JP2002012630A - Metal-containing resin composition and antifouling coating composition - Google Patents
Metal-containing resin composition and antifouling coating compositionInfo
- Publication number
- JP2002012630A JP2002012630A JP2000194584A JP2000194584A JP2002012630A JP 2002012630 A JP2002012630 A JP 2002012630A JP 2000194584 A JP2000194584 A JP 2000194584A JP 2000194584 A JP2000194584 A JP 2000194584A JP 2002012630 A JP2002012630 A JP 2002012630A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- parts
- resin composition
- antifouling
- containing resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属含有樹脂組成
物に関するものであり、より詳しくは、一般的な有機溶
剤に可溶な金属含有樹脂組成物である。この金属含有樹
脂組成物は、特に用途を限定するものではないが、好ま
しくは水中構築物、漁網、船底への海中生物および海藻
類の付着を防止する塗膜を形成させることができる防汚
性塗料組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-containing resin composition, and more particularly, to a metal-containing resin composition soluble in a general organic solvent. The metal-containing resin composition is not particularly limited in use, but is preferably an antifouling paint capable of forming a coating film for preventing the adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. It relates to a composition.
【０００２】[0002]
【従来の技術】従来、金属含有モノマーを重合して得ら
れる金属含有樹脂として、特開昭６３−５６５１０に記
載の崩壊型ビニル樹脂粒子がある。これは、生成重合体
を溶解しない溶剤中で、金属エステル型多官能重合性単
量体を重合させて得られる粒子であり、脱イオン水とア
ルコール系溶剤中に、金属エステル型多官能重合性単量
体とアクリル系重合性単量体と重合開始剤を加えて得ら
れる。2. Description of the Related Art Conventionally, as a metal-containing resin obtained by polymerizing a metal-containing monomer, there are collapsible vinyl resin particles described in JP-A-63-56510. These are particles obtained by polymerizing a metal ester-type polyfunctional polymerizable monomer in a solvent that does not dissolve the produced polymer, and in a deionized water and alcohol-based solvent, a metal ester-type polyfunctional polymerizable It is obtained by adding a monomer, an acrylic polymerizable monomer and a polymerization initiator.
【０００３】このようにして得られる金属含有樹脂は、
一般的な有機溶剤に不溶でり、組成によっては僅かに膨
潤する程度である。また、金属エステル型多官能性重合
性単量体自体は粉末であり、一般的なアクリルモノマー
と混合しにくく、一般的な有機溶剤中でアクリルモノマ
ーとの共重合は困難であった。[0003] The metal-containing resin thus obtained is
It is insoluble in general organic solvents and slightly swells depending on the composition. Further, the metal ester-type polyfunctional polymerizable monomer itself is a powder, is hardly mixed with a general acrylic monomer, and is difficult to copolymerize with an acrylic monomer in a general organic solvent.
【０００４】金属含有樹脂は種々の用途での使用が期待
されており、特に加水分解性付与を目的とした防汚塗料
が上げられ、一般的な有機溶剤に可溶な金属含有樹脂が
望まれている。[0004] Metal-containing resins are expected to be used in various applications. In particular, antifouling paints for imparting hydrolyzability are used, and metal-containing resins soluble in common organic solvents are desired. ing.
【０００５】防汚塗料については、船舶や海洋構造物の
浸水部分には、フジツボ、フナクイムシ、藻類など海中
生物の付着による腐食防止や船舶の航行速度低下の防止
を目的として塗装されている。また養殖用の網において
も、海中生物の付着による魚介類の致死防止等の目的で
同様な防汚塗料が塗装されている。[0005] Antifouling paints are applied to the inundated portions of ships and marine structures for the purpose of preventing corrosion due to the adhesion of marine organisms such as barnacles, barnacles and algae, and preventing the speed of navigation of ships from decreasing. A similar antifouling paint is also applied to aquaculture nets for the purpose of preventing lethality of fish and shellfish due to adhesion of marine organisms.
【０００６】このような防汚塗料から形成される塗膜
は、これに含まれるロジン系化合物や防汚成分が海中に
溶出することによって防汚効果を発揮するものである。
しかし、このような塗膜は、長時間にわたって海中に浸
漬されていると、徐々に溶出分が少なくなって不溶出分
が多くなり、それと共に塗膜面が凹凸状となり、そのた
め海中生物等の生物の付着防止効果が著しく低下する傾
向にある。また、有機錫を含有する塗料から形成される
塗膜は、塗膜表面が徐々に溶解して表面更新し、塗膜表
面に常に防汚成分が露出すること（自己研磨）により、
長期の防汚効果が発揮されるものであるが、有機錫の有
する強い毒性が魚介類に対して悪影響を及ぼすことが懸
念され、有機錫を含有しない塗料が検討されている。A coating film formed from such an antifouling paint exhibits an antifouling effect by dissolving a rosin-based compound and an antifouling component contained therein into the sea.
However, when such a coating film is immersed in the sea for a long time, the elution content gradually decreases and the non-elution content increases, and at the same time, the coating film surface becomes uneven, so that the marine organisms etc. The effect of preventing the adhesion of living organisms tends to be significantly reduced. In addition, the coating film formed from the organic tin-containing coating material gradually dissolves the coating film surface and renews the surface, so that the antifouling component is always exposed on the coating film surface (self-polishing).
Although a long-term antifouling effect is exhibited, there is a concern that the strong toxicity of organotin has a bad effect on fish and shellfish, and paints containing no organotin are being studied.
【０００７】例えば、有機珪素エステルが側鎖に導入さ
れた有機珪素含有共重合体を用いた防汚塗料や、錫以外
の金属を含有する共重合体を用いた防汚塗料が提案され
ており、中でも、錫以外の金属を含有する共重合体を用
いたものが、防汚効果が高く、かつ比較的低コストであ
る点から注目されている。For example, antifouling paints using an organic silicon-containing copolymer having an organic silicon ester introduced into a side chain and antifouling paints using a copolymer containing a metal other than tin have been proposed. Among them, those using a copolymer containing a metal other than tin have attracted attention because of their high antifouling effect and relatively low cost.
【０００８】また例えば、特開昭６１−３８３０号公報
では、金属含有樹脂が提案されているが、この樹脂を製
造するにあたりカルボキシル基を有する重合体もしくは
共重合体を金属塩溶液でイオン交換し、水性媒体で金属
塩を含む金属含有樹脂を沈殿生成している。かかる樹脂
は、イオン交換により水不溶性となた時点で沈殿するこ
とから、側鎖に金属塩となっていないカルボキシル基が
残存している。この様な樹脂を防汚塗料として使用した
場合、塗膜の耐水性の低下や亜酸化銅使用時の塗料のゲ
ル化、長期防汚性の低下という問題がある。For example, Japanese Patent Application Laid-Open No. 61-3830 proposes a metal-containing resin. In producing this resin, a polymer or copolymer having a carboxyl group is ion-exchanged with a metal salt solution. In addition, a metal-containing resin containing a metal salt is precipitated in an aqueous medium. Since such a resin precipitates when it becomes water-insoluble by ion exchange, a carboxyl group that is not a metal salt remains in the side chain. When such a resin is used as an antifouling paint, there are problems such as a decrease in water resistance of the coating film, gelation of the paint when cuprous oxide is used, and a decrease in long-term antifouling properties.
【０００９】特開昭６３−５６５１０号公報では、生成
重合体を溶解しない溶剤中で重合させて得られる金属エ
ステル結合を含む架橋点を有する平均粒子０．０１〜２
５０μｍの崩壊型ビニル樹脂粒子が提案されている。こ
の樹脂自体は一般的な有機溶剤に不溶であり、単体では
粒子であるがため膜形成能を持たず、防汚塗料用ビヒク
ルとして使用ができない。JP-A-63-56510 discloses an average particle having a cross-linking point containing a metal ester bond obtained by polymerizing a polymer in a solvent which does not dissolve the polymer.
50 μm collapsible vinyl resin particles have been proposed. The resin itself is insoluble in a general organic solvent, and since it is a single particle, it has no film-forming ability and cannot be used as a vehicle for antifouling paint.
【００１０】特開昭６２−５７４６４号公報や特開昭６
２−８４１６８号公報には、側鎖の末端部に特定の一価
有機酸の金属塩をもつ樹脂を用いた防汚塗料組成物が提
案されている。しかしながら、金属塩の対イオンとして
有機酸を含んでおり、海水中で金属が分解した場合に、
有機酸を放出するため加水分解効率が悪く、防汚塗膜の
加水分解安定性、長期の防汚性に問題がある。JP-A-62-257464 and JP-A-6-57464
JP-A-2-84168 proposes an antifouling coating composition using a resin having a metal salt of a specific monovalent organic acid at the terminal of a side chain. However, it contains an organic acid as a counter ion of the metal salt, and when the metal is decomposed in seawater,
Since the organic acid is released, the hydrolysis efficiency is poor, and there are problems in the hydrolysis stability of the antifouling coating film and the long-term antifouling property.
【００１１】[0011]
【発明が解決しようとする課題】金属含有樹脂について
は、無機金属化合物とカルボキシル基含有ラジカル重合
性単量体の反応物を重合して得られる重合体が一般的な
有機溶剤に不溶であり、また膜形成能を持たないため防
汚塗料用ビヒクルとして使用ができないという問題があ
った。防汚塗料として金属を含有する樹脂を使用した塗
料が種々提案されているが、特開昭６１−３８３０号公
報や特開平８−２０９００５のような高酸価樹脂に金属
塩を導入する方法は亜酸化銅を配合した塗料において貯
蔵安定性が悪く、長期防汚性も悪い。また、特開昭６２
−５７４６４号公報や特開昭６２−８４１６８号公報の
ような側鎖の末端部に特定の一価有機酸の金属塩をもつ
樹脂を使用した防汚塗膜は、加水分解性の安定性が悪
く、長期の防汚性が不十分であった。As for the metal-containing resin, a polymer obtained by polymerizing a reaction product of an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer is insoluble in a general organic solvent, There is also a problem that it cannot be used as a vehicle for antifouling paint because it has no film forming ability. Various paints using a metal-containing resin as an antifouling paint have been proposed, but the method of introducing a metal salt into a high acid value resin as disclosed in JP-A-61-3830 and JP-A-8-209005 has been proposed. Coatings containing cuprous oxide have poor storage stability and poor long-term antifouling properties. In addition, Japanese Unexamined Patent Publication
An antifouling coating film using a resin having a metal salt of a specific monovalent organic acid at the end of a side chain as disclosed in JP-A-57464 and JP-A-62-84168 has a hydrolytic stability. Poor, poor long-term antifouling properties.
