒素系塩基付加物（ピリジントリフェニルボラン、４−イソプロピルピリジンジフェニルメチルボラン等）、（＋／−）−４−［１−（２，３−ジメチルフェニル）エチル］−１Ｈ−イミダゾール（別名：メデトミジン）、Ｎ，Ｎ−ジメチル−Ｎ’−（３，４−ジクロロフェニル）尿素、Ｎ−（２，４，６−トリクロロフェニル）マレイミド、２−メチルチオ−４−ｔｅｒｔ−ブチルアミノ−６−シクロプロピルアミノ−１，３，５−トリアジン、２，４，５，６−テトラクロロイソフタロニトリル、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、クロロメチル−ｎ−オクチルジスルフィド、Ｎ’，Ｎ'−ジメチル−Ｎ−フェニル−（Ｎ−フルオロジクロロメチルチオ）スルファミド、テトラアルキルチウラムジスルフィド、ジンクジメチルジチオカーバメート、ジンクエチレンビスジチオカーバメート、２，３−ジクロロ−Ｎ−（２'，６'−ジエチルフェニル）マレイミド、及び２，３−ジクロロ−Ｎ−（２'−エチル−６'−メチルフェニル）マレイミドが挙げられる、これらを１種単独で使用してもよく、２種以上を併用してもよい。
前記防汚剤の中では、形成される防汚塗膜の特に動物種の水生生物への防汚性、及び耐水性を向上させる観点から、防汚剤（Ｂ）として、亜酸化銅（Ｂ１）を含むことが好ましい。[Antifouling agent (B)]
In the present invention, the antifouling coating composition of the present invention may contain an antifouling agent (B) for the purpose of imparting antifouling properties to the antifouling coating film.
Examples of the antifouling agent (B) include, for example, cuprous oxide, copper pyrithione, zinc pyrithione, copper thiocyanate (copper rhodan), copper (metallic copper), 4,5-dichloro-2-n-octyl-4-isothiazoline. -3-one (alias: DCOIT), 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (alias: tralopyryl), borane-nitrogen base addition (Pyridine triphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.), (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (alias: medetomidine), N, N-dimethyl-N '-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert -Butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, chloromethyl-n-octyl disulfide, N ', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro-N- (2', 6 '-Diethylphenyl) maleimide and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide. These may be used alone or in combination of two or more. May be.
Among the antifouling agents, cuprous oxide (B1) is used as the antifouling agent (B) from the viewpoint of improving the antifouling properties of the formed antifouling coating film, particularly against aquatic organisms of animal species, and water resistance. ) Is preferable.
前記亜酸化銅（Ｂ１）としては、数平均粒子径が１〜３０μｍ程度のものを含むことが好ましく、形成される防汚塗膜の防汚性と耐水性を向上させる観点から、２〜１０μｍのものを含むことがより好ましい。
前記亜酸化銅（Ｂ１）としては、グリセリン、ステアリン酸、ラウリン酸、ショ糖、レシチン、鉱物油等によって表面処理されているものが、貯蔵時の長期安定性の観点で好ましい。
このような亜酸化銅（Ｂ１）としては市販されているものを用いることができ、例えば、ＮＣ−３０１（エヌシー・テック（株）製、数平均粒子径：２〜４μｍ）、ＮＣ−８０３（エヌシー・テック（株）製、数平均粒子径：６〜１０μｍ）、Ｒｅｄ Ｃｏｐｐ９７Ｎ Ｐｒｅｍｉｕｍ（ＡＭＥＲＩＣＡＮ ＣＨＥＭＥＴ Ｃｏ．製）、Ｐｕｒｐｌｅ Ｃｏｐｐ（ＡＭＥＲＩＣＡＮ ＣＨＥＭＥＴ Ｃｏ.製）、ＬｏＬｏＴｉｎｔ９７（ＡＭＥＲＩＣＡＮ ＣＨＥＭＥＴ Ｃｏ.製）などが挙げられる。The cuprous oxide (B1) preferably contains one having a number average particle diameter of about 1 to 30 μm, and from the viewpoint of improving the antifouling property and water resistance of the formed antifouling coating film, from 2 to 10 μm It is more preferred to include
The cuprous oxide (B1) is preferably surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, or the like, from the viewpoint of long-term stability during storage.
As such cuprous oxide (B1), commercially available ones can be used. For example, NC-301 (manufactured by NC Tech, Inc., number average particle diameter: 2 to 4 μm), NC-803 ( N.Tech Co., Ltd., number average particle size: 6 to 10 μm), Red Cop97N Premium (manufactured by AMERICA CHEMET Co.), Purple Cop (manufactured by AMERICA CHEMET Co.), LoLoTint97 (manufactured by AMERICAN CHEMET Co.), and the like. Can be
塗料組成物が亜酸化銅（Ｂ１）を含有する場合、その含有量は、本発明における防汚塗料組成物の塗装作業性や防汚塗膜の防汚性能及び耐水性の観点から、防汚塗料組成物の固形分中、好ましくは２０〜８０質量％、より好ましくは４０〜７０質量％、更に好ましくは５０〜６５質量％である。 When the coating composition contains cuprous oxide (B1), the content is determined from the viewpoint of the coating workability of the antifouling coating composition and the antifouling performance and water resistance of the antifouling coating film in the present invention. In the solid content of the coating composition, it is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, and still more preferably 50 to 65% by mass.
前記防汚剤の中では、形成される防汚塗膜の特に水生ミクロ生物への防汚性を向上させる観点から銅ピリチオンを含むことも好ましい。
塗料組成物が銅ピリチオンを含有する場合、その含有量は、本発明における防汚塗料組成物の塗装作業性や防汚塗膜の防汚性能及び耐水性の観点から、防汚塗料組成物の固形分中、好ましくは０．５〜１０質量％、より好ましくは１〜５質量％である。Among the antifouling agents, it is also preferable to include copper pyrithione from the viewpoint of improving the antifouling property of the formed antifouling coating film, especially against aquatic micro-organisms.
When the coating composition contains copper pyrithione, the content is from the viewpoint of the coating workability of the antifouling coating composition and the antifouling performance and water resistance of the antifouling coating film of the present invention, In the solid content, it is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.
前記防汚剤としては、上記のほか、亜鉛ピリチオン、ＤＣＯＩＴ、トラロピリル、ボラン−窒素系塩基付加物（ピリジントリフェニルボラン、４−イソプロピルピリジンジフェニルメチルボラン等）、メデトミジンを含むことも防汚塗膜の防汚性が優れる点で好ましい。
また、特にフジツボ等の水生生物に対する防汚性の観点から、本発明の防汚塗料組成物は、防汚剤（Ｂ）として、メデトミジンを含有することも好ましい。メデトミジンは、（＋／−）−４−［１−（２，３−ジメチルフェニル）エチル］−１Ｈ−イミダゾールであり、下記式（IV）で表される。In addition to the above, the antifouling agent may further include zinc pyrithione, DCOIT, tralopyryl, borane-nitrogen base adduct (pyridine triphenylborane, 4-isopropylpyridine diphenylmethylborane, etc.), and medetomidine. Is preferred in that it has excellent antifouling properties.
From the viewpoint of antifouling properties against aquatic organisms such as barnacles, the antifouling coating composition of the present invention also preferably contains medetomidine as the antifouling agent (B). Medetomidine is (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole and is represented by the following formula (IV).
メデトミジンは、光学異性を有するが、その一方のみであっても、任意の比率の混合物であってもよい。
また、メデトミジンの一部又は全部として、イミダゾリウム塩や金属等への付加物を配合してもよく、又は防汚塗料組成物若しくは防汚塗膜中において、イミダゾリウム塩や金属等への付加物を形成していてもよい。Although medetomidine has optical isomerism, it may be only one of them or a mixture of any ratio.
