JPH07150076A - Antifouling coating material - Google Patents
Antifouling coating materialInfo
- Publication number
- JPH07150076A JPH07150076A JP6258168A JP25816894A JPH07150076A JP H07150076 A JPH07150076 A JP H07150076A JP 6258168 A JP6258168 A JP 6258168A JP 25816894 A JP25816894 A JP 25816894A JP H07150076 A JPH07150076 A JP H07150076A
- Authority
- JP
- Japan
- Prior art keywords
- group
- coating material
- acrylate
- antifouling
- copolymer
- 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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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水中構築物、漁網、船
底等への水棲生物の付着を阻止するための防汚性コーテ
ィング材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling coating material for preventing aquatic organisms from adhering to underwater structures, fishing nets, ship bottoms and the like.
【０００２】[0002]
【従来の技術】水中構築物、漁網、船底をはじめ水中で
長期間使用する物品には、使用中に水棲生物が付着、繁
殖して外観を損ねるばかりでなく、その機能に悪影響を
与えることがある。船底の場合においては、水棲生物の
付着が船全体の表面粗度の増加につながり、さらには船
速が低下するとともに燃費が増大する。またこのため、
ドックでの修復期間が長くなり運航効率が著しく低下す
る。このほか、バクテリア類の繁殖により水中構築物の
腐敗、物性の劣化が起こって著しく寿命が低下する等の
莫大な被害を生ずる。2. Description of the Related Art Aquatic organisms adhere to and propagate during use for a long time in water, such as underwater structures, fishing nets and ship bottoms, which not only impairs the appearance but also adversely affects their functions. . In the case of the bottom of the ship, the adhesion of aquatic organisms leads to an increase in the surface roughness of the entire ship, which further reduces the ship speed and increases fuel consumption. Also because of this,
The dock repair period will be extended and the operating efficiency will be significantly reduced. In addition, the propagation of bacteria causes rot of the underwater structure and deterioration of physical properties, resulting in enormous damage such as shortening of life.
【０００３】従来より、このような被害を回避するため
に使用される防汚剤としては、有機塩素系化合物、亜酸
化銅、有機スズ化合物等が知られている。Conventionally, as antifouling agents used to avoid such damage, organic chlorine compounds, cuprous oxide, organic tin compounds and the like are known.
【０００４】有機スズ化合物や亜酸化銅のような重金属
を含有する生理活性物質は、特に優れた防汚効果を有
し、漁網や船底用の塗料に必須の成分と考えられてい
る。例えば、米国特許第 3,167,473号明細書には、有機
スズ化合物を用いた防汚処理剤のなかで「ポリマータイ
プ」といわれているものが記載されている。この防汚処
理剤は、共重合体の側鎖に有機スズ含有基を有し、微ア
ルカリ性の海水中で加水分解されて有機スズ化合物を放
出し、防汚効果を発揮すると同時に、加水分解された共
重合体自身も水溶化して海水中に溶解していくため、樹
脂残渣層を残すことなく、常に活性な表面を保つことが
できる。また、特開昭 60-231771号公報には、含有する
有機スズ化合物や亜酸化銅等の生理活性物質の溶出性を
促進させる目的で、これに併用する有機スズ含有共重合
体の単量体の一部として、加水分解性のシリル（メタ）
アクリレート、例えばトリブチルシリルアクリレートや
トリフェニルシリル（メタ）アクリレートを用いる方法
が記載されている。A physiologically active substance containing an organic tin compound or a heavy metal such as cuprous oxide has a particularly excellent antifouling effect and is considered to be an essential component for paints for fishing nets and ship bottoms. For example, U.S. Pat. No. 3,167,473 describes an antifouling treatment agent using an organotin compound, which is called "polymer type". This antifouling treatment agent has an organotin-containing group in the side chain of the copolymer, is hydrolyzed in slightly alkaline seawater to release an organotin compound, exerts an antifouling effect, and is simultaneously hydrolyzed. Since the copolymer itself also becomes water-soluble and dissolves in seawater, an active surface can always be maintained without leaving a resin residue layer. Further, JP-A-60-231771 discloses that a monomer of an organotin-containing copolymer used in combination therewith for the purpose of promoting elution of a physiologically active substance such as an organotin compound or cuprous oxide contained therein. Hydrolyzable silyl (meta) as part of
Methods using acrylates such as tributylsilyl acrylate and triphenylsilyl (meth) acrylate are described.