【００１２】本発明の目的は、無機金属化合物とカルボ
キシル基含有ラジカル重合性単量体の反応物を重合して
得られる重合体が一般的な有機溶剤に可溶であり、得ら
れた重合体を用いた防汚塗料が、長期の加水分解性を維
持するとともに、海中での優れた防汚効果を長期間発揮
する自己研磨型防汚性塗料組成物を提供することにあ
る。An object of the present invention is to provide a polymer obtained by polymerizing a reaction product of an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer in a general organic solvent, An object of the present invention is to provide a self-polishing antifouling paint composition in which an antifouling paint using the composition maintains a long-term hydrolyzability and exhibits an excellent antifouling effect in the sea for a long time.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意検討した結果、特定の無機金属化合物
とカルボキシル基含有ラジカル重合性単量体の反応物
と、特定の有機溶剤と、特定量の水分とを構成成分とす
る金属含有モノマー混合物を重合して得られる金属含有
樹脂組成物、および、この金属含有樹脂組成物をビヒク
ル成分とする防汚塗料から形成される塗膜が、上記課題
を解決することを見い出し、本発明を完成させた。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a reaction product of a specific inorganic metal compound and a carboxyl group-containing radical polymerizable monomer and a specific organic solvent And a metal-containing resin composition obtained by polymerizing a metal-containing monomer mixture containing a specific amount of water as a component, and a coating film formed from an antifouling paint containing the metal-containing resin composition as a vehicle component However, they have found that the above-mentioned problems can be solved, and have completed the present invention.
【００１４】すなわち本発明は、無機金属化合物とカル
ボキシル基含有ラジカル重合性単量体の反応物と、少な
くともアルコール系溶剤を含む有機溶剤と、水とからな
り、水の含有量が０．０１〜３０質量％である金属含有
モノマー混合物（Ａ）と、その他のラジカル重合性不飽
和単量体（Ｂ）とを共重合して得られる金属含有樹脂組
成物である。That is, the present invention comprises a reaction product of an inorganic metal compound and a carboxyl group-containing radically polymerizable monomer, an organic solvent containing at least an alcohol solvent, and water, wherein the water content is 0.01 to 10%. It is a metal-containing resin composition obtained by copolymerizing a metal-containing monomer mixture (A) of 30% by mass and another radically polymerizable unsaturated monomer (B).
【００１５】さらに本発明は、この金属含有樹脂組成物
を用いたことを特徴とする防汚性塗料組成物である。こ
こで金属含有樹脂組成物を用いたとは、代表的には、防
汚性塗料のビヒクルとして含有する場合をいう。Further, the present invention is an antifouling paint composition using the metal-containing resin composition. Here, the use of the metal-containing resin composition typically means a case where the composition is contained as a vehicle of an antifouling paint.
【００１６】[0016]
【発明の実施の形態】本発明において、金属含有モノマ
ー混合物（Ａ）は、金属含有樹脂組成物の構成成分とし
て使用されるものであり、これを使用することによって
一般的な有機溶剤に可溶な金属含有重合体組成物を得る
ことができる。例えば、防汚塗料用ビヒクルとして使用
した場合は、得られる塗膜に高い自己研磨性を長期間付
与し、優れた防汚効果を発揮させる成分となる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a metal-containing monomer mixture (A) is used as a constituent of a metal-containing resin composition. A metal-containing polymer composition can be obtained. For example, when used as a vehicle for antifouling paints, it is a component that imparts high self-polishing properties to the resulting coating film for a long period of time and exhibits an excellent antifouling effect.
【００１７】金属含有モノマー混合物（Ａ）の製法は、
特に限定されず、例えば、金属塩の分解温度以下で、無
機金属化合物と、カルボキシル基含有ラジカル重合性単
量体と、少なくともアルコール系化合物を含む有機溶剤
と、水とを加熱、攪拌することによって得られる。The method for producing the metal-containing monomer mixture (A) is as follows:
There is no particular limitation, for example, by heating and stirring an inorganic metal compound, a carboxyl group-containing radically polymerizable monomer, an organic solvent containing at least an alcoholic compound, and water at a decomposition temperature of the metal salt or lower. can get.
【００１８】金属含有モノマー混合物（Ａ）において、
無機金属化合物は、有機溶剤可溶な金属含有モノマー混
合物の構成成分として使用されるものであり、カルボキ
シル基含有ラジカル重合性単量体と反応して金属塩を形
成するものである。無機金属化合物としては、例えば、
金属の酸化物、水酸化物、塩化物等が挙げられる。ただ
し、これらに限定されず、カルボキシル基と反応して金
属塩を形成するものであれば使用可能である。In the metal-containing monomer mixture (A),
The inorganic metal compound is used as a constituent component of a metal-containing monomer mixture soluble in an organic solvent, and reacts with a carboxyl group-containing radical polymerizable monomer to form a metal salt. As the inorganic metal compound, for example,
Metal oxides, hydroxides, chlorides and the like can be mentioned. However, the material is not limited to these, and any material can be used as long as it reacts with a carboxyl group to form a metal salt.
【００１９】金属の酸化物としては、酸化亜鉛、酸化ア
ルミニウム、酸化カルシウム、酸化第二銅、酸化マグネ
シウム、酸化マンガン等、金属の水酸化物としては、水
酸化亜鉛、水酸化アルミニウム、水酸化カルシウム、水
酸化第二銅、水酸化マグネシウム等、金属の塩化物とし
ては、塩化亜鉛、塩化アルミニウム、塩化カルシウム、
塩化第二銅、塩化マグネシウム、塩化マンガン等を挙げ
ることができる。Metal oxides include zinc oxide, aluminum oxide, calcium oxide, cupric oxide, magnesium oxide, and manganese oxide. Metal hydroxides include zinc hydroxide, aluminum hydroxide, and calcium hydroxide. , Cupric hydroxide, magnesium hydroxide, etc., as metal chlorides, zinc chloride, aluminum chloride, calcium chloride,
Examples thereof include cupric chloride, magnesium chloride, and manganese chloride.
【００２０】無機金属化合物の金属は、周期律表のＩ
ｂ、IIａ、IIｂ、IIIａ、IIIｂ、IVａ、IVｂ、Ｖａ、Ｖ
ｂ、VIｂ、VIIｂ、およびVIII属金属等から選ばれるも
のであり、必要に応じて２種以上を併用して使用しても
良い。Ｃｕを使用する場合は、アクリルモノマーとの共
重合性を上げる目的でＺｎを併用して使用することが好
ましい。樹脂の透明性に優れる傾向の点からは、Ｚｎ、
Ｍｇ、Ｃａ、Ａｌが好ましい。特に２価のＺｎ、Ｍｇ
は、樹脂製造時において粘度上昇を抑えることができる
ので好ましい。防汚塗料として使用する場合、また、Ｚ
ｎ、Ｍｇを用いると、得られる金属含有樹脂の透明性が
高いため塗装された塗膜の色調が美しくなる傾向にあ
り、また一般的に使用される有機溶剤への溶解性が高い
ため作業性が良好となる傾向にある。特にＺｎを使用す
る場合は、樹脂の耐水性が良好となり、より好ましい。The metal of the inorganic metal compound is represented by I in the periodic table.
b, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, V
b, VIb, VIIb, and metals belonging to Group VIII, and may be used in combination of two or more if necessary. When Cu is used, it is preferable to use Zn in combination for the purpose of increasing the copolymerizability with the acrylic monomer. From the viewpoint of excellent transparency of the resin, Zn,
Mg, Ca and Al are preferred. In particular, divalent Zn, Mg
Is preferred because the increase in viscosity can be suppressed during resin production. When used as an antifouling paint, Z
When n and Mg are used, the obtained metal-containing resin has high transparency, so that the color tone of the coated film tends to be beautiful. In addition, since it has high solubility in commonly used organic solvents, workability is high. Tends to be good. In particular, when Zn is used, the water resistance of the resin is improved, which is more preferable.
【００２１】金属含有モノマー混合物（Ａ）において、
カルボキシル基含有ラジカル重合性単量体としては、例
えば、メタクリル酸、アクリル酸、イタコン酸、（無
水）マレイン酸、イタコン酸モノアルキル（例えば、メ
チル、エチル、ブチル、２−エチルヘキシル等）、マレ
イン酸モノアルキル（例えば、メチル、エチル、ブチ
ル、２−エチルヘキシル等）等が挙げられ、これらの１
種あるいは２種以上の組み合わせを用いることができ
る。In the metal-containing monomer mixture (A),
Examples of the carboxyl group-containing radical polymerizable monomer include, for example, methacrylic acid, acrylic acid, itaconic acid, maleic acid (anhydride), monoalkyl itaconate (eg, methyl, ethyl, butyl, 2-ethylhexyl), maleic acid Monoalkyl (for example, methyl, ethyl, butyl, 2-ethylhexyl, etc.) and the like;
Species or a combination of two or more can be used.
【００２２】金属含有モノマー混合物（Ａ）において、
有機溶剤は、少なくともアルコール系化合物を含むもの
である。特に、金属塩化合物の溶解性の点から、エタノ
ール、イソプロパノール、ブタノール、プロピレングリ
コールモノメチルエーテル等のアルコール系溶剤が好ま
しい。アルコール系溶剤を含まない場合は、金属含有モ
ノマー混合物（Ａ）を製造中に溶液が流動性を失い固化
するため、一般的なアクリルモノマーと混合して重合す
ることができない。In the metal-containing monomer mixture (A),
The organic solvent contains at least an alcohol compound. In particular, alcohol solvents such as ethanol, isopropanol, butanol, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility of the metal salt compound. When the alcohol-based solvent is not contained, the solution loses fluidity and solidifies during the production of the metal-containing monomer mixture (A), so that it cannot be mixed with a general acrylic monomer and polymerized.
【００２３】有機溶剤として、必要に応じて、ペンタ
ン、ヘキサン、ヘプタンなどの脂肪族炭化水素系溶剤、
ベンゼン、トルエン、キシレンなどの芳香族炭化水素系
溶剤、酢酸エチル、酢酸ブチル、酢酸イソブチルなどの
エステル系溶剤、メチルエチルケトン、メチルイソブチ
ルケトン、シクロヘキサノンなどのケトン系溶剤をアル
コール系溶剤と混合して使用することができる。混合し
て使用する場合の有機溶剤中のアルコール系溶剤は５質
量％以上とすることが好ましい。５質量％以上とするこ
とにより反応生成物の溶剤への溶解性が向上して結晶物
が生成せず、貯蔵安定性が発現する。より好ましくは、
２５質量％以上である。As the organic solvent, if necessary, an aliphatic hydrocarbon solvent such as pentane, hexane and heptane;
Use aromatic hydrocarbon solvents such as benzene, toluene and xylene, ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone in combination with alcohol solvents. be able to. When mixed and used, the content of the alcohol solvent in the organic solvent is preferably 5% by mass or more. When the content is 5% by mass or more, the solubility of the reaction product in a solvent is improved, and a crystal is not generated, thereby exhibiting storage stability. More preferably,
It is at least 25% by mass.
【００２４】金属含有モノマ−混合物（Ａ）中に含まれ
る金属の含有量は、金属の種類によって異なるが、０．
１〜６０質量％が好ましい。６０質量％以下とすること
によって有機溶剤に可溶となり、アクリルモノマーと混
合して重合することが可能となる。また、０．１質量％
以上とすることによって金属含有樹脂組成物を重合する
際の作業性が良くなる。より好ましくは３〜２５質量％
である。The content of the metal contained in the metal-containing monomer mixture (A) varies depending on the type of the metal.