Further, as part or all of medetomidine, an adduct to an imidazolium salt, a metal, or the like may be blended, or an addition to an imidazolium salt, a metal, or the like in an antifouling paint composition or an antifouling coating film. An object may be formed.
本発明の防汚塗料組成物がメデトミジンを含有する場合、その含有量は、長期間において高い防汚性を維持する観点から、防汚塗料組成物の固形分中、好ましくは０．０１〜１０質量％、より好ましくは０．０３〜５質量％、更に好ましくは０．０５〜３質量％である。 When the antifouling coating composition of the present invention contains medetomidine, its content is preferably from 0.01 to 10% in the solid content of the antifouling coating composition from the viewpoint of maintaining high antifouling properties over a long period of time. %, More preferably 0.03 to 5% by mass, even more preferably 0.05 to 3% by mass.
〔モノカルボン酸化合物（Ｃ）〕
本発明において、モノカルボン酸化合物（Ｃ）は、それが含有される防汚塗膜の水中での表面からの更新性を促進し、また、その防汚塗膜が防汚剤を含む場合には、防汚剤の水中への放出を促進することで防汚塗膜の防汚性を高めるものであり、更に防汚塗膜に適度な耐水性を付与する機能も有する。
モノカルボン酸化合物（Ｃ）としては、例えば、炭素原子数１０〜４０の飽和若しくは不飽和の脂肪族炭化水素にカルボキシ基が１つ置換した化合物、又は炭素原子数３〜４０の飽和若しくは不飽和の脂環式炭化水素にカルボキシ基が１つ置換した化合物、或いは脂肪族炭化水素又は脂環式炭化水素の変性物にカルボキシ基が１つ置換した化合物が好ましい。
これらの中でも、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、パラストリン酸、イソピマル酸、ピマル酸、トリメチルイソブテニルシクロヘキセンカルボン酸、バーサチック酸、ステアリン酸、ナフテン酸等が好ましい。
また、アビエチン酸、パラストリン酸、イソピマル酸等を主成分とするロジン類も好ましい。ロジン類としてはガムロジン、ウッドロジン、トール油ロジン等のロジン、水添ロジン、不均化ロジン、ロジン金属塩等のロジン誘導体、パインタールなどが挙げられる。
また、トリメチルイソブテニルシクロヘキセンカルボン酸としては、例えば、２，６−ジメチルオクタ−２，４，６−トリエンとメタクリル酸との反応生成物が挙げられ、これは１，２，３−トリメチル−５−（２−メチルプロパ−１−エン−１−イル）シクロヘキサ−３−エン−１−カルボン酸、及び１，４，５−トリメチル−２−（２−メチルプロパ−１−エン−１−イル）シクロヘキサ−３−エン−１−カルボン酸を主成分（８５質量％以上）とするものである。
モノカルボン酸化合物（Ｃ）は、１種単独で使用してもよく、２種以上を併用してもよい。[Monocarboxylic acid compound (C)]
In the present invention, the monocarboxylic acid compound (C) promotes the renewability of the antifouling coating film containing the same from the surface in water, and when the antifouling coating film contains an antifouling agent. Is to enhance the antifouling property of the antifouling coating by promoting the release of the antifouling agent into water, and further has a function of imparting appropriate water resistance to the antifouling coating.
As the monocarboxylic acid compound (C), for example, a compound in which a saturated or unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms is substituted with one carboxy group, or a saturated or unsaturated having 3 to 40 carbon atoms A compound in which a single carboxy group is substituted on the alicyclic hydrocarbon or a compound in which one modified carboxy group is substituted on a modified aliphatic hydrocarbon or alicyclic hydrocarbon is preferred.
Among these, abietic acid, neoabietic acid, dehydroabietic acid, parastolic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexenecarboxylic acid, versatic acid, stearic acid, naphthenic acid and the like are preferable.
Rosins containing abietic acid, parastolic acid, isopimaric acid and the like as main components are also preferable. Examples of the rosins include rosins such as gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salt, and pine tar.
Examples of trimethylisobutenylcyclohexenecarboxylic acid include, for example, a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which is 1,2,3-trimethyl- 5- (2-methylprop-1-en-1-yl) cyclohex-3-en-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl) It has cyclohex-3-ene-1-carboxylic acid as a main component (85% by mass or more).
The monocarboxylic acid compound (C) may be used alone or in combination of two or more.
本発明におけるモノカルボン酸化合物（Ｃ）は、その一部又は全てが塩を形成していてもよい。モノカルボン酸（Ｃ）の塩は、例えば亜鉛塩や銅塩などが挙げられ、防汚塗料組成物の調製前に予め塩が形成されていても、防汚塗料組成物の調製時に他の塗料成分との反応により形成されてもよい。 A part or all of the monocarboxylic acid compound (C) in the present invention may form a salt. Examples of the salt of the monocarboxylic acid (C) include a zinc salt and a copper salt. Even if the salt is formed in advance before the preparation of the antifouling paint composition, other paints may be used during the preparation of the antifouling paint composition. It may be formed by reaction with a component.
本発明の防汚塗料組成物がモノカルボン酸化合物（Ｃ）を含有する場合、その含有量は防汚塗料組成物の固形分中、好ましくは１〜５０質量％、より好ましくは２〜３０質量％、更に好ましくは２〜２０質量％、より更に好ましくは３〜１２質量％である。また、形成される塗膜の防汚性と物性が良好である観点からシリルエステル系共重合体（Ａ）の固形分１００質量部に対して、好ましくは１０〜１５０質量部、より好ましくは２０〜１００質量部、更に好ましくは２０〜５０質量部、より更に好ましくは２０〜３０質量部である。 When the antifouling paint composition of the present invention contains the monocarboxylic acid compound (C), the content is preferably 1 to 50% by mass, more preferably 2 to 30% by mass in the solid content of the antifouling paint composition. %, More preferably 2 to 20% by mass, even more preferably 3 to 12% by mass. In addition, from the viewpoint that the antifouling property and physical properties of the formed coating film are good, the content is preferably 10 to 150 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the solid content of the silyl ester copolymer (A). To 100 parts by mass, more preferably 20 to 50 parts by mass, even more preferably 20 to 30 parts by mass.
〔その他バインダー成分（Ｄ）〕
本発明において、防汚塗膜に静置防汚性や耐水性、耐クラック性や強度を付与する目的から、本発明の防汚塗料組成物は、前記シリルエステル系共重合体（Ａ）以外のその他バインダー成分（Ｄ）を含んでいてもよい。
その他バインダー成分（Ｄ）としては、例えば、アクリル系共重合体（アクリル樹脂）、ビニル系重合体、塩素化パラフィン、ｎ−パラフィン、テルペンフェノール、ポリビニルエチルエーテル等が挙げられ、これらを１種単独で使用してもよく、２種以上を併用してもよい。[Other binder components (D)]
In the present invention, the antifouling coating composition of the present invention is other than the silyl ester-based copolymer (A) for the purpose of imparting standing antifouling property, water resistance, crack resistance and strength to the antifouling coating film. And other binder components (D).
Other binder components (D) include, for example, acrylic copolymers (acrylic resins), vinyl polymers, chlorinated paraffins, n-paraffins, terpene phenols, polyvinyl ethyl ether, and the like. Or two or more of them may be used in combination.