【０００５】しかしながら、これらの防汚処理剤は保存
安定性が悪く、特に亜酸化銅を併用した場合には数日の
内にゲル化してしまうという問題があった。しかも、こ
れらの防汚処理剤は、重金属や加水分解性の有機スズ含
有基を含有するため、毒性が高く、特に有機スズ化合物
は刺激性が強く、皮膚に触れると炎症を起こす等、安全
衛生面で問題があるのみならず、海水中への流出による
海洋汚染、奇形魚の発生、生態濃縮による人体への貯蓄
性等、重大な問題を抱えていた。However, these antifouling agents have poor storage stability, and there is a problem that gelation occurs within a few days especially when cuprous oxide is used in combination. Moreover, since these antifouling agents contain heavy metals and hydrolyzable organotin-containing groups, they are highly toxic, and especially organotin compounds are highly irritating and cause irritation when they come into contact with the skin. Not only was there a problem in terms of aspects, but it also had serious problems such as marine pollution due to runoff into seawater, generation of malformed fish, and savings in human body due to ecological concentration.
【０００６】[0006]
【発明が解決しようとする課題】上述したような問題に
対処するために、例えば特表昭 60-500452号公報には、
有機スズ含有共重合体を用いることなく、防汚効果を示
す船底塗料が記載されている。この船底塗料は毒性およ
び自己研磨型ポリマーより構成されており、該ポリマー
単量体としてはトリス（4-メチル -2-ペントキシ）シリ
ルアクリレートのような加水分解性のシリル（メタ）ア
クリレートが記載されている。In order to solve the above-mentioned problems, for example, Japanese Patent Publication No. Sho 60-500452 discloses
A ship bottom paint that exhibits an antifouling effect without using an organotin-containing copolymer is described. This ship bottom paint is composed of a toxic and self-polishing polymer, and as the polymer monomer, a hydrolyzable silyl (meth) acrylate such as tris (4-methyl-2-pentoxy) silyl acrylate is described. ing.
【０００７】しかしながらこの船底塗料において、自己
研磨型ポリマーは毒物供給系（del-ivery system）とし
て働くのみで、これ自身には防汚性能はないため、毒物
成分が必須のものである。この船底塗料においても、毒
物によって付着した水棲生物を殺すという防汚を果たす
基本的な原理は、従来の防汚処理剤と変っておらず、重
大な環境問題を回避することはできなかった。しかも、
毒物として亜酸化銅を使用した場合には、保全安定性が
悪く、数日の内にゲル化してしまうという問題もあっ
た。さらに、ここに挙げられているトリス（4-メチル -
2-ペントキシ）シリルアクリレートは、ケイ素原子とア
ルコキシ基の間およびケイ素原子とエステル結合の間の
2種類の結合がいずれも加水分解性をもつので、加水分
解による共重合体の水への溶解度の制御が困難になると
いう問題もあった。However, in this ship bottom paint, the self-polishing polymer only acts as a poison-feeding system (del-ivery system) and does not have antifouling performance by itself, so that the poison component is essential. Even in this ship bottom paint, the basic principle of antifouling that kills aquatic organisms attached by poisons is the same as that of conventional antifouling treatments, and it was not possible to avoid serious environmental problems. Moreover,
When cuprous oxide is used as a poison, there is a problem that the preservation stability is poor and gelation occurs within a few days. In addition, the tris (4-methyl-
2-Pentoxy) silyl acrylate is a compound between the silicon atom and the alkoxy group and between the silicon atom and the ester bond.
There is also a problem that it is difficult to control the solubility of the copolymer in water due to hydrolysis because both kinds of bonds are hydrolyzable.