1-60 mass% is preferred. When the content is 60% by mass or less, the polymer becomes soluble in an organic solvent and can be mixed with an acrylic monomer for polymerization. 0.1% by mass
By doing so, workability when polymerizing the metal-containing resin composition is improved. More preferably 3 to 25% by mass
It is.
【００２５】金属含有モノマー混合物（Ａ）中の無機金
属化合物とカルボキシル基含有ラジカル重合性単量体の
比率は特に限定はしないが、カルボキシル基含有重合性
単量体１モルに対して、無機金属化合物の比率（モル
数）が０．６モル以下であることが好ましい。これが
０．６モル以下の場合は特に混合物の透明性には問題な
いが、０．６モルよりも多い場合は未反応の無機金属化
合物が混合物中に残りやすくなり、モノマーの透明性が
悪くなるため、これを用いて重合したワニスは僅かに濁
る。The ratio of the inorganic metal compound to the carboxyl group-containing radically polymerizable monomer in the metal-containing monomer mixture (A) is not particularly limited. It is preferable that the ratio (number of moles) of the compound is 0.6 mol or less. If this is 0.6 mol or less, there is no particular problem with the transparency of the mixture, but if it is more than 0.6 mol, unreacted inorganic metal compounds tend to remain in the mixture, resulting in poor monomer transparency. Therefore, the varnish polymerized by using this becomes slightly turbid.
【００２６】本発明の樹脂組成物を防汚塗料用ビヒクル
として使用する場合は、金属含有モノマー混合物（Ａ）
中の無機金属化合物とカルボキシル基含有ラジカル重合
性単量体の比率は、最適には０.５モル：１モル程度で
ある。カルボキシル基含有重合性単量体に対して、無機
金属化合物の比率（モル数）が多い場合は、塗膜性能に
与える問題は特に無い。逆に少ない場合は塗膜の耐水性
の低下や亜酸化銅を配合すると塗料の貯蔵安定性が低下
する。When the resin composition of the present invention is used as a vehicle for an antifouling paint, the metal-containing monomer mixture (A)
The ratio of the inorganic metal compound and the carboxyl group-containing radical polymerizable monomer therein is optimally about 0.5 mol: 1 mol. When the ratio (molar number) of the inorganic metal compound to the carboxyl group-containing polymerizable monomer is large, there is no particular problem on the coating film performance. On the other hand, when the amount is small, the water resistance of the coating film is lowered, and the storage stability of the coating material is reduced when cuprous oxide is added.
【００２７】金属含有モノマー混合物（Ａ）中に含有す
る水の量は無機金属化合物とカルボキシル基含有ラジカ
ル重合性単量体との反応によって生成される水を除外し
たもの（本発明において「水の量」はこの意味を示す）
であり、０．０１〜３０質量％の範囲である。水は反応
中に全て加えてもよく、反応中と反応終了後に再度加え
ても良い。The amount of water contained in the metal-containing monomer mixture (A) excludes water produced by the reaction between the inorganic metal compound and the carboxyl group-containing radically polymerizable monomer (in the present invention, “water”). "Amount" indicates this meaning)
And is in the range of 0.01 to 30% by mass. Water may be added during the reaction, or may be added again during the reaction and after the reaction.
【００２８】反応中に水を添加しない場合は、無機金属
化合物とカルボキシル基含有ラジカル重合性単量体の反
応中あるいは反応直後に溶液が流動性を失い固化する傾
向にあるので、アクリルモノマーと混合して重合するこ
とが困難になる。いったん固化すると、再度溶解させる
には多量の水および溶剤を必要とするため、アクリルモ
ノマーとの分離や固形分が下がることによる作業性の低
下により、好ましくない。反応中に水を加えることによ
って、反応溶液は流動性を失うことなく有機溶剤に溶解
した状態で得られ、アクリルモノマーと混合して共重合
することができる。If water is not added during the reaction, the solution tends to lose fluidity and solidify during or immediately after the reaction of the inorganic metal compound and the carboxyl group-containing radical polymerizable monomer. And it becomes difficult to polymerize. Once solidified, a large amount of water and a solvent are required for re-dissolving, which is not preferable because of the separation from the acrylic monomer and a decrease in workability due to a decrease in solid content. By adding water during the reaction, the reaction solution is obtained in a state of being dissolved in an organic solvent without losing fluidity, and can be mixed with an acrylic monomer and copolymerized.
【００２９】反応中に加える水の量については、０．０
１質量％以上加えることにより反応中に溶液が流動性を
失うことなく溶液状態で得られ、アクリルモノマーや一
般的な有機溶剤と混合して重合することが可能となる。
より好ましくは、０．２質量％以上である。The amount of water added during the reaction is 0.0
By adding 1% by mass or more, the solution can be obtained in a solution state without losing fluidity during the reaction, and can be polymerized by mixing with an acrylic monomer or a general organic solvent.
More preferably, it is 0.2% by mass or more.
【００３０】金属含有モノマー混合物（Ａ）中の水の量
を３０質量％以下とすることによって、一般的なアクリ
ルモノマーや有機溶剤等との溶解性が良好となり種々の
アクリルモノマーと共重合できるため好ましい。より好
ましくは、１５質量％以下である。By setting the amount of water in the metal-containing monomer mixture (A) to 30% by mass or less, the solubility in general acrylic monomers and organic solvents is improved, and copolymerization with various acrylic monomers is possible. preferable. More preferably, the content is 15% by mass or less.
【００３１】金属含有モノマー混合物（Ａ）中の水の含
有量を低下させる目的で、有機溶剤の使用量を増やすと
固形分が低下し、重合時の作業性が悪くなり好ましくな
い。金属含有モノマーのハイソリッド化による重合時の
作業性を良くするには、無機金属化合物の使用モル数に
対して０．０１〜５倍モルの範囲の水を含有することが
好ましく、金属含有モノマー混合物（Ａ）の固形分は２
５〜７０％の範囲であることが好ましい。特に、０．０
５〜３倍モルの範囲の水を含有することが好ましく、混
合物（Ａ）の固形分は４５〜６０％の範囲であることが
好ましい。When the amount of the organic solvent used is increased for the purpose of reducing the water content in the metal-containing monomer mixture (A), the solid content decreases, and the workability during polymerization deteriorates. In order to improve the workability at the time of polymerization by making the metal-containing monomer into a high solid, it is preferable that water is contained in the range of 0.01 to 5 moles per mole of the inorganic metal compound used, and the metal-containing monomer is used. The solid content of the mixture (A) is 2
Preferably, it is in the range of 5 to 70%. In particular, 0.0
It preferably contains water in a range of 5 to 3 moles, and the solid content of the mixture (A) is preferably in the range of 45 to 60%.
【００３２】本発明の金属含有樹脂組成物を防汚塗料と
して使用する場合、特に限定するものではないが、金属
含有モノマー混合物（Ａ）中の水分量を２０質量％以下
の範囲にすると樹脂中に含まれる水分量が少なくなり、
塗料化した際に粘度上昇の抑制や塗膜の加水分解性の低
下を抑えることができる。より好ましくは、１５質量％
以下の範囲である。When the metal-containing resin composition of the present invention is used as an antifouling paint, there is no particular limitation. However, when the water content in the metal-containing monomer mixture (A) is set to 20% by mass or less, Contains less water,
It is possible to suppress a rise in viscosity and a decrease in hydrolyzability of a coating film when a coating is formed. More preferably, 15% by mass
The range is as follows.
【００３３】本発明の金属含有樹脂組成物は、以上説明
した金属含有モノマー混合物（Ａ）と、これと共重合可
能なその他のラジカル重合性不飽和単量体（Ｂ）を共重
合させて得られるものである。The metal-containing resin composition of the present invention is obtained by copolymerizing the metal-containing monomer mixture (A) described above with another radically polymerizable unsaturated monomer (B) copolymerizable therewith. It is something that can be done.
【００３４】本発明の金属含有樹脂組成物を防汚塗料と
して使用する場合、その他のラジカル重合性不飽和単量
体（Ｂ）の使用量は、成分（Ａ）と成分（Ｂ）の合計１
００質量部を基準として、１６〜９７質量部であること
が好ましい。１６質量部以上とすることによって、得ら
れる防汚塗料の諸特性のバランスを整えることができる
傾向にあり、９７質量部以下とすることによって、形成
される塗膜に長期に亘る良好な加水分解性が付与され、
塗膜の耐クラック性や加水分解性とのバランスが良好と
なる傾向にある。より好ましくは４０〜９０質量部であ
り、特に好ましくは６０〜８５質量部である。When the metal-containing resin composition of the present invention is used as an antifouling paint, the amount of the other radically polymerizable unsaturated monomer (B) used is a total of 1 (A) and (B).
It is preferably 16 to 97 parts by mass based on 00 parts by mass. When the amount is 16 parts by mass or more, the balance of various properties of the obtained antifouling paint tends to be able to be adjusted, and when the amount is 97 parts by mass or less, good hydrolysis over a long period of time is applied to the formed coating film. Is given,
The balance between the crack resistance and the hydrolyzability of the coating film tends to be good. It is more preferably 40 to 90 parts by mass, particularly preferably 60 to 85 parts by mass.
【００３５】ラジカル重合性不飽和単量体（Ｂ）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、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、フ
ェノキシエチル（メタ）アクリレート、２−（２−エチ
ルヘキサオキシ）エチル（メタ）アクリレート、１−メ
チル−２−メトキシエチル（メタ）アクリレート、３−
メトキシブチル（メタ）アクリレート、３−メチル−３
−メトキシブチル（メタ）アクリレート、ｍ−メトキシ
フェニル（メタ）アクリレート、ｐ−メトキシフェニル
（メタ）アクリレート、ｏ−メトキシフェニルエチル
（メタ）アクリレート、ｍ−メトキシフェニルエチル
（メタ）アクリレート、ｐ−メトキシフェニルエチル
（メタ）アクリレート、ｎ−プロピル（メタ）アクリレ
ート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル
（メタ）アクリレート、ｉ−ブチル（メタ）アクリレー
ト、ｔ−ブチル（メタ）アクリレート、２−エチルヘキ
シル（メタ）アクリレート、ラウリル（メタ）アクリレ
ート、ステアリル（メタ）アクリレート、ベンジル（メ
タ）アクリレート、フェニル（メタ）アクリレート、イ
ソボルニル（メタ）アクリレート、シクロヘキシル（メ
タ）アクリレート、グリシジル（メタ）アクリレート等
の（メタ）アクリル酸エステル単量体；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、３−ヒドロキシプロピル（メ
タ）アクリレート、２−ヒドロキシブチル（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
等の水酸基含有単量体；２−ヒドロキシエチル（メタ）
アクリレートとエチレンオキサイド、プロピレンオキサ
イド、γ−ブチロラクトンまたはε−カプロラクトン等
との付加物；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）アクリレート等の
二量体または三量体；グリセロール（メタ）アクリレー
ト等の水酸基を複数有する単量体；ブチルアミノエチル
（メタ）アクリレート、（メタ）アクリルアミド等の第
一級および第二級アミノ基含有ビニル単量体；ジメチル
アミノエチル（メタ）アクリレート、ジエチルアミノエ
チル（メタ）アクリレート、ジメチルアミノプロピル
（メタ）アクリレート、ジメチルアミノブチル（メタ）
アクリレート、ジブチルアミノエチル（メタ）アクリレ
ート、ジメチルアミノエチル（メタ）アクリルアミド、
ジメチルアミノプロピル（メタ）アクリルアミド等の第
三級アミノ基含有ビニル単量体；ビニルピロリドン、ビ
ニルピリジン、ビニルカルバゾール等の複素環族系塩基
性単量体等；スチレン、ビニルトルエン、α−メチルス
チレン、（メタ）アクリロニトリル、酢酸ビニル、プロ
ピオン酸ビニル等のビニル系単量体を挙げることができ
る。なお、本発明において「（メタ）アクリル」とは、
「アクリルおよび／またはメタクリル」を意味する。Examples of the radical polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and phenoxy. Ethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-
Methoxybutyl (meth) acrylate, 3-methyl-3
-Methoxybutyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenylethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenyl Ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid ester monomers such as zir (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Hydroxyl-containing monomers such as acrylate and 4-hydroxybutyl (meth) acrylate; 2-hydroxyethyl (meth)
Adducts of acrylates with ethylene oxide, propylene oxide, γ-butyrolactone or ε-caprolactone; dimers or trimers of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; glycerol ( Monomers having a plurality of hydroxyl groups such as meth) acrylate; primary and secondary amino group-containing vinyl monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide; dimethylaminoethyl (meth) acrylate; Diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth)
Acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide,
Tertiary amino group-containing vinyl monomers such as dimethylaminopropyl (meth) acrylamide; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; styrene, vinyltoluene, α-methylstyrene And vinyl monomers such as (meth) acrylonitrile, vinyl acetate and vinyl propionate. In the present invention, “(meth) acryl” refers to
"Acrylic and / or methacrylic" is meant.