前記アクリル系共重合体としては、前記その他の単量体（ａ３）と、任意に前記化合物（ａ２１）及び／又は（ａ２２）とを重合して得られるものを用いてよい。
前記アクリル系共重合体は、静置防汚性の観点から、前記単量体（ａ３１）や金属エステル基含有不飽和単量体（ａ３２）に由来する構成単位を含むことが好ましい。
前記「金属エステル基」とは、金属とカルボン酸とが結合することにより生成した基を指す。また、後述する「多価金属エステル基」又は「二価金属エステル基」とは、多価金属又は二価金属とカルボン酸とが結合することにより生成した基を指す。
金属エステル基としては多価金属エステル基が好ましく、下記式（Ｖ）で表される二価金属エステル基がより好ましい。As the acrylic copolymer, those obtained by polymerizing the other monomer (a3) and optionally the compound (a21) and / or (a22) may be used.
The acrylic copolymer preferably contains a structural unit derived from the monomer (a31) or the metal ester group-containing unsaturated monomer (a32) from the viewpoint of standing soil resistance.
The “metal ester group” refers to a group formed by bonding a metal and a carboxylic acid. Further, the “polyvalent metal ester group” or “divalent metal ester group” described later refers to a group formed by bonding a polyvalent metal or a divalent metal and a carboxylic acid.
As the metal ester group, a polyvalent metal ester group is preferable, and a divalent metal ester group represented by the following formula (V) is more preferable.
（式（Ｖ）中、Ｍは金属を示し、＊は結合位置を示す。）
(In the formula (V), M represents a metal, and * represents a bonding position.)
金属エステル基を構成する金属としては、例えば、マグネシウム、カルシウム、ネオジム、チタン、ジルコニウム、鉄、ルテニウム、コバルト、ニッケル、銅、亜鉛、及びアルミニウム等が挙げられる。
式（Ｖ）中、Ｍは二価の金属であり、上述した金属の中から、二価金属を適宜選択して用いることができる。これらの中でも、Ｍがニッケル、銅、及び亜鉛等の第１０〜１２族の金属であることが好ましく、銅及び亜鉛よりなる群から選択されることがより好ましく、亜鉛が更に好ましい。
このような単量体（ａ３２）としては、例えばジ（メタ）アクリル酸亜鉛、ジ（メタ）アクリル酸銅、アクリル酸（メタクリル酸）亜鉛、アクリル酸（メタクリル酸）銅、ジ（３−アクリロイルオキシプロピオン酸）亜鉛、ジ（３−アクリロイルオキシプロピオン酸）銅、（メタ）アクリル酸（ナフテン酸）亜鉛、（メタ）アクリル酸（ナフテン酸）銅、等が挙げられる。Examples of the metal constituting the metal ester group include magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, and aluminum.
In the formula (V), M is a divalent metal, and a divalent metal can be appropriately selected and used from the above-described metals. Among these, M is preferably a metal of Groups 10 to 12 such as nickel, copper, and zinc, more preferably selected from the group consisting of copper and zinc, and zinc is even more preferable.
Examples of such a monomer (a32) include zinc di (meth) acrylate, copper di (meth) acrylate, zinc acrylate (methacrylic acid), copper acrylate (methacrylic acid), and di (3-acryloyl). Zinc oxypropionate, copper di (3-acryloyloxypropionate), zinc (meth) acrylate (naphthenate), copper (meth) acrylate (naphthenate), and the like.
その他バインダー成分（Ｄ）としては市販品を用いてもよく、例えば、三菱レイヨン（株）製「ダイヤナールＢＲ−１０６」（アクリル系重合体）、東ソー（株）製「トヨパラックス Ａ−４０／Ａ−５０／Ａ−７０／Ａ−１４５／Ａ−１５０」等（塩素化パラフィン）を挙げることができる。 As the other binder component (D), commercially available products may be used. For example, "Dianal BR-106" (acrylic polymer) manufactured by Mitsubishi Rayon Co., Ltd., and "Toyoparax A-40 / A" manufactured by Tosoh Corporation. -50 / A-70 / A-145 / A-150 "(chlorinated paraffin).
本発明におけるその他バインダー成分（Ｄ）としては、上記の他に、例えば国際公開第２０１４／０１０７０２号に記載のような、２以上の酸基を含有する重合体（ｄ１）（以下、「酸基含有重合体（ｄ１）」ともいう。）と前記モノカルボン酸化合物（Ｃ）と金属化合物とを反応させることによって得られる重合体が挙げられる。
このような酸基含有重合体（ｄ１）としては、ポリエステル系重合体（ｄ１１）やアクリル系重合体（ｄ１２）が挙げられ、好ましくはポリエステル系重合体（ｄ１１）である。
このようなポリエステル系重合体（ｄ１１）としては、固形分酸価が５０〜２５０ｍｇＫＯＨ／ｇのものが好ましく、８０〜２００ｍｇＫＯＨ／ｇのものがより好ましい。
このようなポリエステル系重合体（ｄ１１）は１以上の多価のアルコールと１以上の多価カルボン酸及び／又はその無水物との反応により得られ、任意の種類を任意の量で用いることができ、その組み合わせにより酸価や粘度を調整できる。
このようなポリエステル系重合体（ｄ１１）としては、例えば、三価以上のアルコール（ｄ１１１）と、二塩基酸及び／又はその無水物（ｄ１１２）と、二価のアルコール（ｄ１１３）とを反応させた後、更に脂環式二塩基酸及び／又はその無水物（ｄ１１４）を反応させて得られるものが好ましい。
このようなポリエステル系重合体（ｄ１１）と反応させるモノカルボン酸化合物（Ｃ）としては前述のようなものを用いることができ、中でもロジン類を用いることが好ましく、金属化合物としては、例えば酸化亜鉛や亜酸化銅などの金属酸化物を用いることができ、中でも酸化亜鉛を用いることが好ましい。As the other binder component (D) in the invention, in addition to the above, for example, a polymer (d1) containing two or more acid groups (hereinafter referred to as “acid group”) described in WO 2014/010702. Polymer (d1) "), the monocarboxylic acid compound (C), and a metal compound.
Examples of such an acid group-containing polymer (d1) include a polyester polymer (d11) and an acrylic polymer (d12), and preferably a polyester polymer (d11).
As such a polyester polymer (d11), those having a solid content acid value of 50 to 250 mgKOH / g are preferable, and those having an acid value of 80 to 200 mgKOH / g are more preferable.
Such a polyester polymer (d11) is obtained by reacting one or more polyhydric alcohols with one or more polyhydric carboxylic acids and / or anhydrides, and any kind may be used in any amount. The acid value and the viscosity can be adjusted by the combination.
As such a polyester polymer (d11), for example, a trihydric or higher alcohol (d111), a dibasic acid and / or its anhydride (d112), and a dihydric alcohol (d113) are reacted. After that, those obtained by further reacting an alicyclic dibasic acid and / or an anhydride thereof (d114) are preferable.
As the monocarboxylic acid compound (C) to be reacted with such a polyester-based polymer (d11), those described above can be used. Among them, rosins are preferable, and as the metal compound, for example, zinc oxide And a metal oxide such as cuprous oxide, and among them, zinc oxide is preferable.
〔顔料（Ｅ）〕
本発明において、塗膜への着色や下地の隠ぺいを目的として、また、適度な塗膜強度に調整することを目的として、本発明の防汚塗料組成物は顔料（Ｅ）を含んでいてもよい。
顔料（Ｅ）としては、例えば、タルク、マイカ、クレー、カリ長石、酸化亜鉛、炭酸カルシウム、カオリン、アルミナホワイト、ホワイトカーボン、水酸化アルミニウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、硫酸カルシウム、硫化亜鉛等の体質顔料や、弁柄（赤色酸化鉄）、チタン白（酸化チタン）、黄色酸化鉄、カーボンブラック、ナフトールレッド、フタロシアニンブルー等が挙げられ、中でもタルク、酸化亜鉛を含むことが好ましい。これらの顔料は、１種単独で使用してもよく、２種以上を併用してもよい。
本発明の防汚塗料組成物が顔料（Ｅ）を含有する場合、その含有量は、形成される防汚塗膜に求められる隠ぺい性や、塗料組成物の塗布形態等に応じた所望の粘度によって好ましい量が決定されるが、それぞれの塗料組成物の固形分中、１〜５０質量％となる量が好ましい。[Pigment (E)]
In the present invention, the antifouling coating composition of the present invention may contain the pigment (E) for the purpose of coloring the coating film or hiding the base, and for the purpose of adjusting the coating film strength to an appropriate level. Good.