【０００８】本発明は、重金属や毒物を含有せず、海洋
の生態系に悪影響を与えることのない防汚性コーティン
グ材を提供することを目的とする。An object of the present invention is to provide an antifouling coating material which does not contain heavy metals or poisons and does not adversely affect the marine ecosystem.
【０００９】[0009]
【課題を解決するための手段と作用】本発明者らは、防
汚性コーティング材における自己研磨性に注目し、毒物
の併用がなくとも優れた防汚性を有し、しかも保存安定
性の良好なコーティング用組成物を見出して本発明をな
すに至った。Means and Actions for Solving the Problems The present inventors have paid attention to the self-polishing property of an antifouling coating material and have an excellent antifouling property without the use of poisonous substances, and have a good storage stability. The present invention has been accomplished by finding a good coating composition.
【００１０】すなわち、本発明の防汚性コーティング材
は、共重合体側鎖のシリル基が加水分解によって放出さ
れ、次いで共重合体自身も水溶化する自己研磨作用のみ
で防汚性を発揮するものであり、That is, the antifouling coating material of the present invention exhibits antifouling property only by the self-polishing action in which the silyl group of the side chain of the copolymer is released by hydrolysis, and then the copolymer itself is also solubilized. And
【化２】 （式中、Ｒ1 は水素原子またはメチル基、Ｒ2 、Ｒ3 、
Ｒ4 はそれぞれ炭素数 1〜18のアルキル基、シクロアル
キル基およびフェニル基からなる群より選ばれる1価の
炭化水素基で、うち少なくとも 1個は炭素数 4以上の 1
価の炭化水素基を示す）で表される少なくとも 1種の不
飽和トリオルガノシリル単量体と、（メタ）アクリル系
およびビニル系化合物から選ばれる少なくとも 1種の有
機単量体とを重合させて得られる共重合体と、海水反応
性顔料とを含有することを特徴としている。[Chemical 2] (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 , R 3 ,
R 4 is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and a phenyl group, at least one of which is a C 4 or more 1
(Which represents a valent hydrocarbon group) and at least one unsaturated triorganosilyl monomer represented by (1) and at least one organic monomer selected from (meth) acrylic and vinyl compounds are polymerized. It is characterized by containing a copolymer obtained by the above and a seawater-reactive pigment.
【００１１】本発明に用いられる共重合体は、本発明に
おいて特徴的な成分であり、トリオルガノシリル基のケ
イ素原子に結合した有機基を選択することによって適度
の加水分解性を示し、水中で除々に加水分解して親水性
を増すため、水に対して制御された溶解特性を示す。こ
のような共重合体は、 1種または 2種以上の不飽和トリ
オルガノシリル単量体と、 1種または 2種以上の有機単
量体とを重合度50〜10000程度に重合させることによっ
て得られる。The copolymer used in the present invention is a characteristic component in the present invention. It exhibits moderate hydrolyzability by selecting an organic group bonded to the silicon atom of the triorganosilyl group, It exhibits controlled dissolution characteristics in water as it gradually hydrolyzes and becomes more hydrophilic. Such a copolymer is obtained by polymerizing one or more unsaturated triorganosilyl monomers and one or more organic monomers to a polymerization degree of about 50 to 10,000. To be
【００１２】不飽和トリオルガノシリル単量体と有機単
量体との構成比は、特に限定されるものではないが、好
ましくは不飽和トリオルガノシリル単量体の量が10〜95
重量％、さらに好ましくは20〜70重量％の範囲である。
不飽和トリオルガノシリル単量体の量が10重量％未満で
は必要な加水分解速度が得られず、充分な防汚性を発揮
しない。また95重量％を超えると塗膜の物性が悪く、さ
らに加水分解速度が過剰となるため、短期間に溶解して
しまい防汚力が持続しない。The composition ratio of the unsaturated triorganosilyl monomer and the organic monomer is not particularly limited, but the amount of the unsaturated triorganosilyl monomer is preferably 10 to 95.
%, More preferably 20 to 70% by weight.
If the amount of the unsaturated triorganosilyl monomer is less than 10% by weight, the required hydrolysis rate cannot be obtained and sufficient antifouling property is not exhibited. On the other hand, if it exceeds 95% by weight, the physical properties of the coating film are poor and the hydrolysis rate becomes excessive, so that it dissolves in a short time and the antifouling power does not continue.