【００３６】本発明の金属含有樹脂組成物を防汚塗料と
して使用する場合、樹脂中の金属含有量は０．５〜２５
質量％の範囲であることが好ましい。０．５質量％以上
とすることによって、形成される塗膜の自己研磨性が発
現される傾向にあり、２５質量％以下とすることによっ
て、耐クラック性と加水分解性のバランスを向上させる
効果が顕著となり、長期の自己研磨性を維持し、防汚効
果が向上する傾向にある。より好ましくは、１〜１０質
量％である。When the metal-containing resin composition of the present invention is used as an antifouling paint, the metal content in the resin is 0.5 to 25.
It is preferably in the range of mass%. When the content is 0.5% by mass or more, the self-polishing property of the formed coating film tends to be exhibited, and when the content is 25% by mass or less, the effect of improving the balance between the crack resistance and the hydrolysis property is improved. Are prominent, and a long-term self-polishing property is maintained, and the antifouling effect tends to be improved. More preferably, it is 1 to 10% by mass.
【００３７】本発明の金属含有樹脂組成物を防汚塗料と
して使用する場合の樹脂の重量平均分子量は１０００〜
２００００が好ましい。加水分解性を発現する金属量を
樹脂中に組み込む場合、分子量２００００以下とするこ
とによって樹脂溶液粘度を下げて、ポリマー間での金属
架橋を低減し樹脂のゲル化を抑えることができ、分子量
１０００以上とすることによって、耐クラック性を発現
することができる傾向にある。より好ましくは、３００
０〜１００００である。When the metal-containing resin composition of the present invention is used as an antifouling paint, the resin has a weight average molecular weight of 1,000 to 1,000.
20000 is preferred. When the amount of a metal exhibiting hydrolyzability is incorporated into a resin, the viscosity of the resin solution can be reduced by setting the molecular weight to 20,000 or less, metal cross-linking between polymers can be reduced, and gelation of the resin can be suppressed. With the above, crack resistance tends to be exhibited. More preferably, 300
0 to 10,000.
【００３８】本発明のビヒクル成分として使用される共
重合体の製造方法は、特に限定されるものではないが、
例えば、上記した単量体を混合し、この混合物をラジカ
ル開始剤の存在下に６０〜１８０℃の反応温度で５〜１
４時間反応させることによって製造することができる。
また、共重合体中の金属含有量を多くする場合、ハイソ
リッド化や生産性の向上、特に重合時のカレットの生成
抑制のために連鎖移動剤を使用することができる。金属
含有重合性モノマーとの相溶性の点からは、メルカプタ
ン以外の連鎖移動剤が好ましく、スチレンダイマー等が
好ましい。重合方法は、有機溶剤中で行う溶液重合法の
ほかに、乳化重合法、懸濁重合法等が採用できるが、ト
ルエン、キシレン、メチルイソブチルケトン、酢酸ｎ−
ブチル等の一般の有機溶剤を用いる溶液重合方法を採用
するのが生産性、塗装性能の点で有利である。[0038] The method for producing the copolymer used as the vehicle component of the present invention is not particularly limited.
For example, the above-mentioned monomers are mixed, and the mixture is reacted at a reaction temperature of 60 to 180 ° C. and a reaction temperature of 5 to 1 in the presence of a radical initiator.
It can be produced by reacting for 4 hours.
When the metal content in the copolymer is increased, a chain transfer agent can be used to increase the solid content and improve the productivity, particularly to suppress the generation of cullet during polymerization. From the viewpoint of compatibility with the metal-containing polymerizable monomer, a chain transfer agent other than mercaptan is preferable, and styrene dimer and the like are preferable. As the polymerization method, in addition to a solution polymerization method performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method, and the like can be employed, but toluene, xylene, methyl isobutyl ketone, and n-acetic acid can be used.
Adopting a solution polymerization method using a general organic solvent such as butyl is advantageous in terms of productivity and coating performance.
【００３９】防汚性塗料組成物におけるビヒクルとして
の共重合体の割合は特に限定されないが、防汚性塗料組
成物中、樹脂成分として通常２０〜２５質量％（固形
分）の範囲で使用するのが好ましい。これは樹脂成分を
適度に含有させることによって、耐クラック性等の塗膜
性能が良好になり、過度に含有させないことによって、
良好な防汚能力を保持させるのに十分な量の防汚剤を防
汚性塗料組成物中に含有させることが容易になる傾向に
あるためである。The proportion of the copolymer as a vehicle in the antifouling coating composition is not particularly limited, but is usually used as a resin component in the range of 20 to 25% by mass (solid content) in the antifouling coating composition. Is preferred. This is because by appropriately containing the resin component, the coating performance such as crack resistance becomes good, and by not excessively containing,
This is because it tends to easily include an antifouling agent in an antifouling coating composition in an amount sufficient to maintain good antifouling ability.
【００４０】本発明の防汚性塗料組成物は、上記の金属
含有共重合体をビヒクル成分として含有することによっ
て、形成される塗膜に防汚性能を保持させることができ
るが、例えば、防汚剤を配合することによって、防汚性
能をさらに向上させることができる。The antifouling coating composition of the present invention can maintain the antifouling performance of the formed coating film by containing the above-mentioned metal-containing copolymer as a vehicle component. By adding a soiling agent, the antifouling performance can be further improved.
【００４１】防汚剤としては、要求性能に応じて適宜選
択して使用することができる。例えば、亜酸化銅、チオ
シアン銅、銅粉末等の銅系防汚剤を始め、鉛、亜鉛、ニ
ッケル等その他の金属化合物、ジフェニルアミン等のア
ミン誘導体、ニトリル化合物、ベンゾチアゾール系化合
物、マレイミド系化合物、ピリジン系化合物等が挙げら
れる。これらは、単独あるいは複数で使用することがで
きる。特に（社）日本造船工業会等によって、調査研究
の対象とされ選定されたものが好ましく、具体的には、
例えば、マンガニーズエチレンビスジチオカーバメイ
ト、ジンクジメチルジチオカーバメート、２−メチルチ
オ−４−ｔ−ブチルアミノ−６−シクロプロピルアミノ
−ｓ−トリアジン、２，４，５，６−テトラクロロイソ
フタロニトリル、Ｎ,Ｎ−ジメチルジクロロフェニル尿
素、ジンクエチレンビスジチオカーバメイ−ト、ロダン
銅、４，５−ジクロロ−２−ｎオクチル−３（２Ｈ）イ
ソチアゾロン、Ｎ−（フルオロジクロロメチルチオ）フ
タルイミド、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、２
−ピリジンチオール−１−オキシド亜鉛塩、テトラメチ
ルチウラムジサルファイド、Ｃｕ−１０％Ｎｉ個溶合
金、２,４,６−トリクロロフェニルマレイミド２,３，
５，６−テトラクロロ−４−（メチルスルホニル）ピリ
ジン、３−ヨード−２−プロピニールブチルカーバメイ
ート、ジヨードメチルパラトリスルホン、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、フェニル（ビスピリジル）ビスマスジクロライ
ド、２−（４−チアゾリル）−ベンツイミダゾール、ピ
リジン−トリフェニルボランを挙げることができる。The antifouling agent can be appropriately selected and used according to the required performance. For example, cuprous oxide, copper thiocyanate, copper antifouling agents such as copper powder, lead, zinc, other metal compounds such as nickel, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds, maleimide compounds, Pyridine compounds and the like can be mentioned. These can be used alone or in combination. In particular, those selected and selected by the Japan Shipbuilding Manufacturers Association and the like for research and investigation are preferred.
For example, manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N , N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, rhodan copper, 4,5-dichloro-2-noctyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'- Dimethyl-N'-phenyl-
(N-fluorodichloromethylthio) sulfamide, 2
Pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid alloy, 2,4,6-trichlorophenylmaleimide 2,3
5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatrisulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, phenyl (bispyridyl) bismuth Examples thereof include dichloride, 2- (4-thiazolyl) -benzimidazole, and pyridine-triphenylborane.
【００４２】本発明の防汚性塗料組成物には、その他、
塗膜表面に潤滑性を付与し、生物の付着を防止する目的
でジメチルポリシロキサン、シリコーンオイル等のシリ
コン化合物やフッ化炭素等の含フッ素化合物等も配合す
ることができる。さらに、体質顔料、着色顔料、可塑
剤、各種塗料用添加剤、その他の樹脂等を必要に応じて
配合することができる。The antifouling coating composition of the present invention further comprises:
Silicon compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbon can also be added for the purpose of imparting lubricity to the surface of the coating film and preventing the adhesion of organisms. Further, extenders, coloring pigments, plasticizers, various paint additives, other resins, and the like can be blended as required.
【００４３】本発明の防汚性塗料組成物を用いて塗膜を
形成するには、上記した防汚性塗料組成物を、船舶、各
種漁網、港湾施設、オイルフェンス、橋梁、海底基地等
の水中構造物等の基材表面に直接に、もしくは基材にウ
オッシュプライマー、塩化ゴム系、エポキシ系等のプラ
イマー、中塗り塗料等を塗布した塗膜の上に刷毛塗り、
吹き付け塗り、ローラー塗り、沈漬塗り等の手段で塗布
する。塗布量は、一般的には乾燥塗膜として５０〜４０
０μｍの厚さになるような量である。塗膜の乾燥は一般
的には室温で行われるが、加熱乾燥を行っても差し支え
ない。In order to form a coating film using the antifouling paint composition of the present invention, the above antifouling paint composition is applied to ships, various fishing nets, port facilities, oil fences, bridges, submarine bases and the like. Brush coating directly on the surface of a base material such as underwater structures, or on a coating film obtained by applying a wash primer, a chlorinated rubber type, an epoxy type primer, an intermediate coating, etc.