Examples of the pigment (E) include talc, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and zinc sulfide. Extenders, red iron oxide (red iron oxide), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, phthalocyanine blue, and the like. Among them, talc and zinc oxide are preferable. These pigments may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains the pigment (E), the content is determined by the desired viscosity according to the concealing property required for the antifouling coating film to be formed and the application form of the coating composition. The preferred amount is determined depending on the amount, but the amount is preferably 1 to 50% by mass in the solid content of each coating composition.
〔有機溶剤（Ｆ）〕
本発明において、塗料組成物の粘度を低く保ち、スプレー霧化性を向上させることを目的として、防汚塗料組成物が有機溶剤（Ｆ）を含有してもよい。
有機溶剤（Ｆ）としては、芳香族炭化水素系、脂肪族炭化水素系、脂環族炭化水素系、ケトン系、エステル系、アルコール系の有機溶剤を用いることができ、好ましくは芳香族炭化水素系の有機溶剤である。
芳香族炭化水素系の有機溶剤としては、例えば、トルエン、キシレン、スチレン、メシチレン等が挙げられる。
脂肪族炭化水素系の有機溶剤としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン等が挙げられる。
脂環族炭化水素系の有機溶剤としては、例えば、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等が挙げられる。
ケトン系の有機溶剤としては、例えば、アセチルアセトン、アセトン、メチルエチルケトン、メチルイソブチルケトン、炭酸ジメチル等が挙げられる。
エステル系の有機溶剤としては、例えば、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。
アルコール系の有機溶剤としては、例えば、イソプロパノール、ｎ−ブタノール、プロピレングリコールモノメチルエーテル等が挙げられる。
有機溶剤（Ｆ）は、１種単独で使用してもよく、２種以上を併用してもよい。
本発明の防汚塗料組成物が有機溶剤（Ｆ）を含有する場合、塗料組成物の塗布形態等に応じた所望の粘度によって塗料組成物中の好ましい含有量が決定されるが、好ましくは０〜５０質量％、より好ましくは１０〜４０質量％、更に好ましくは２０〜３５質量％である。含有量が多すぎる場合、タレ止め性の低下等の不具合が発生することがある。[Organic solvent (F)]
In the present invention, the antifouling coating composition may contain an organic solvent (F) for the purpose of keeping the viscosity of the coating composition low and improving spray atomization.
As the organic solvent (F), aromatic hydrocarbon-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, ketone-based, ester-based, or alcohol-based organic solvents can be used, and aromatic hydrocarbons are preferred. It is a system organic solvent.
Examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, mesitylene and the like.
Examples of the aliphatic hydrocarbon-based organic solvent include pentane, hexane, heptane, octane and the like.
Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, ethylcyclohexane and the like.
Examples of the ketone-based organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate.
Examples of the ester-based organic solvent include propylene glycol monomethyl ether acetate and the like.
Examples of the alcohol-based organic solvent include isopropanol, n-butanol, propylene glycol monomethyl ether and the like.
The organic solvent (F) may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains an organic solvent (F), the desired content in the coating composition is determined by the desired viscosity according to the coating form of the coating composition and the like. -50 mass%, more preferably 10-40 mass%, even more preferably 20-35 mass%. If the content is too large, problems such as a decrease in anti-sagging properties may occur.
＜タレ止め剤・沈降防止剤（Ｇ）＞
本発明において、防汚塗料組成物の粘度を調整することを目的として、防汚塗料組成物はタレ止め剤・沈降防止剤（Ｇ）を含有してもよい。
タレ止め剤・沈降防止剤（Ｇ）としては、有機粘土系ワックス（Ａｌ、Ｃａ、Ｚｎのステアレート塩、レシチン塩、アルキルスルホン酸塩等）、有機系ワックス（ポリエチレンワックス、酸化ポリエチレンワックス、アマイドワックス、ポリアマイドワックス、水添ヒマシ油ワックス等）、有機粘土系ワックスと有機系ワックスの混合物、合成微粉シリカ等が挙げられる。
タレ止め剤・沈降防止剤（Ｇ）としては市販品を用いてもよく、例えば、楠本化成（株）製の「ディスパロン３０５」、「ディスパロン４２００−２０」、「ディスパロンＡ６３０−２０Ｘ」、「ディスパロン６９００−２０Ｘ」、伊藤製油（株）製の「Ａ−Ｓ−Ａ Ｄ−１２０」等が挙げられる。タレ止め剤・沈降防止剤（Ｇ）は、１種単独で使用してもよく、２種以上を併用してもよい。
本発明の防汚塗料組成物がタレ止め剤・沈降防止剤（Ｇ）を含有する場合、その含有量は、防汚塗料組成物の固形分中、好ましくは０．０１〜１０質量％、より好ましくは０．１〜３質量％、更に好ましくは０．５〜２質量％である。<Anti-sagging agent / Anti-settling agent (G)>
In the present invention, for the purpose of adjusting the viscosity of the antifouling coating composition, the antifouling coating composition may contain an anti-sagging agent / anti-settling agent (G).
Examples of anti-sagging agents and anti-settling agents (G) include organoclay waxes (such as Al, Ca, and Zn stearate salts, lecithin salts, and alkyl sulfonate salts), and organic waxes (polyethylene wax, polyethylene oxide wax, and amide). Wax, polyamide wax, hydrogenated castor oil wax, etc.), a mixture of an organoclay wax and an organic wax, and synthetic finely divided silica.
A commercially available product may be used as the anti-sagging agent / anti-settling agent (G). For example, "DISPARON 305", "DISPARON 4200-20", "DISPARON A630-20X", "DISPARON" manufactured by Kusumoto Kasei Co., Ltd. 6900-20X "and" AS-AD-120 "manufactured by Ito Oil Co., Ltd. The anti-sagging agent / anti-settling agent (G) may be used alone or in combination of two or more.
When the antifouling paint composition of the present invention contains an anti-sagging agent / anti-settling agent (G), its content is preferably from 0.01 to 10% by mass in the solid content of the antifouling paint composition. Preferably it is 0.1 to 3% by mass, more preferably 0.5 to 2% by mass.
〔脱水剤（Ｈ）〕
本発明において、塗料組成物の貯蔵安定性を向上させることを目的として、防汚塗料組成物は脱水剤（Ｈ）を含有してもよい。
脱水剤（Ｈ）としては、例えば、アルコキシシラン、「モレキュラーシーブ」の一般名称で知られるゼオライト、多孔質アルミナ、オルトギ酸アルキルエステル等のオルトエステル、オルトホウ酸、イソシアネート等を挙げることができる。これらの中でも、入手容易性及び貯蔵安定性向上の観点から、アルコキシシランが好ましい。これらの脱水剤は、１種単独で使用してもよく、２種以上を併用してもよい。
発明の防汚塗料組成物が脱水剤（Ｈ）を含有する場合、その含有量は、塗料組成物の固形分中、好ましくは０．１〜１０質量％、より好ましくは０．２〜２質量％、更に好ましくは０．５〜１質量％である。脱水剤（Ｈ）の含有量が前記範囲内であると塗料組成物の貯蔵安定性を良好に保つことができる。[Dehydrating agent (H)]
In the present invention, the antifouling coating composition may contain a dehydrating agent (H) for the purpose of improving the storage stability of the coating composition.