【００１３】共重合体の一方の出発原料である不飽和ト
リオルガノシリル単量体において、Ｒ1 は水素原子また
はメチル基であり、Ｒ2 、Ｒ3 、Ｒ4 はそれぞれ炭素数
1〜18の独立した 1価の炭化水素基で、直鎖状または分
岐状のアルキル基、シクロアルキル基およびフェニル基
から選ばれるものである。このアルキル基としては、メ
チル基、エチル基、プロピル基、ブチル基、ヘキシル
基、オクチル基、デシル基、ドデシル基、ミリスチル
基、ステアリル基等が例示され、シクロアルキル基とし
ては、シクロペンチル基、シクロヘキシル基等が例示さ
れる。適度な加水分解性を持ち、そのことによってコー
ティング材の水に対する徐溶性を制御するには、Ｒ2 、
Ｒ3 、Ｒ4 のうち少なくとも 1個が炭素数 4以上のもの
であることが必要である。In the unsaturated triorganosilyl monomer which is one starting material of the copolymer, R 1 is a hydrogen atom or a methyl group, and R 2 , R 3 and R 4 are each a carbon number.
1 to 18 independent monovalent hydrocarbon groups, which are selected from linear or branched alkyl groups, cycloalkyl groups and phenyl groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a myristyl group, and a stearyl group, and examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples include groups. In order to control the sustained solubility of the coating material in water, which has moderate hydrolyzability, R 2 ,
At least one of R 3 and R 4 must have 4 or more carbon atoms.
【００１４】このような不飽和トリオルガノシリル単量
体としては、ジメチルブチルシリルアクリレート、ジメ
チルヘキシルシリルアクレレート、ジメチルオクチルシ
リルアクリレート、ジメチルデシルシリルアクリレー
ト、ジメチルドデシルシリルアクリレート、ジメチルシ
クロヘキシルシリルアクリレート、ジメチルフェニルシ
リルアクリレート、メチルジブチルシリルアクリレー
ト、エチルジブチルシリルアクリレート、ジブチルヘキ
シルシリルアクリレート、ジブチルフェニルシリルアク
リレート、トリブチルシリルアクリレート、トリフェニ
ルシリルアクリレート等；およびこれらに対応するメタ
クリレートが例示される。これらのうち、加水分解速度
が遅く、合成の容易なことと、造膜性の良いことでは、
ジメチルヘキシルシリル（メタ）アクリレート、ジメチ
ルデシルシリル（メタ）アクリレートのような、Ｒ2 、
Ｒ3 、Ｒ4 のうち 2個がメチル基で残余が炭素数 6以上
の長鎖アルキル基であるものが優れているが、水中で制
御された加水分解速度をもち、適度の除溶性を得るため
には、トリブチルシリル（メタ）アクリレートが好まし
い。Examples of such unsaturated triorganosilyl monomers include dimethylbutylsilyl acrylate, dimethylhexylsilyl acrylate, dimethyloctylsilyl acrylate, dimethyldecylsilyl acrylate, dimethyldodecylsilyl acrylate, dimethylcyclohexylsilyl acrylate, dimethylphenyl. Examples are silyl acrylate, methyldibutyl silyl acrylate, ethyl dibutyl silyl acrylate, dibutyl hexyl silyl acrylate, dibutyl phenyl silyl acrylate, tributyl silyl acrylate, triphenyl silyl acrylate, and the corresponding methacrylates. Among them, the hydrolysis rate is slow, the synthesis is easy, and the film-forming property is good.
R 2 , such as dimethylhexylsilyl (meth) acrylate, dimethyldecylsilyl (meth) acrylate,
It is excellent that two of R 3 and R 4 are methyl groups and the rest is a long-chain alkyl group having 6 or more carbon atoms, but it has a controlled hydrolysis rate in water and obtains an appropriate dissolution property. For this purpose, tributylsilyl (meth) acrylate is preferred.