It is applied by means such as spray coating, roller coating, and immersion coating. The coating amount is generally 50 to 40 as a dry coating film.
The amount is such that the thickness becomes 0 μm. The coating film is generally dried at room temperature, but may be dried by heating.
【００４４】[0044]
【実施例】以下、本発明を実施例および比較例によりさ
らに詳しく説明するが、本発明はこれらの例によって何
ら限定されるものではない。なお、例中の部は質量部を
表す。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the part in an example represents a mass part.
【００４５】［製造例Ｍ１］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）８５．４部および酸
化亜鉛４０．７部を仕込み、撹拌しながら７５℃に昇温
した。続いて、滴下ロートからメタクリル酸４３．１
部、アクリル酸３６．１部、水５部からなる混合物を３
時間で等速滴下した。滴下終了後反応溶液は乳白色状態
から透明となった。さらに２時間撹拌した後ＰＧＭを３
６部添加して透明な金属含有モノマー混合物Ｍ１を得
た。固形分は４４．８％であった。[Production Example M1] 85.4 parts of PGM (propylene glycol methyl ether) and 40.7 parts of zinc oxide were charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred. The temperature was raised to 75 ° C. Subsequently, methacrylic acid 43.1 was added from the dropping funnel.
Parts of a mixture consisting of 36.1 parts of acrylic acid and 5 parts of water.
The solution was dropped at a constant speed over time. After completion of the dropwise addition, the reaction solution became transparent from a milky white state. After stirring for an additional 2 hours,
6 parts were added to obtain a transparent metal-containing monomer mixture M1. The solids content was 44.8%.
【００４６】［製造例Ｍ２］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにｎＢｕＯＨ
（ｎ−ブタノール）２４．３部、キシレン６１．１部お
よび酸化亜鉛４０．７部を仕込み、撹拌しながら７５℃
に昇温した。続いて、滴下ロートからメタクリル酸４
３．１部、アクリル酸３６．１部、水５部からなる混合
物を３時間で等速滴下した。滴下終了後反応溶液は乳白
色状態から透明となった。さらに２時間撹拌した後キシ
レンを３６部添加して透明な金属含有モノマー混合物Ｍ
２を得た。固形分は４４．９％であった。[Production Example M2] nBuOH was placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer.
(N-Butanol) 24.3 parts, 61.1 parts of xylene and 40.7 parts of zinc oxide were charged and stirred at 75 ° C.
The temperature rose. Subsequently, methacrylic acid 4 was added from the dropping funnel.
A mixture consisting of 3.1 parts, 36.1 parts of acrylic acid, and 5 parts of water was dropped at a constant speed in 3 hours. After completion of the dropwise addition, the reaction solution became transparent from a milky white state. After stirring for an additional 2 hours, 36 parts of xylene was added and a transparent metal-containing monomer mixture M was added.
2 was obtained. The solids content was 44.9%.
【００４７】［製造例Ｍ３］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）８５．４部および酸
化亜鉛４６．８部を仕込み、撹拌しながら７５℃に昇温
した。続いて、滴下ロートからメタクリル酸４６．１
部、アクリル酸３６．１部、水５部からなる混合物を３
時間で等速滴下した。滴下終了後反応溶液は乳白色状態
から半透明となった。さらに４時間撹拌した後ＰＧＭを
４３．５部添加して僅かに濁った金属含有モノマー混合
物Ｍ３を得た。固形分は４４．９％であった。[Production Example M3] 85.4 parts of PGM (propylene glycol methyl ether) and 46.8 parts of zinc oxide were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and stirred. The temperature was raised to 75 ° C. Subsequently, methacrylic acid 46.1 was added from the dropping funnel.
Parts of a mixture consisting of 36.1 parts of acrylic acid and 5 parts of water.
The solution was dropped at a constant speed over time. After the completion of the dropwise addition, the reaction solution became translucent from a milky white state. After further stirring for 4 hours, 43.5 parts of PGM was added to obtain a slightly turbid metal-containing monomer mixture M3. The solids content was 44.9%.
【００４８】［製造例Ｍ４］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）７０部、水１５．４
部および酸化亜鉛４０．７部を仕込み、撹拌しながら７
５℃に昇温した。続いて、滴下ロートからメタクリル酸
４３．１部、アクリル酸３６．１部、水２０．６部から
なる混合物を３時間で等速滴下した。滴下終了後反応溶
液は乳白色状態から透明となった。さらに２時間撹拌し
た後ＰＧＭを２０．４部添加して透明な金属含有モノマ
ー混合物Ｍ４を得た。固形分は４４．２％であった。[Production Example M4] A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 70 parts of PGM (propylene glycol methyl ether) and 15.4 parts of water.
Parts and 40.7 parts of zinc oxide, 7
The temperature was raised to 5 ° C. Subsequently, a mixture composed of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 20.6 parts of water was dropped at a constant rate over 3 hours from the dropping funnel. After completion of the dropwise addition, the reaction solution became transparent from a milky white state. After further stirring for 2 hours, 20.4 parts of PGM was added to obtain a transparent metal-containing monomer mixture M4. The solids content was 44.2%.
【００４９】［製造例Ｍ５］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）８５．４部および酸
価マグネシウム２０．２部を仕込み、撹拌しながら７５
℃に昇温した。続いて、滴下ロートからメタクリル酸４
３．１部、アクリル酸３６．１部、水５部からなる混合
物を３時間で等速滴下した。滴下終了後反応溶液は乳白
色状態から透明となった。さらに２時間撹拌した後ＰＧ
Ｍを１１部添加して透明な金属含有モノマー混合物Ｍ５
を得た。固形分は４４．６％であった。Production Example M5 85.4 parts of PGM (propylene glycol methyl ether) and 20.2 parts of an acid value magnesium were charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred. While 75
The temperature was raised to ° C. Subsequently, methacrylic acid 4 was added from the dropping funnel.
A mixture consisting of 3.1 parts, 36.1 parts of acrylic acid, and 5 parts of water was dropped at a constant speed in 3 hours. After completion of the dropwise addition, the reaction solution became transparent from a milky white state. After stirring for another 2 hours
M is added to 11 parts of a transparent metal-containing monomer mixture M5.
I got The solids content was 44.6%.
【００５０】［製造例Ｍ６］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）８５．４部および酸
価亜鉛４０．５部、酸化第二銅０．２部を仕込み、撹拌
しながら７５℃に昇温した。続いて、滴下ロートからメ
タクリル酸４３．１部、アクリル酸３６．１部、水５部
からなる混合物を３時間で等速滴下した。滴下終了後反
応溶液は緑色となった。さらに２時間撹拌した後ＰＧＭ
を１１部添加して透明な金属含有モノマー混合物Ｍ６を
得た。固形分は４４．９％であった。Production Example M6 85.4 parts of PGM (propylene glycol methyl ether), 40.5 parts of acid value zinc, and cupric oxide were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer. 0.2 part was charged, and the temperature was raised to 75 ° C. while stirring. Subsequently, a mixture consisting of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was dropped at a constant speed over 3 hours from the dropping funnel. After completion of the dropwise addition, the reaction solution turned green. After stirring for another 2 hours, PGM
Was added to obtain a transparent metal-containing monomer mixture M6. The solids content was 44.9%.
【００５１】［実施例１］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
５７部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１部、エチルアクリレート６６．２
部、２−メトキシエチルアクリレート５．４部、製造例
Ｍ１記載の金属含有モノマー混合物５２部、キシレン１
０部、連鎖移動剤（日本油脂社製ノフマーＭＳＤ）１
部、ＡＩＢＮ２．５部、ＡＭＢＮ７部からなるからなる
透明な混合物を６時間で等速滴下した。滴下終了後にｔ
−ブチルパーオクトエート０．５部とキシレン７部を３
０分で滴下し、さらに１時間３０分撹拌した後キシレン
を４．４部添加して、加熱残分４５．６％、ガードナー
粘度−Ｙを有する不溶解物のない淡黄色透明な金属含有
樹脂組成物Ｐ１を得た。Example 1 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 1 part of methyl methacrylate and 66.2 of ethyl acrylate were added from the dropping funnel.
Part, 5.4 parts of 2-methoxyethyl acrylate, 52 parts of the metal-containing monomer mixture described in Production Example M1, xylene 1
0 parts, chain transfer agent (NOFMER MSD manufactured by NOF Corporation) 1
, 2.5 parts of AIBN and 7 parts of AMBN, were dropped at a constant rate over 6 hours. After completion of dropping, t
0.5 parts of butyl peroctoate and 7 parts of xylene in 3 parts
After 0 minutes, the mixture was stirred for 1 hour and 30 minutes, and then 4.4 parts of xylene was added. The residue was heated at 45.6% and had a Gardner viscosity-Y. Composition P1 was obtained.
【００５２】［実施例２］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
６０部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１０部、エチルアクリレート６２．
６部、２−メトキシエチルアクリレート５．４部、製造
例Ｍ１記載の金属含有モノマー混合物４０部、キシレン
１０部、連鎖移動剤（日本油脂社製ノフマーＭＳＤ）１
部、ＡＩＢＮ２．５部、ＡＭＢＮ５．５部からなるから
なる透明な混合物を６時間で等速滴下した。滴下終了後
にｔ−ブチルパーオクトエート０．５部とキシレン７部
を３０分で滴下し、さらに１時間３０分撹拌した後キシ
レンを８部添加して、加熱残分４６．１％、ガードナー
粘度＋Ｖを有する不溶解物のない淡黄色透明な金属含有
樹脂組成物Ｐ２を得た。Example 2 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 60 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 10 parts of methyl methacrylate and ethyl acrylate 62.
6 parts, 5.4 parts of 2-methoxyethyl acrylate, 40 parts of the metal-containing monomer mixture described in Production Example M1, 10 parts of xylene, and a chain transfer agent (NOFMER MSD manufactured by NOF Corporation) 1
, 2.5 parts of AIBN and 5.5 parts of AMBN were dropped at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes. After stirring for 1 hour and 30 minutes, 8 parts of xylene was added, and the heating residue was 46.1%. A pale yellow transparent metal-containing resin composition P2 having + V and no insolubles was obtained.
【００５３】［実施例３］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
５７部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１４．６部、エチルアクリレート５
２．６部、ｎ−ブチルアクリレート７．５部、製造例Ｍ
１記載の金属含有モノマー混合物４７．４部、キシレン
１０部、連鎖移動剤（日本油脂社製ノフマーＭＳＤ）１
部、ＡＩＢＮ２．５部、ＡＭＢＮ８．５部からなるから
なる透明な混合物を６時間で等速滴下した。滴下終了後
にｔ−ブチルパーオクトエート０．５部とキシレン７部
を３０分で滴下し、さらに１時間３０分撹拌した後キシ
レンを６．９部添加して、加熱残分４５．８％、ガード
ナー粘度−Ｚ２を有する不溶解物のない淡黄色透明な金
属含有樹脂組成物Ｐ３を得た。Example 3 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 14.6 parts of methyl methacrylate and 5 parts of ethyl acrylate were added through a dropping funnel.