Examples of the dehydrating agent (H) include alkoxysilane, zeolite known under the general name of "molecular sieve", porous alumina, orthoesters such as alkyl orthoformate, orthoboric acid, and isocyanate. Of these, alkoxysilanes are preferred from the viewpoints of easy availability and improved storage stability. These dehydrating agents may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains a dehydrating agent (H), its content is preferably 0.1 to 10% by mass, more preferably 0.2 to 2% by mass in the solid content of the coating composition. %, More preferably 0.5 to 1% by mass. If the content of the dehydrating agent (H) is within the above range, the storage stability of the coating composition can be kept good.
〔可塑剤（Ｉ）〕
本発明の防汚塗料組成物は、防汚塗膜に可塑性を付与することを目的として、可塑剤（Ｉ）を含んでいてもよい。
可塑剤（Ｉ）としては、例えば、トリクレジルホスフェート（ＴＣＰ）、ジオクチルフタレート（ＤＯＰ）、ジイソデシルフタレート（ＤＩＤＰ）等を挙げることができる。これらの可塑剤は、１種単独で使用してもよく、２種以上を併用してもよい。
本発明の防汚塗料組成物が可塑剤（Ｉ）を含有する場合、その含有量は塗料組成物の固形分中、好ましくは０．１〜１０質量％、より好ましくは０．５〜５質量％である。可塑剤（Ｉ）の含有量が前記範囲内であると、防汚塗膜の可塑性を良好に保つことができる。[Plasticizer (I)]
The antifouling coating composition of the present invention may contain a plasticizer (I) for the purpose of imparting plasticity to the antifouling coating film.
Examples of the plasticizer (I) include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), and the like. These plasticizers may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains a plasticizer (I), the content is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass in the solid content of the coating composition. %. When the content of the plasticizer (I) is within the above range, the plasticity of the antifouling coating film can be kept good.
［防汚塗料組成物の製造方法］
本発明の防汚塗料組成物はそれぞれ、公知の一般的な防汚塗料と同様の装置、手段等を用いて調製することができる。具体的には、シリルエステル系共重合体（Ａ）を調製した後、この重合体の溶液と必要に応じてその他の添加剤とを、一度に、又は順次に添加して、撹拌、混合して製造することができる。[Method for producing antifouling paint composition]
Each of the antifouling paint compositions of the present invention can be prepared using the same apparatus, means, and the like as known general antifouling paints. Specifically, after preparing the silyl ester-based copolymer (A), a solution of this polymer and other additives as needed are added at once or sequentially, followed by stirring and mixing. Can be manufactured.
［防汚塗膜、防汚塗膜付き基材及びその製造方法、防汚方法］
本発明の防汚塗膜は、前記防汚塗料組成物を乾燥させて得られる。
また、本発明の防汚方法は、上述した防汚塗膜を使用するものであり、種々の基材に対して、本発明の防汚塗料組成物を用いて防汚塗膜を設けることで、防汚する方法である。
防汚塗膜を形成する方法として、具体的には、例えば、本発明の防汚塗料組成物を塗膜や基材上に塗布した後、乾燥させることにより防汚塗膜を得ることができる。
本発明の塗料組成物を塗布する方法としては、刷毛、ローラー、及びスプレーを用いる方法等の公知の方法を挙げることができる。
前述の方法により塗布した防汚塗料組成物は、例えば、２５℃の条件下、好ましくは０．５〜１４日間程度、より好ましくは１〜７日間程度放置することにより乾燥し、塗膜を得ることができる。なお、防汚塗料組成物の乾燥にあたっては、加熱下で送風しながら行ってもよい。[Anti-fouling coating film, substrate with anti-fouling coating film, method for producing the same, and anti-fouling method]
The antifouling coating film of the present invention is obtained by drying the antifouling coating composition.
In addition, the antifouling method of the present invention uses the above-described antifouling coating film, and by providing an antifouling coating film to various substrates using the antifouling coating composition of the present invention. It is a method of antifouling.
As a method of forming the antifouling coating film, specifically, for example, after applying the antifouling coating composition of the present invention on a coating film or a substrate, the antifouling coating film can be obtained by drying. .
Examples of the method for applying the coating composition of the present invention include known methods such as a method using a brush, a roller, and a spray.
The antifouling coating composition applied by the method described above is dried, for example, by leaving it at 25 ° C., preferably for about 0.5 to 14 days, more preferably for about 1 to 7 days to obtain a coating film. be able to. The drying of the antifouling coating composition may be performed while blowing air under heating.
防汚塗膜の乾燥後の厚さは、防汚塗膜の更新速度や、使用される期間等に応じて任意に選択されるが、例えば３０〜１，０００μｍ程度が好ましい。この厚さの塗膜を製造する方法としては、塗料組成物を１回の塗布あたり、好ましくは１０〜３００μｍ、より好ましくは３０〜２００μｍの厚さで、１回〜複数回塗布する方法が挙げられる。 The thickness of the antifouling coating film after drying is arbitrarily selected depending on the renewal speed of the antifouling coating film, the period of use, and the like. Examples of a method for producing a coating film having this thickness include a method in which the coating composition is applied once to a plurality of times, preferably 10 to 300 μm, more preferably 30 to 200 μm per application. Can be
本発明の防汚塗料組成物付き基材は、前記防汚塗料組成物により形成された防汚塗膜で基材が被覆されており、前記防汚塗膜を基材上に有するものである。
本発明の防汚塗膜付き基材は、前記のような方法により基材上に前記防汚塗膜を形成することで製造することができる。
本発明の防汚塗膜付き基材の製造方法は特に限定されないが、例えば、本発明の防汚塗料組成物を基材に塗布又は含浸し、塗布体又は含浸体を得る工程（１）、及び前記塗布体又は含浸体を乾燥する工程（２）を有する製造方法により得ることができる。
前記工程（１）において、塗料組成物を基材に塗布する方法は、前述の塗布方法を採用することができる。また、含浸させる方法に特に制限はなく、含浸させるのに十分な量の塗料組成物中に基材を浸すことにより行うことができる。更に、前記塗布体又は含浸体を乾燥させる方法に特に制限はなく、防汚塗膜を製造する際の方法と同様の方法で乾燥させることができる。The substrate with an antifouling paint composition of the present invention has a substrate coated with an antifouling coating formed by the antifouling coating composition, and has the antifouling coating on the substrate. .
The substrate with an antifouling coating film of the present invention can be produced by forming the antifouling coating film on a substrate by the method as described above.
The method for producing the substrate with an antifouling coating film of the present invention is not particularly limited. For example, a step (1) of applying or impregnating a substrate with the antifouling coating composition of the present invention to obtain a coated body or an impregnated body. And a step of drying the coated body or the impregnated body (2).
In the step (1), the coating method described above can be adopted as a method of applying the coating composition to the substrate. The method of impregnation is not particularly limited, and the impregnation can be performed by immersing the base material in a sufficient amount of the coating composition for impregnation. Further, there is no particular limitation on the method of drying the coated body or the impregnated body, and the coating body or the impregnated body can be dried by the same method as that for producing the antifouling coating film.
また、本発明の防汚塗膜付き基材は、本発明の防汚塗料組成物を乾燥させてなる塗膜を形成する工程（１’）、及び前記塗膜を基材に貼付する工程（２’）を有する製造方法により得ることもできる。
工程（１’）において塗膜を形成する方法に特に制限はなく、防汚塗膜を製造する際の方法と同様の方法により製造することができる。
工程（２’）において塗膜を基材に貼付する方法に特に制限はなく、例えば、特開２０１３−１２９７２４号公報に記載の方法により貼付することができる。The substrate with an antifouling coating film of the present invention comprises a step (1 ′) of forming a coating film obtained by drying the antifouling coating composition of the present invention, and a step of attaching the coating film to the substrate ( 2 ').