【００１５】共重合体の他方の出発原料である有機単量
体は、（メタ）アクリル系およびビニル系化合物から選
ばれるものである。この（メタ）アクリル系化合物とし
ては、メチルアクリレート、エチルアクリレート、ブチ
ルアクリレート、ヘキシルアクリレート、オクチルアク
リレート（以上のアルキル基は直鎖状でも分岐状でもよ
い）、2-ヒドロキシエチルアクリレート、2-ヒドロキシ
プロピルアクリレート、ジメチルアミノエチルアクリレ
ート、アクリルアミド、アクリルニトリル等；およびこ
れらに対応するメタクリル化合物が例示され、ビニル系
化合物としては、酢酸ビニル、塩化ビニル、ビニルメチ
ルエーテル、ビニルエチルエーテル、ビニルプロピルエ
ーテル、ビニルイソブチルエーテル、ビニルピロリドン
等が例示される。The organic monomer which is the other starting material of the copolymer is selected from (meth) acrylic compounds and vinyl compounds. This (meth) acrylic compound includes methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate (the above alkyl groups may be linear or branched), 2-hydroxyethyl acrylate, 2-hydroxypropyl. Acrylate, dimethylaminoethyl acrylate, acrylamide, acrylonitrile and the like; and corresponding methacrylic compounds are exemplified. Examples of vinyl compounds are vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl. Examples include ether and vinylpyrrolidone.
【００１６】重合は、例えば有機溶剤の存在下で不飽和
トリオルガノシリル単量体と有機単量体とを混合し、重
合開始剤を用いて行われる。The polymerization is carried out, for example, by mixing the unsaturated triorganosilyl monomer and the organic monomer in the presence of an organic solvent and using a polymerization initiator.
【００１７】有機溶剤は、重合の制御と反応中のゲルの
形成防止のためのものであり、ベンゼン、トルエン、キ
シレンのような炭化水素系溶剤；酢酸エチル、酢酸ブチ
ルのようなエステル系溶剤；メタノール、エタノールの
ようなアルコール系溶剤；メチルエチルケトン、メチル
イソブチルケトンのようなケトン系溶剤；およびジメチ
ルホルムアミド、ジメチルスルホキシドのような非プロ
トン系極性溶剤が例示される。The organic solvent is for controlling the polymerization and preventing the formation of gel during the reaction, and is a hydrocarbon solvent such as benzene, toluene and xylene; an ester solvent such as ethyl acetate and butyl acetate; Examples thereof include alcohol solvents such as methanol and ethanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
【００１８】有機溶剤の量は、単量体の合計 100重量部
に対して20〜1000重量部が好ましく、さらに好ましくは
50〜 500重量部である。有機溶剤の量が20重量部未満で
は反応の制御が困難となり、また1000重量部を超えると
コーティング材を形成する際に濃縮工程が必要となる。
また、重合中および保存中の加水分解を避けるために、
これらの有機溶剤は水分を除去して用いたほうがよい。The amount of the organic solvent is preferably 20 to 1000 parts by weight, more preferably 100 parts by weight of the total amount of the monomers.
50 to 500 parts by weight. If the amount of the organic solvent is less than 20 parts by weight, it becomes difficult to control the reaction, and if it exceeds 1000 parts by weight, a concentration step is required when forming the coating material.
Also, to avoid hydrolysis during polymerization and storage,
It is better to use these organic solvents after removing water.
【００１９】重合開始剤としては、ベンゾイルパーオキ
サイド、t-ブチルパーベンゾエート、メチルエチルケト
ンパーオキサイド、クメンヒドロパーオキサイド等の有
機過酸化物およびアゾビスイソブチロニトリル等のアゾ
化合物が例示される。重合開始剤の量は単量体の合計量
100重量部に対して0.01〜10重量部が一般的である。重
合条件は特に限定されないが、窒素気流中で行うことが
好ましく、また一般に重合開始剤が有機過酸化物の場合
には60〜 120℃、アゾ化合物の場合には45〜100℃の温
度で行われる。Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide and cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile. The amount of polymerization initiator is the total amount of monomers
0.01 to 10 parts by weight is generally used with respect to 100 parts by weight. The polymerization conditions are not particularly limited, but it is preferable to carry out in a nitrogen stream, and generally, when the polymerization initiator is an organic peroxide, it is carried out at a temperature of 60 to 120 ° C, and when it is an azo compound, it is carried out at a temperature of 45 to 100 ° C. Be seen.