2.6 parts, n-butyl acrylate 7.5 parts, Production Example M
47.4 parts of the metal-containing monomer mixture described in 1, 1 part of xylene, and a chain transfer agent (NOFMER MSD manufactured by NOF Corporation)
, 2.5 parts of AIBN and 8.5 parts of AMBN were dropped at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 6.9 parts of xylene was added. A light yellow transparent metal-containing resin composition P3 having a Gardner viscosity of -Z2 and no insolubles was obtained.
【００５４】［実施例４］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
６１部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１８部、エチルアクリレート６１
部、製造例Ｍ１記載の金属含有モノマー混合物３７．８
部、キシレン１０部、連鎖移動剤（日本油脂社製ノフマ
ーＭＳＤ）１部、ＡＩＢＮ２．５部、ＡＭＢＮ７部から
なるからなる透明な混合物を６時間で等速滴下した。滴
下終了後にｔ−ブチルパーオクトエート０．５部とキシ
レン７部を３０分で滴下し、さらに１時間３０分撹拌し
た後キシレンを８．２部添加して、加熱残分４６．０
％、ガードナー粘度＋Ｔを有する不溶解物のない淡黄色
透明な金属含有樹脂組成物Ｐ４を得た。Example 4 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 61 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 18 parts of methyl methacrylate and 61 parts of ethyl acrylate were added from the dropping funnel.
Part, metal-containing monomer mixture 37.8 described in Production Example M1
, 10 parts of xylene, 1 part of a chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION), 2.5 parts of AIBN, and 7 parts of AMBN, were dropped at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes. After stirring for 1 hour and 30 minutes, 8.2 parts of xylene was added, and the residue after heating was 46.0.
%, And a pale yellow transparent metal-containing resin composition P4 having a Gardner viscosity + T and no insoluble matter was obtained.
【００５５】［実施例５］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
５７部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて滴下ロートからメチ
ルメタクリレート５部、エチルアクリレート６４．９
部、２−メトキシエチルアクリレート５．４部、製造例
Ｍ１記載の金属含有モノマー混合物４０部、製造例Ｍ５
記載の金属含有モノマー混合物６部、キシレン１０部、
連鎖移動剤（日本油脂社製ノフマーＭＳＤ）１部、ＡＩ
ＢＮ２．５部、ＡＭＢＮ６部からなるからなる透明な混
合物を６時間で等速滴下した。滴下終了後にｔ−ブチル
パーオクトエート０．５部とキシレン７部を３０分で滴
下し、さらに１時間３０分撹拌した後キシレンを７．７
部添加して、加熱残分４６．２％、ガードナー粘度＋Ｕ
を有する不溶解物のない淡黄色透明な金属含有樹脂組成
物Ｐ５を得た。Example 5 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 5 parts of methyl methacrylate and 64.9 of ethyl acrylate were added from the dropping funnel.
Parts, 5.4 parts of 2-methoxyethyl acrylate, 40 parts of the metal-containing monomer mixture described in Production Example M1, Production Example M5
6 parts of the metal-containing monomer mixture described above, 10 parts of xylene,
1 part of chain transfer agent (NOFMER MSD manufactured by NOF Corporation), AI
A transparent mixture consisting of 2.5 parts of BN and 6 parts of AMBN was dropped at a constant rate over 6 hours. After the completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then xylene was added at 7.7.
Part, add heating residue 46.2%, Gardner viscosity + U
And a pale yellow, transparent, metal-containing resin composition P5 having no insolubles was obtained.
【００５６】［実施例６］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
５７部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１部、エチルアクリレート６６．２
部、２−メトキシエチルアクリレート５．４部、製造例
Ｍ６記載の金属含有モノマー混合物５２部、キシレン１
０部、連鎖移動剤（日本油脂社製ノフマーＭＳＤ）１
部、ＡＩＢＮ２．５部、ＡＭＢＮ７部からなるからなる
緑色な混合物を６時間で等速滴下した。滴下終了後にｔ
−ブチルパーオクトエート０．５部とキシレン７部を３
０分で滴下し、さらに１時間３０分撹拌した後キシレン
を４．４部添加して、加熱残分４５．２％、ガードナー
粘度＋Ｖを有する不溶解物のない緑色な金属含有樹脂組
成物Ｐ６を得た。Example 6 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 1 part of methyl methacrylate and 66.2 of ethyl acrylate were added from the dropping funnel.
Part, 2-methoxyethyl acrylate 5.4 parts, metal-containing monomer mixture 52 parts described in Production Example M6, xylene 1
0 parts, chain transfer agent (NOFMER MSD manufactured by NOF Corporation) 1
, 2.5 parts of AIBN and 7 parts of AMBN, were dropped at a constant rate over 6 hours. After completion of dropping, t
0.5 parts of butyl peroctoate and 7 parts of xylene in 3 parts
After 0 minutes, the mixture was further stirred for 1 hour and 30 minutes, and then 4.4 parts of xylene was added. The residue was heated to 45.2%, and a green metal-containing resin composition P6 having a Gardner viscosity + V and having no insoluble matter was added. I got
【００５７】［実施例７］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
６１部を仕込み、撹拌しながら１００℃に昇温した。続
いて、滴下ロートからメチルメタクリレート４９．５５
部、エチルアクリレート５０部、製造例Ｍ１記載の金属
含有モノマー混合物１部、ＡＩＢＮ２．５部、ＡＭＢＮ
２部からなるからなる透明な混合物を４時間で等速滴下
した。滴下終了後にｔ−ブチルパーオクトエート０．５
部とキシレン７部を３０分で滴下し、さらに１時間３０
分撹拌した後キシレンを３８．４５部添加して、加熱残
分４４．７％、ガードナー粘度＋Ｂを有する不溶解物の
ない透明な金属含有樹脂組成物Ｐ７を得た。Example 7 A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 61 parts of xylene, and heated to 100 ° C. while stirring. did. Subsequently, methyl methacrylate 49.55 was added from the dropping funnel.
Parts, 50 parts of ethyl acrylate, 1 part of the metal-containing monomer mixture described in Production Example M1, 2.5 parts of AIBN, AMBN
A transparent mixture consisting of 2 parts was added dropwise at a constant rate in 4 hours. After completion of the dropwise addition, t-butyl peroctoate 0.5
And 7 parts of xylene were added dropwise over 30 minutes, and then 1 hour 30
After stirring for 38 minutes, 38.45 parts of xylene was added to obtain a transparent metal-containing resin composition P7 having a heating residue of 44.7% and a Gardner viscosity of + B and having no insoluble matter.
【００５８】［実施例８］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
６１部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１８部、エチルアクリレート６１
部、製造例Ｍ２記載の金属含有モノマー混合物３７．８
部、キシレン１０部、連鎖移動剤（日本油脂社製ノフマ
ーＭＳＤ）１部、ＡＩＢＮ２．５部、ＡＭＢＮ７部から
なるからなる透明な混合物を６時間で等速滴下した。滴
下終了後にｔ−ブチルパーオクトエート０．５部とキシ
レン７部を３０分で滴下し、さらに１時間３０分撹拌し
た後キシレンを８．２部添加して、加熱残分４６．２
％、ガードナー粘度＋Ｙを有する不溶解物のない淡黄色
透明な金属含有樹脂組成物Ｐ８を得た。Example 8 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 61 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 18 parts of methyl methacrylate and 61 parts of ethyl acrylate were added from the dropping funnel.
Part, metal-containing monomer mixture 37.8 described in Production Example M2
, 10 parts of xylene, 1 part of a chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION), 2.5 parts of AIBN, and 7 parts of AMBN, were dropped at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes. After stirring for 1 hour and 30 minutes, 8.2 parts of xylene was added, and the remaining residue was 46.2.
%, And a pale yellow transparent metal-containing resin composition P8 having a Gardner viscosity + Y and no insoluble matter was obtained.
【００５９】［実施例９］冷却器、温度計、滴下ロート
および攪拌機を備えた四つ口フラスコにＰＧＭ（プロピ
レングリコールメチルエーテル）１５部およびキシレン
５７部およびエチルアクリレート４部を仕込み、撹拌し
ながら１００℃に昇温した。続いて、滴下ロートからメ
チルメタクリレート１部、エチルアクリレート６４．９
部、２−メトキシエチルアクリレート５．４部、製造例
Ｍ３記載の金属含有モノマー混合物５５部、キシレン１
０部、連鎖移動剤（日本油脂社製ノフマーＭＳＤ）１
部、ＡＩＢＮ２．５部、ＡＭＢＮ７．５部からなるから
なる透明な混合物を６時間で等速滴下した。滴下終了後
にｔ−ブチルパーオクトエート０．５部とキシレン７部
を３０分で滴下し、さらに１時間３０分撹拌した後キシ
レンを３．１部添加して、加熱残分４６．３％、ガード
ナー粘度＋Ｗを有する僅かに濁った淡黄色な金属含有樹
脂組成物Ｐ９を得た。Example 9 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 1 part of methyl methacrylate and 64.9 of ethyl acrylate were added from the dropping funnel.
Part, 2-methoxyethyl acrylate 5.4 parts, metal-containing monomer mixture 55 parts described in Production Example M3, xylene 1
0 parts, chain transfer agent (NOFMER MSD manufactured by NOF Corporation) 1
, 2.5 parts of AIBN and 7.5 parts of AMBN were dropped at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes. After stirring for 1 hour and 30 minutes, 3.1 parts of xylene was added. A slightly turbid, pale yellow, metal-containing resin composition P9 having a Gardner viscosity + W was obtained.
【００６０】［実施例１０］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）４６．８部およびキ
シレン２５．２部およびエチルアクリレート４部を仕込
み、撹拌しながら９０℃に昇温した。続いて、滴下ロー
トからメチルメタクリレート１部、エチルアクリレート
６６．２部、２−メトキシエチルアクリレート５．４
部、製造例Ｍ４記載の金属含有モノマー混合物５２部、
ＰＧＭ１０部、連鎖移動剤（日本油脂社製ノフマーＭＳ
Ｄ）１部、ＡＩＢＮ２．５部、ＡＭＢＮ８部からなるか
らなる透明な混合物を６時間で等速滴下した。滴下終了
後にｔ−ブチルパーオクトエート０．５部とキシレン７
部を３０分で滴下した後１００℃に昇温し、さらに１時
間撹拌した後キシレンを４．４部添加して、加熱残分４
５．９％、ガードナー粘度＋Ｖを有する僅かに濁った淡
黄色な金属含有樹脂組成物Ｐ１０を得た。Example 10 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 46.8 parts of PGM (propylene glycol methyl ether), 25.2 parts of xylene and 4 parts of ethyl acrylate. The temperature was raised to 90 ° C. while stirring. Subsequently, 1 part of methyl methacrylate, 66.2 parts of ethyl acrylate, and 5.4 of 2-methoxyethyl acrylate were added from the dropping funnel.