There is no particular limitation on the method of forming the coating film in the step (1 ′), and the coating film can be produced by the same method as that for producing the antifouling coating film.
There is no particular limitation on the method of attaching the coating film to the substrate in step (2 ′), and for example, it can be applied by the method described in JP-A-2013-129724.
本発明の防汚塗料組成物は、船舶、漁業、海洋構造物等の広範な産業分野において、基材の防汚性を長期間にわたって維持するために利用することができる。そのような基材としては、例えば、船舶（コンテナ船、タンカー等の大型鋼鉄船、漁船、ＦＲＰ船、木船、ヨット等の船体外板、これらの新造船又は修繕船等）、漁業資材（ロープ、漁網、漁具、浮き子、ブイ等）、石油パイプライン、導水配管、循環水管、ダイバースーツ、水中メガネ、酸素ボンベ、水着、魚雷、火力・原子力発電所の給排水口等の水中構造物、海底ケーブル、海水利用機器類（海水ポンプ等）、メガフロート、湾岸道路、海底トンネル、港湾設備、及び運河・水路等における各種海洋土木工事用構造物等が挙げられる。これらの中でも、基材は、船舶、水中構造物、及び漁業資材よりなる群から選択されることが好ましく、船舶及び水中構造物よりなる群から選択されることがより好ましく、船舶であることが更に好ましい。
また、本発明の防汚塗料組成物を表面に形成する対象の基材は、防錆剤等のその他の処理剤により処理された面や、表面にすでにプライマー等の塗膜が形成されているものであってもよく、本発明の防汚塗料組成物が既に塗装されている面に上塗りするものでもよく、本発明に係る防汚塗膜が直接に接する塗膜の種類は特に限定されるものではない。The antifouling paint composition of the present invention can be used in a wide range of industrial fields such as ships, fisheries, and marine structures to maintain the antifouling property of a base material for a long period of time. Such base materials include, for example, ships (large steel boats such as container ships and tankers, fishing boats, FRP boats, wooden boats, boat hulls such as yachts, these newly built or repaired ships, etc.), fishing materials (ropes) , Fishing nets, fishing gear, floats, buoys, etc.), oil pipelines, water pipes, circulating water pipes, diver suits, underwater glasses, oxygen cylinders, swimwear, torpedoes, underwater structures such as water supply / drainage outlets for thermal and nuclear power plants, and the sea floor Examples include cables, seawater utilization equipment (seawater pumps and the like), megafloats, gulf roads, submarine tunnels, port facilities, and various structures for marine civil engineering work in canals and waterways. Among these, the substrate is preferably selected from the group consisting of ships, underwater structures, and fishing materials, more preferably selected from the group consisting of ships and underwater structures, and is preferably a ship. More preferred.
In addition, the substrate on which the antifouling coating composition of the present invention is formed on the surface, the surface treated with another treatment agent such as a rust preventive agent, or a coating film such as a primer is already formed on the surface. The antifouling coating composition according to the present invention may be applied to a surface already coated with the antifouling coating composition of the present invention. Not something.
以下、本発明を実施例により更に具体的に説明するが、本発明はかかる実施例により何ら制限されるものではない。以下では、特にその趣旨に反しない限り、「部」は質量部の意味である。
なお、実施例において用いる各成分の「固形分」とは、各成分に溶剤として含まれる揮発成分を除いた成分を指し、各成分を１０８℃の熱風乾燥機中で３時間乾燥させて得られたものを固形分としてみなす。Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. In the following, "part" means "part by mass" unless specifically contradicting the purpose.
The “solid content” of each component used in the examples refers to a component excluding a volatile component contained as a solvent in each component, and is obtained by drying each component in a hot air dryer at 108 ° C. for 3 hours. Are regarded as solids.
［シリルエステル系共重合体（Ａ）の製造］
＜製造例１：シリルエステル系共重合体溶液（Ａ−１）の製造＞
撹拌機、コンデンサー、温度計、滴下装置、窒素導入管、及び加熱冷却ジャケットを備えた反応容器にキシレン４３質量部、トリイソプロピルシリルメタクリレート１０質量部、ＦＭ−０７１１（ＪＮＣ（株）製、片末端メタクリレート変性オルガノポリシロキサン、平均分子量Ｍｎ＝１，０００）２質量部を仕込み、窒素気流下で８０±５℃の温度条件下にて加熱撹拌を行った。同温度を保持しつつ滴下装置より、前記反応容器内にトリイソプロピルシリルメタクリレート４０質量部、ＦＭ−０７１１（ＪＮＣ（株）製、片末端メタクリレート変性オルガノポリシロキサン、平均分子量Ｍｎ＝１，０００）８質量部、２−メトキシエチルメタクリレート２０質量部、メチルメタクリレート２０質量部、及び２，２'−アゾビスイソブチロニトリル１．１質量部からなる混合物を２時間かけて滴下した。その後、同温度で２時間撹拌を行った後、２，２'−アゾビスイソブチロニトリルを更に０．４質量部を加え、３時間かけて１０５℃まで昇温を行い、キシレン２４質量部を加えて、無色透明のシリルエステル系共重合体溶液（Ａ−１）を得た。
使用された単量体混合物の構成、及びシリルエステル系共重合体溶液（Ａ−１）の特性値を表１に示す。[Production of silyl ester copolymer (A)]
<Production Example 1: Production of silyl ester-based copolymer solution (A-1)>
43 parts by mass of xylene, 10 parts by mass of triisopropylsilyl methacrylate, FM-0711 (manufactured by JNC, one end) in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket. 2 parts by mass of methacrylate-modified organopolysiloxane, average molecular weight Mn = 1,000) were charged, and heated and stirred under a temperature of 80 ± 5 ° C. under a nitrogen stream. While maintaining the same temperature, 40 parts by mass of triisopropylsilyl methacrylate and FM-0711 (manufactured by JNC, methacrylate-modified organopolysiloxane at one end, average molecular weight Mn = 1,000) were introduced into the reaction vessel from the dropping device. A mixture consisting of 20 parts by mass of 2-methoxyethyl methacrylate, 20 parts by mass of methyl methacrylate, and 1.1 parts by mass of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. Then, after stirring at the same temperature for 2 hours, 0.4 parts by mass of 2,2′-azobisisobutyronitrile was further added, and the temperature was raised to 105 ° C. over 3 hours. Was added to obtain a colorless and transparent silyl ester copolymer solution (A-1).
Table 1 shows the constitution of the monomer mixture used and the characteristic values of the silyl ester-based copolymer solution (A-1).
＜製造例２〜１１：シリルエステル系共重合体溶液（Ａ−２）〜（Ａ−１１）の製造＞
製造例１において使用した単量体混合物の仕込み比及び滴下時に用いる重合開始剤の種類及び量を表１のように変更した以外は、製造例１と同様にして、シリルエステル系共重合体溶液（Ａ−２）〜（Ａ−１１）を調製した。
使用された単量体混合物の構成、並びに後述の方法により測定したシリルエステル系共重合体溶液（Ａ−２）〜（Ａ−１１）及びこれらに含まれる共重合体の特性値を表１に示す。<Production Examples 2 to 11: Production of Silyl Ester Copolymer Solutions (A-2) to (A-11)>
A silyl ester-based copolymer solution was prepared in the same manner as in Production Example 1, except that the charging ratio of the monomer mixture used in Production Example 1 and the type and amount of the polymerization initiator used for dropping were changed as shown in Table 1. (A-2) to (A-11) were prepared.
Table 1 shows the composition of the monomer mixture used, and the characteristic values of the silyl ester-based copolymer solutions (A-2) to (A-11) and the copolymers contained therein measured by the method described below. Show.
表１中の各成分は以下の通りである。
＊１ ＦＭ−０７１１：ＪＮＣ（株）製、片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１，０００
＊２ ＦＭ−０７２１：ＪＮＣ（株）製、片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝５，０００
＊３ ＦＭ−０７２５：ＪＮＣ（株）製、片末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１０，０００
＊４ ＦＭ−７７１１：ＪＮＣ（株）製、両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、平均分子量Ｍｎ＝１，０００
＊５ ＫＦ−２００１：信越化学工業（株）製、側鎖メルカプトアルキル変性オルガノポリシロキサン、官能基当量＝１，９００ｇ／ｍｏｌEach component in Table 1 is as follows.
* 1 FM-0711: methacryloyloxyalkyl-modified organopolysiloxane at one end, manufactured by JNC Corporation, average molecular weight Mn = 1,000
* 2 FM-0721: methacryloyloxyalkyl-modified organopolysiloxane at one end, manufactured by JNC Corporation, average molecular weight Mn = 5,000
* 3 FM-0725: methacryloyloxyalkyl-modified organopolysiloxane at one end, manufactured by JNC Corporation, average molecular weight Mn = 10,000
* 4 FM-7711: manufactured by JNC, methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 1,000
* 5 KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd., side-chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent = 1,900 g / mol
得られた重合体溶液（Ａ−１）〜（Ａ−１１）の粘度、それに含まれる重合体の数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）の測定方法は以下の通りである。
＜重合体溶液の粘度＞
重合体溶液の２５℃における粘度は、Ｅ型粘度計（東機産業（株）製）により測定した。
＜重合体の数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）の測定＞
重合体の数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）を下記条件でＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用いて測定した。
ＧＰＣ条件
装置：「ＨＬＣ−８１２０ＧＰＣ」（東ソー（株）製）
カラム：「ＳｕｐｅｒＨ２０００＋Ｈ４０００」（東ソー（株）製、６ｍｍ（内径）、各１５ｃｍ（長さ））
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：０．５００ｍｌ／ｍｉｎ
検出器：ＲＩ
カラム恒温槽温度：４０℃
標準物質：ポリスチレン
サンプル調製法：各製造例で調製された重合体溶液に少量の塩化カルシウムを加えて
脱水した後、メンブレムフィルターで濾過して得られた濾物をＧＰＣ測定サンプルとした。The methods for measuring the viscosities of the obtained polymer solutions (A-1) to (A-11) and the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer contained therein are as follows.
<Viscosity of polymer solution>
The viscosity of the polymer solution at 25 ° C. was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
<Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) of polymer>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer were measured using GPC (gel permeation chromatography) under the following conditions.
GPC conditions Apparatus: "HLC-8120GPC" (manufactured by Tosoh Corporation)
Column: "SuperH2000 + H4000" (Tosoh Corporation, 6 mm (inner diameter), each 15 cm (length))
Eluent: tetrahydrofuran (THF)
Flow rate: 0.500 ml / min
Detector: RI
Column bath temperature: 40 ° C
Standard substance: polystyrene Sample preparation method: A small amount of calcium chloride was added to the polymer solution prepared in each of the production examples to dehydrate it, and then filtered through a membrane filter to obtain a filtrate, which was used as a GPC measurement sample.
［実施例１〜１６、並びに比較例１及び２：防汚塗料組成物及び防汚塗膜の製造］
・配合成分
防汚塗料組成物に用いた各配合成分を表２に示す。[Examples 1 to 16 and Comparative Examples 1 and 2: Production of antifouling paint composition and antifouling coating film]
Table 2 shows the components used in the antifouling paint composition.
＜防汚塗料組成物の製造＞
表３に記載された配合（質量部）で、各配合成分を混合撹拌し防汚塗料組成物を得た。なお、表３に記載された各成分の配合量は、有姿での配合量を示している。例えば、実施例１において、脂肪酸アマイドの有姿での（全体としての）配合量は２．０質量部であり、固形分２０％であるので、そのうちの有効成分である脂肪酸アマイド自身の配合量は、０．４質量部である。<Manufacture of antifouling paint composition>
The components described in Table 3 (parts by mass) were mixed and stirred to obtain an antifouling paint composition. In addition, the compounding amount of each component described in Table 3 shows the compounding amount in a tangible state. For example, in Example 1, the amount (as a whole) of the fatty acid amide in the form (as a whole) is 2.0 parts by mass and the solid content is 20%. Is 0.4 parts by mass.
＜防汚塗膜の製造＞
サンドブラスト処理鋼板（縦３００ｍｍ×横１００ｍｍ×厚み３．２ｍｍ）に、エポキシ樹脂系防錆塗料組成物（エポキシＡＣ塗料、商品名「バンノー５００」、中国塗料（株）製）をその乾燥膜厚が１５０μｍとなるように塗布した後、ビニル樹脂系バインダー塗料組成物（商品名「シルバックスＳＱ―Ｋ」、中国塗料（株）製）をその乾燥膜厚が４０μｍとなるように塗布した。続いて、前記表３に示す防汚塗料組成物をその乾燥膜厚が２００μｍとなるように１回塗布し、２５℃条件下で７日間乾燥させて、防汚塗膜付き試験板を作製した。なお、前記３回の塗装は１日当たり１回のペースで行った。
防汚試験板は、後述の各評価に用いるため塗料組成物ごとに複数作製した。<Manufacture of antifouling coating film>
An epoxy resin-based rust-preventive paint composition (Epoxy AC paint, trade name "Banno 500", made by Chugoku Paint Co., Ltd.) is applied to a sandblasted steel sheet (300 mm in length x 100 mm in width x 3.2 mm in thickness). After coating to a thickness of 150 μm, a vinyl resin-based binder coating composition (trade name “SILVACS SQ-K”, manufactured by China Paint Co., Ltd.) was applied to a dry film thickness of 40 μm. Subsequently, the antifouling coating composition shown in Table 3 was applied once so that the dry film thickness became 200 μm, and dried at 25 ° C. for 7 days to prepare a test plate with an antifouling coating film. . The three coatings were performed once a day.
A plurality of antifouling test plates were prepared for each coating composition for use in each evaluation described below.
＜評価＞
〔半没水浸漬防汚性〕
前述のように作製した防汚塗膜付き試験板を、広島湾内にてその試験面が海水面と垂直になるように、また、試験面と海水面の交差する喫水線が試験面の中央付近となるよう、更に、波による上下動により上下する喫水線が試験面の上端と下端の範囲内に収まるよう設置して浸漬した。本条件での浸漬を開始してから６ヶ月後に、防汚塗膜上のスライム状のものも含めた海生生物の付着面積を測定し、下記（防汚性評価基準）に従って、防汚塗膜の半没水浸漬防汚性を評価した。その結果を表３に示す。
（防汚性評価基準）
５：試験面において海生生物が付着した面積が全体の１％未満
４：同上面積が全体の１％以上１０％未満
３：同上面積が全体の１０％以上３０％未満
２：同上面積が全体の３０％以上７０％未満
１：同上面積が全体の７０％以上<Evaluation>
(Semi-immersion antifouling property)
The test plate with the antifouling coating film prepared as described above, so that the test surface is perpendicular to the sea surface in Hiroshima Bay, and the draft line where the test surface and the sea surface intersect is near the center of the test surface In addition, the immersion line was immersed in such a manner that the waterline moving up and down due to the vertical movement of the wave was within the range of the upper end and the lower end of the test surface. Six months after the start of immersion under these conditions, the area of marine organisms including slime on the antifouling coating film was measured, and the antifouling coating was performed according to the following (fouling resistance evaluation criteria). The membrane was evaluated for anti-fouling properties by immersion in submerged water. Table 3 shows the results.