Parts, 52 parts of the metal-containing monomer mixture described in Production Example M4,
10 parts of PGM, chain transfer agent (NOFMER MS manufactured by NOF Corporation)
D) A transparent mixture consisting of 1 part, 2.5 parts of AIBN and 8 parts of AMBN was dropped at a constant speed over 6 hours. After dropping, 0.5 part of t-butyl peroctoate and xylene 7
Was added dropwise over 30 minutes, the temperature was raised to 100 ° C., and the mixture was further stirred for 1 hour.
A slightly turbid pale yellow metal-containing resin composition P10 having 5.9% and Gardner viscosity + V was obtained.
【００６１】［製造例Ｃ１］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにＰＧＭ（プロ
ピレングリコールメチルエーテル）１５部およびキシレ
ン６１部およびエチルアクリレート４部を仕込み、撹拌
しながら１００℃に昇温した。続いて、滴下ロートから
メチルメタクリレート１８部、エチルアクリレート６１
部、粉末である亜鉛のジアクリレート塩（浅田化学社
製）７．７５部、粉末である亜鉛のジメタクリレート塩
（浅田化学社製）９．２５部、ＰＧＭ１８．７９部、水
２．２部、キシレン１０部、連鎖移動剤（日本油脂社製
ノフマーＭＳＤ）１部、ＡＩＢＮ２．５部、ＡＭＢＮ６
部からなるからなる亜鉛のジ（メタ）アクリレート塩が
溶解しないため不透明となっている溶液を６時間で等速
滴下した。滴下終了後にｔ−ブチルパーオクトエート
０．５部とキシレン７部を３０分で滴下した、さらに２
時間撹拌した後キシレンを７．４６部添加して、加熱残
分４４．２％、ガードナー粘度Ａ以下を有する不溶解物
が混合した白色溶液Ｃ１を得た。[Production Example C1] A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 61 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Subsequently, 18 parts of methyl methacrylate and 61 parts of ethyl acrylate were added from the dropping funnel.
Parts, 7.75 parts of zinc diacrylate salt (manufactured by Asada Chemical Co., Ltd.), 9.25 parts of zinc dimethacrylate salt (manufactured by Asada Chemical Co., Ltd.), 18.79 parts of PGM, 2.2 parts of water , 10 parts of xylene, 1 part of chain transfer agent (NOFMER MSD manufactured by NOF Corporation), 2.5 parts of AIBN, AMBN6
The solution, which was opaque because the di (meth) acrylate salt of zinc consisting of 1 part was not dissolved, was dropped at a constant speed in 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes.
After stirring for 7 hours, 7.46 parts of xylene was added to obtain a white solution C1 in which an insoluble matter having a heating residue of 44.2% and a Gardner viscosity of A or less was mixed.
【００６２】［製造例Ｃ２］冷却器、温度計、滴下ロー
トおよび攪拌機を備えた四つ口フラスコにキシレン１２
０部、ｎ−ブタノール３０部を仕込み、撹拌しながら１
１０℃に昇温した。続いて、滴下ロートからアクリル酸
エチル６０部、アクリル酸２−エチルヘキシル２５部、
アクリル酸１５部、 アゾビスイソブチロニトリル２部
からなる混合物を３時間で等速滴下した。滴下終了後２
時間撹拌して、加熱残分３９．７％、ガードナー粘度＋
Ｊの特性値を有するワニスを得た。[Production Example C2] Xylene 12 was placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer.
0 parts and 30 parts of n-butanol were charged, and 1 part was stirred.
The temperature was raised to 10 ° C. Subsequently, 60 parts of ethyl acrylate, 25 parts of 2-ethylhexyl acrylate from the dropping funnel,
A mixture consisting of 15 parts of acrylic acid and 2 parts of azobisisobutyronitrile was dropped at a constant speed over 3 hours. After dripping 2
After stirring for 3 hours, heating residue 39.7%, Gardner viscosity +
A varnish having the characteristic value of J was obtained.
【００６３】次に、冷却器、温度計、滴下ロートおよび
攪拌機を備えた四つ口フラスコに、得られたワニス１０
０部、ナフテン酸２０部、水酸化銅７部を加え、１２０
℃に昇温して２時間攪拌し、この間生成する水（２．６
ｇ）を脱水後、加熱残分５１．９％、ガードナー粘度＋
Ｈの特性値を有する金属含有樹脂Ｃ２を得た。Next, the obtained varnish 10 was placed in a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer.
0 parts, 20 parts of naphthenic acid and 7 parts of copper hydroxide,
° C and stirred for 2 hours, and the water generated during this time (2.6
g) after dehydration, heating residue 51.9%, Gardner viscosity +
A metal-containing resin C2 having a characteristic value of H was obtained.
【００６４】表１に製造例Ｍ１〜Ｍ６の金属含有モノマ
ー混合物の仕込み量（モル比）、金属含有モノマー混合
物中の溶剤量および水の含有量（質量％）、金属含有モ
ノマー混合物の固形分を記載した。Table 1 shows the charged amounts (molar ratio) of the metal-containing monomer mixtures of Production Examples M1 to M6, the amounts of solvent and water in the metal-containing monomer mixtures (% by mass), and the solid contents of the metal-containing monomer mixtures. Described.
【００６５】表２に実施例Ｐ１〜Ｐ１０の金属含有樹脂
組成物の仕込み量（質量比）、得られた樹脂組成物の粘
度（ガードナー）、固形分（％）および樹脂の分子量
（ＭＷ）を記載した。Table 2 shows the charged amounts (mass ratio) of the metal-containing resin compositions of Examples P1 to P10, the viscosity (Gardner), the solid content (%), and the molecular weight (MW) of the obtained resin composition. Described.
【００６６】[0066]
【表１】 [Table 1]
【００６７】[0067]
【表２】 [Table 2]
【００６８】分子量は、ＨＬＣ−８１２０ＧＰＣによる
金属含有樹脂の分子量をＴＳＫ−ｇｅｌ αタイプ（α
−Ｍ）２本を用いて２０ｍＭ ＬｉＢｒを添加したＤＭ
Ｆ溶離液で測定した。重量平均分子量は、ポリスチレン
換算として求めた。For the molecular weight, the molecular weight of the metal-containing resin measured by HLC-8120GPC was measured using TSK-gel α type (α
-M) DM to which 20 mM LiBr was added using two tubes
Measured with F eluent. The weight average molecular weight was determined in terms of polystyrene.
【００６９】次いで、このようにして得られた共重合体
溶液Ｐ１〜Ｐ６、Ｐ８〜Ｐ１０を用いて、表３に示す配
合割合により本発明の防汚性塗料（実施例１１〜１９）
を調製した。また、共重合体溶液Ｃ１、Ｃ２を用いて、
表３に示す配合割合により比較例１、２の防汚性塗料を
調製した。Next, using the copolymer solutions P1 to P6 and P8 to P10 obtained in this manner, the antifouling paints of the present invention (Examples 11 to 19) at the compounding ratios shown in Table 3
Was prepared. Further, using the copolymer solutions C1 and C2,
The antifouling paints of Comparative Examples 1 and 2 were prepared according to the mixing ratios shown in Table 3.
【００７０】[0070]
【表３】 [Table 3]
【００７１】次いで、上記調製の各防汚性塗料を用い
て、下記の要領で貯蔵安定性試験、塗膜の消耗度試験、
防汚性試験、耐クラック・耐剥離性試験を行った。Next, using each of the antifouling paints prepared as described above, a storage stability test, a consumption test of the paint film,
An antifouling test and a crack / peeling resistance test were performed.
【００７２】（１）貯蔵安定性試験 各防汚塗料の塗料作成直後と４０℃で１ヶ月間恒温水槽
中で保管後の塗料粘度の測定結果を表４に記載した。(1) Storage stability test Table 4 shows the measurement results of the viscosity of the paint immediately after preparation of the paint for each antifouling paint and after storage in a thermostatic water bath at 40 ° C. for one month.
【００７３】[0073]
【表４】 [Table 4]
【００７４】（２）塗膜の消耗度試験 各防汚性塗料を、それぞれ５０×５０×２ｍｍ（厚さ）
の硬質塩化ビニル板に、乾燥膜厚２４０μｍになるよう
にアプリケーターで塗布し、海水に設置した回転ドラム
に取り付け、周速１５ノットで回転させて、３カ月間毎
の消耗膜厚を測定した。その結果を表５に示した。(2) Test for Degree of Consumption of Coating Film Each of the antifouling paints was 50 × 50 × 2 mm (thickness).
Was applied with an applicator so as to have a dry film thickness of 240 μm, attached to a rotating drum placed in seawater, and rotated at a peripheral speed of 15 knots, and the consumable film thickness was measured every three months. Table 5 shows the results.
【００７５】[0075]
【表５】 [Table 5]
【００７６】（３）防汚性試験 各防汚性塗料を、あらかじめ防錆塗料を塗布してあるサ
ンドブラスト鋼板に、乾燥膜厚が２４０μｍになるよう
に塗布して試験板を作成し、広島県広島湾内で３６カ月
間静置浸漬し、６カ月毎に付着性物の付着面積（％）を
調べた。その結果を表６に示した。(3) Antifouling test Each of the antifouling paints was applied to a sandblasted steel plate to which a rustproof paint had been applied in advance so that the dry film thickness was 240 μm, and a test plate was prepared. The sample was immersed in Hiroshima Bay for 36 months, and the area (%) of the adhered substance was examined every 6 months. Table 6 shows the results.
【００７７】[0077]
【表６】 [Table 6]
【００７８】（４）クラック・剥離性試験 下記の基盤（１）、基盤（２）上に、それぞれ実施例１
１〜１９と比較例１、２の防汚性塗料組成物を乾燥膜厚
が２４０μｍになるように塗布して試験板、を作成
した。試験板は、基盤（２）を作成する際に塗布した
防汚塗料と同一のものを塗装した。 基盤（１）：あらかじめ防錆塗料を塗布してあるサンド
ブラスト鋼板からなる基盤。 基盤（２）：実施例１１〜１９と比較例１、２の防汚性
塗料組成物による膜厚２４０μｍの塗膜をそれぞれ基盤
（１）上に形成させたものに、滅菌濾過海水中に３ヶ月
間浸漬した後、室温で１週間乾燥して得られる基盤。(4) Crack / peelability test Example 1 was placed on the following base (1) and base (2), respectively.
Test plates were prepared by applying the antifouling paint compositions of Examples 1 to 19 and Comparative Examples 1 and 2 so that the dry film thickness was 240 µm. The test plate was coated with the same antifouling paint applied when the substrate (2) was prepared. Base (1): A base made of a sandblasted steel sheet to which a rust-preventive paint has been applied in advance. Substrate (2): A 240 μm-thick coating film of the antifouling coating compositions of Examples 11 to 19 and Comparative Examples 1 and 2 was formed on the substrate (1). A base obtained by immersing for months and drying at room temperature for one week.
【００７９】上記、の試験板を、滅菌濾過海水中に
２４カ月間浸漬し、６ヶ月毎に海水中から取り出した試
験板を温度２０℃の室温で１週間乾燥し、塗膜のクラッ
ク・剥離状況を観察した。クラックおよび剥離が全くな
いものを○、クラックが僅かに生じているもの△、クラ
ックが全面に生じている、或いは剥離が生じているもの
を×と表示した。その結果を表７に示した。The above test plate was immersed in sterile filtered seawater for 24 months, and the test plate taken out of the seawater every six months was dried at a room temperature of 20 ° C. for one week, and the coating film was cracked and peeled. The situation was observed.も の indicates that there was no crack and no peeling, Δ indicates that a slight crack occurred, and × indicates that a crack occurred on the entire surface or where peeling occurred. Table 7 shows the results.