(Stain resistance evaluation standard)
5: The area where marine organisms adhered on the test surface is less than 1% of the whole 4: The same area is 1% or more and less than 10% of the whole 3: The same area is 10% or more and less than 30% of the whole 2: The same area is the whole 30% or more and less than 70% of 1: The same area is 70% or more of the whole
〔長期動的浸漬後防汚性〕
前述のように作製した防汚塗膜付き試験板を、表面速度が１０ノットとなる速度で回転水流を生じさせた円筒の内壁に固定して、３０℃の海水中で６ヵ月動的浸漬環境下においた。この処理により、防汚塗膜が高温下での水流に曝されることで、促進的に長期水流に曝された場合に近い塗膜状態になる。その後、東京湾内にて水面下約２メートルの位置で試験面が水面に対して垂直となる向きで浸漬した。本条件での浸漬を開始してから６ヶ月後に防汚塗膜上の海生生物の付着面積を測定し、下記（防汚性評価基準）に従って、防汚塗膜の長期動的浸漬後防汚性を評価した。その結果を表３に示す。
（防汚性評価基準）
５：試験面において海生生物が付着した面積が全体の１％未満
４：同上面積が全体の１％以上１０％未満
３：同上面積が全体の１０％以上３０％未満
２：同上面積が全体の３０％以上７０％未満
１：同上面積が全体の７０％以上(Stain resistance after long-term dynamic immersion)
The test plate with the antifouling coating film prepared as described above was fixed to the inner wall of a cylinder where a rotating water flow was generated at a surface speed of 10 knots, and was dynamically immersed in seawater at 30 ° C. for 6 months. I put it down. By this treatment, the antifouling coating film is exposed to a water stream at a high temperature, so that the antifouling coating film becomes a coating state close to that when exposed to a long-term water flow. Thereafter, the test surface was immersed in Tokyo Bay at a position about 2 meters below the water surface in such a direction that the test surface was perpendicular to the water surface. Six months after the start of immersion under these conditions, the area of marine organisms on the antifouling coating film was measured, and after a long-term dynamic immersion of the antifouling coating film according to the following (fouling resistance evaluation criteria). The fouling was evaluated. Table 3 shows the results.
(Stain resistance evaluation standard)
5: The area where marine organisms adhered on the test surface is less than 1% of the whole 4: The same area is 1% or more and less than 10% of the whole 3: The same area is 10% or more and less than 30% of the whole 2: The same area is the whole 30% or more and less than 70% of 1: The same area is 70% or more of the whole
〔上塗り付着性〕
前述のように作製した防汚塗膜付き試験板を、５０℃の海水中に３か月浸漬した後、同一の各防汚塗料組成物をその乾燥膜厚が２００μｍとなるように１回塗布し、２５℃条件下で７日間乾燥させた後、更に５０℃の海水中に１か月浸漬した。この積層塗膜をＪＩＳ Ｋ ５４００ ８．５．２（碁盤目テープ法）に準じて、試験板の上の塗膜を貫通して、素地に達する切り傷を間隔４ｍｍ、ます目の数２５の碁盤目状にカッターナイフで付け、この碁盤目の上にセロハン粘着テープをはりつけて引き剥がし、素地と塗膜又は積層塗膜間での剥離が発生したマス目の個数をもとに、以下の評価基準に従って評価した。結果を表３に示す。
（上塗り付着性評価基準）
５：剥離の発生したマス目がない
４：剥離の発生したマス目が１個〜３個
３：剥離の発生したマス目が４個〜１０個
２：剥離の発生したマス目が１１個〜２０個
１：剥離の発生したマス目が２１個以上(Overcoat adhesion)
After immersing the test plate with the antifouling coating film prepared as described above in seawater at 50 ° C. for 3 months, the same antifouling coating composition was applied once so that the dry film thickness became 200 μm. Then, after drying at 25 ° C. for 7 days, it was further immersed in seawater at 50 ° C. for one month. According to JIS K 5400 8.5.2 (cross-cut tape method), this laminated coating film cuts through the coating film on the test plate and reaches the substrate with a cut of 4 mm at intervals of 25 squares. A cellophane adhesive tape was stuck on the grid and peeled off, and the following evaluation was performed based on the number of squares where peeling occurred between the substrate and the coating film or the laminated coating film. It was evaluated according to the standard. Table 3 shows the results.
(Evaluation criteria for top coat adhesion)
5: There is no square where peeling occurred. 4: 1 to 3 squares where peeling occurred. 3: 4 to 10 squares where peeling occurred 2: 11 squares where peeling occurred. 20 pieces 1: 21 or more squares where peeling occurred
実施例及び比較例の結果より明らかなように、本発明によれば、半没水状態にある乾湿交互部での防汚性に優れ、長期に動的な水流下に置かれた後でも防汚性能を維持することができ、更に上塗り付着性にも優れる防汚塗膜、該塗膜を形成できる防汚塗料組成物、及びこれを基材上に有する防汚塗膜付き基材及びその製造方法、並びに該防汚塗膜を用いた防汚方法を提供することができる。
As is clear from the results of the examples and comparative examples, according to the present invention, the anti-fouling property in the dry-wet alternate portion in a semi-submerged state is excellent, and the anti-fouling property is maintained even after being placed under a dynamic water flow for a long time. Soil performance can be maintained, and an antifouling coating film further excellent in top coat adhesion, an antifouling coating composition capable of forming the coating film, a substrate with an antifouling coating film having the same on a substrate, and the same A production method and an antifouling method using the antifouling coating film can be provided.
Claims (16)
該シリルエステル系共重合体（Ａ）が、（ｉ）トリアルキルシリルメタクリレート（ａ１）に由来する構成単位、及び（ii）下記式（Ｉ）で表される化合物（ａ２）に由来する構成単位を有することを特徴とする、
防汚塗料組成物。
（式（Ｉ）中、Ｒ１、Ｒ２及びＲ３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）Containing a silyl ester-based copolymer (A),
The silyl ester copolymer (A) is (i) a structural unit derived from a trialkylsilyl methacrylate (a1), and (ii) a structural unit derived from a compound (a2) represented by the following formula (I). Characterized by having
Antifouling paint composition.
(In the formula (I), R 1 , R 2 and R 3 each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and m And n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)
（式（II）中、Ｒ４は水素原子又はメチル基を示し、Ｒ５は水素原子又は一価の炭化水素基を示し、Ｒ６は二価の炭化水素基を示し、ｓは１〜６の整数を示す。）The antifouling coating composition according to claim 4, wherein the other monomer (a3) contains a monomer (a31) represented by the following formula (II).
(In the formula (II), R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrogen atom or a monovalent hydrocarbon group, R 6 represents a divalent hydrocarbon group, and s represents 1 to 6 Represents an integer.)
前記塗布体又は含浸体を乾燥する工程（２）を有する、
防汚塗膜付き基材の製造方法。A step (1) of applying or impregnating a substrate with the antifouling paint composition according to any one of claims 1 to 12 to obtain an applied body or an impregnated body, and a step of drying the applied body or the impregnated body. Having (2),
A method for producing a substrate with an antifouling coating film.
An antifouling method using the antifouling coating film according to claim 13.
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| JP2021155728A (en) * | 2020-03-26 | 2021-10-07 | 中国塗料株式会社 | Antifouling coating composition |
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| US20230416565A1 (en) * | 2022-06-28 | 2023-12-28 | Nippon Paint Marine Coatings Co., Ltd. | Coating composition and coating film |
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| KR101035342B1 (en) * | 2002-07-10 | 2011-05-20 | 시그마칼론 서비시즈 비.브이. | Process for the preparation of polyorganosilylated carboxylate monomers or polymers thereof |
| TWI303654B (en) * | 2003-03-14 | 2008-12-01 | Mitsubishi Rayon Co | Antifouling coating composition |
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