【００８０】[0080]
【表７】 [Table 7]
【００８１】防汚性塗料組成物（比較例１、２）につい
ては、自己研磨性や防汚性が初期において見られるが、
長期に亘ると見られなくなり防汚性が不良であった。ま
た、高酸価ポリマーに金属塩を付加反応した比較例２に
ついては、塗料の粘度上昇が見られ貯蔵安定性が不十分
であり、金属塩の粉末を重合した比較例１については、
耐クラック・耐耐離性が悪く、リコート性が不良であっ
た。In the antifouling paint composition (Comparative Examples 1 and 2), the self-polishing property and the antifouling property were observed at the initial stage.
It was not seen over a long period of time and the antifouling property was poor. Further, in Comparative Example 2 in which a metal salt was added to a high acid value polymer, the viscosity of the paint was increased and storage stability was insufficient. In Comparative Example 1 in which a metal salt powder was polymerized,
Poor crack and separation resistance and poor recoating properties.
【００８２】一方、共重合体Ｐ１〜Ｐ６、Ｐ８〜Ｐ１０
を用いた本発明の防汚性塗料組成物（実施例１１〜１
９）は、長期の自己研磨性と優れた防汚性能を示し、さ
らに、耐クラック性や耐剥離性が優れており、リコート
性が良好であった。On the other hand, copolymers P1 to P6, P8 to P10
Antifouling paint composition of the present invention using phenol (Examples 11 to 1)
No. 9) exhibited long-term self-polishing properties and excellent antifouling performance, and also had excellent crack resistance and peeling resistance, and good recoating properties.
【００８３】[0083]
【発明の効果】以上説明したように、本発明によれば、
無機金属化合物とカルボキシル基含有ラジカル重合性単
量体の反応物を重合して得られる重合体が一般的な有機
溶剤に可溶な金属含有樹脂組成物を提供できる。ここで
得られた重合体を用いた防汚塗料は、これを防汚塗料用
ビヒクルとして使用した場合、適切な速度で、かつ均一
に海中へ溶解し、長期にわたって自己研磨性を維持する
ことができるという優れた防汚効果を発揮するととも
に、耐クラック性や剥離性に優れた特徴を有しており、
工業上非常に有益なものである。As described above, according to the present invention,
It is possible to provide a metal-containing resin composition in which a polymer obtained by polymerizing a reaction product of an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer is soluble in a general organic solvent. When the antifouling paint using the polymer obtained here is used as a vehicle for the antifouling paint, it dissolves in the sea at an appropriate speed and uniformly, and can maintain self-polishing properties for a long time. While exhibiting an excellent antifouling effect that it can be done, it has features that are excellent in crack resistance and peelability,
It is very useful industrially.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀田 一彦 愛知県名古屋市東区砂田橋四町目１番60号 三菱レイヨン株式会社商品開発研究所内 (72)発明者 長坂 俊夫 愛知県名古屋市東区砂田橋四町目１番60号 三菱レイヨン株式会社商品開発研究所内 (72)発明者 岩瀬 国男 愛知県名古屋市東区砂田橋四町目１番60号 三菱レイヨン株式会社商品開発研究所内 Ｆターム(参考） 4J038 CC011 CF011 CF021 CG031 CG141 CG161 CH031 CH041 CH071 CH081 CH111 CH121 CH171 CH201 CJ131 CK031 CK041 GA06 HA126 HA156 HA216 JA18 JA27 KA06 MA14 NA05 PB05 PB07 PC02 4J100 AB02Q AG04Q AK12P AK21P AK26P AL03Q AL08Q AL09Q AM02Q AM15Q BA04Q BA05Q BA06Q BC43Q CA04 JA01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhiko Hotta 1-60, Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture Inside Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Inventor Toshio Nagasaka Sunadabashi Yomachi, Higashi-ku, Nagoya City, Aichi Prefecture No. 1-60 Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Inventor Kunio Iwase 1-60 Sunadabashi Yomachi, Higashi-ku, Nagoya City, Aichi Prefecture F-term in Mitsubishi Rayon Co., Ltd. Product Development Laboratory 4J038 CC011 CF011 CF021 CG031 CG141 CG161 CH031 CH041 CH071 CH081 CH111 CH121 CH171 CH201 CJ131 CK031 CK041 GA06 HA126 HA156 HA216 JA18 JA27 KA06 MA14 NA05 PB05 PB07 PC02 4J100 AB02Q AG04Q AK12P AK21P AK26P AL03QAL08Q04 BA09Q04
Claims (6)
ジカル重合性単量体の反応物と、少なくともアルコール
系溶剤を含む有機溶剤と、水とからなり、水の含有量が
０．０１〜３０質量％である金属含有モノマー混合物
（Ａ）と、その他のラジカル重合性不飽和単量体（Ｂ）
とを共重合して得られる金属含有樹脂組成物。1. A reaction product of an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer, an organic solvent containing at least an alcohol solvent, and water, wherein the water content is 0.01 to 30% by mass. And a radical-polymerizable unsaturated monomer (B)
And a metal-containing resin composition obtained by copolymerizing
金属化合物のモル数に対して、水を０．０１〜５倍モル
含有する請求項１記載の金属含有樹脂組成物。2. The metal-containing resin composition according to claim 1, wherein the metal-containing monomer mixture (A) contains water in an amount of 0.01 to 5 moles per mole of the inorganic metal compound.
有機溶剤は、アルコール系溶剤を５〜１００質量％含有
するものである請求項１または２記載の金属含有樹脂組
成物。3. The metal-containing resin composition according to claim 1, wherein the organic solvent in the metal-containing monomer mixture (A) contains 5 to 100% by mass of an alcohol solvent.
鉛、銅あるいはマグネシウムからなる金属の酸化物、水
酸化物あるいは塩化物と、（メタ）アクリル酸と、少な
くともアルコール系溶剤を含む有機溶剤と、水とからな
り、亜鉛、銅あるいはマグネシウムからなる金属の酸化
物、水酸化物あるいは塩化物のモル数に対して０．０５
〜３倍モルの水を含有する請求項１〜３の何れか一項記
載の金属含有樹脂組成物。4. A metal-containing monomer mixture (A) comprising a metal oxide, hydroxide or chloride consisting of zinc, copper or magnesium, (meth) acrylic acid, and an organic solvent containing at least an alcohol solvent. , Water, and 0.05 to the moles of oxides, hydroxides or chlorides of metals consisting of zinc, copper or magnesium.
The metal-containing resin composition according to any one of claims 1 to 3, wherein the metal-containing resin composition contains water in an amount of up to three times the amount of water.
有樹脂組成物を用いた防汚性塗料組成物。5. An antifouling paint composition using the metal-containing resin composition according to claim 1.
２００００の範囲である請求項５記載の防汚性塗料組成
物。6. The resin component having a weight average molecular weight of 1,000 to 1,000.
The antifouling coating composition according to claim 5, wherein the composition is in the range of 20,000.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000194584A JP3483524B2 (en) | 2000-06-28 | 2000-06-28 | Metal-containing resin composition and antifouling paint composition |
| US09/886,111 US6727304B2 (en) | 2000-06-28 | 2001-06-22 | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| EP01305457A EP1167398B1 (en) | 2000-06-28 | 2001-06-22 | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| NO20013214A NO331090B1 (en) | 2000-06-28 | 2001-06-26 | Metal-containing monomer-dissolved mixture, metal-containing resin, antifouling paint mixture and use thereof |
| SG200103972A SG125887A1 (en) | 2000-06-28 | 2001-06-26 | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| KR10-2001-0036927A KR100461479B1 (en) | 2000-06-28 | 2001-06-27 | Metal-containing Resin and Antifouling Paint Compositon |
| TW090115548A TW534912B (en) | 2000-06-28 | 2001-06-27 | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| CNB031603807A CN1241957C (en) | 2000-06-28 | 2001-06-28 | Mono soluble mixture containing metal, composition containing metal resin and dirt-proof paint |
| CNB011248939A CN1274755C (en) | 2000-06-28 | 2001-06-28 | Dissolved mixer containing metallic monomer, metal-containing resin and antifouling paint composition |
| HK02104417.5A HK1043601B (en) | 2000-06-28 | 2002-06-12 | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| KR10-2003-0075738A KR100451064B1 (en) | 2000-06-28 | 2003-10-29 | Metal-containing Monomer Dissolved Mixture |
| KR10-2004-0041690A KR100496580B1 (en) | 2000-06-28 | 2004-06-08 | Antifouling Paint Compositon |
| NO20085361A NO337425B1 (en) | 2000-06-28 | 2008-12-22 | Antifouling paint mixture and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000194584A JP3483524B2 (en) | 2000-06-28 | 2000-06-28 | Metal-containing resin composition and antifouling paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002012630A true JP2002012630A (en) | 2002-01-15 |
| JP3483524B2 JP3483524B2 (en) | 2004-01-06 |
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ID=18693386
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|---|---|---|---|
| JP2000194584A Expired - Lifetime JP3483524B2 (en) | 2000-06-28 | 2000-06-28 | Metal-containing resin composition and antifouling paint composition |
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| Country | Link |
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| JP (1) | JP3483524B2 (en) |
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| JP2002371166A (en) * | 2001-06-14 | 2002-12-26 | Mitsubishi Rayon Co Ltd | Aqueous metal-containing resin composition and coated resin |
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|---|---|---|---|---|
| JP2002371166A (en) * | 2001-06-14 | 2002-12-26 | Mitsubishi Rayon Co Ltd | Aqueous metal-containing resin composition and coated resin |
| US8741983B2 (en) | 2002-10-23 | 2014-06-03 | Chugoku Marine Paints, Ltd. | Antifouling coating composition including a metal-containing copolymer, 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one, and metal-pyrithione compound and using thereof |
| US7928175B2 (en) | 2003-03-14 | 2011-04-19 | Mitsubishi Rayon Co., Ltd. | Antifouling paint composition |
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| JP5417599B2 (en) * | 2005-12-28 | 2014-02-19 | 中国塗料株式会社 | High solid antifouling paint composition, antifouling paint film, base material with paint film, antifouling base material, method of forming a paint film on the surface of the base material, antifouling method of base material, and high solid multi-component antifouling Paint composition set |
| JP2008291141A (en) * | 2007-05-25 | 2008-12-04 | Chugoku Marine Paints Ltd | High-solid antifouling coating composition, coating film composed of the composition, substrate coated with the coating film and antifouling method |
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| WO2013183637A1 (en) * | 2012-06-04 | 2013-12-12 | 三菱レイヨン株式会社 | Resin composition for anti-fouling coating material, anti-fouling coating material, and anti-fouling film |
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| KR20170086090A (en) | 2015-04-16 | 2017-07-25 | 미쯔비시 케미컬 주식회사 | Antifouling coating composition |
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