【００２０】本発明のコーティング材は、前述の共重合
体単独か必要に応じて顔料、有機溶剤、揺変剤等を配合
することによって得られる。防汚処理の対象が水中構築
物、漁網、船底等と多岐にわたるため、配合割合は特に
限定できないが、共重合体の配合量が 1〜60重量％の範
囲が好ましい。共重合体の配合量が 1重量％未満では塗
膜を形成しにくく、また60重量％を超えると見掛け粘度
が上って作業性が低下する。The coating material of the present invention can be obtained by using the above-mentioned copolymer alone or, if necessary, incorporating a pigment, an organic solvent, a thixotropic agent and the like. Since the target of antifouling treatment is various such as underwater structures, fishing nets, ship bottoms, etc., the blending ratio is not particularly limited, but the blending amount of the copolymer is preferably 1 to 60% by weight. If the amount of the copolymer compounded is less than 1% by weight, it is difficult to form a coating film, and if it exceeds 60% by weight, the apparent viscosity increases and the workability deteriorates.
【００２１】顔料としては、べんがら、チタン白、タル
ク、シリカ、炭酸カルシウム、硫酸バリウムのような海
水不活性顔料や、酸化亜鉛、酸化カルシウムのような海
水反応性顔料が例示され、 1種でもまた 2種以上の併用
でも差支えない。有機溶剤としては、前述した共重合体
を得るための重合工程で用いたものと同様なものが用い
られる。揺変材としては、ベントナイト、酸化ポリエチ
レンおよびアミド化合物が例示される。Examples of the pigment include seawater inert pigments such as red iron oxide, titanium white, talc, silica, calcium carbonate and barium sulfate, and seawater reactive pigments such as zinc oxide and calcium oxide. It does not matter if two or more kinds are used together. As the organic solvent, the same one as used in the polymerization step for obtaining the above-mentioned copolymer is used. Examples of the thixotropic material include bentonite, polyethylene oxide and amide compounds.
【００２２】[0022]
【実施例】以下、本発明を実施例および比較例によって
説明する。なお、以下の実施例中の部は重量部を示す。EXAMPLES The present invention will be described below with reference to examples and comparative examples. In the following examples, parts are parts by weight.
【００２３】（共重合体の合成）冷却器、撹拌器および
温度計を備えた反応容器にキシレン 300部を仕込み、こ
れにジメチルヘキシルシリルメタクリレート 120部、メ
チルメタクリレート 180部、およびアゾビスイソブチロ
ニトリル 2部を加え、80℃で 8時間加熱撹拌することに
よって重合を行った。室温に冷却後、酢酸エチル66部を
追加して淡黄色透明の共重合体溶液Ｖ−１を得た。Ｖ−
１の25℃における粘度は 480cP、固形分濃度は44.8％で
あった。(Synthesis of Copolymer) 300 parts of xylene was charged into a reaction vessel equipped with a condenser, a stirrer and a thermometer, and 120 parts of dimethylhexylsilyl methacrylate, 180 parts of methyl methacrylate, and azobisisobutyro Polymerization was carried out by adding 2 parts of nitrile and heating and stirring at 80 ° C. for 8 hours. After cooling to room temperature, 66 parts of ethyl acetate was added to obtain a pale yellow transparent copolymer solution V-1. V-
The viscosity of No. 1 at 25 ° C. was 480 cP and the solid content concentration was 44.8%.
【００２４】Ｖ−１と重合後の有機溶剤の追加を行わな
い以外は同様にして、表１に示す有機溶剤、単量体およ
び反応開始剤から、淡黄色透明の共重合体溶液Ｖ−２〜
Ｖ−７を得た。得られた共重合体溶液の粘度と固形分濃
度は表１に示す通りである。なお、表中の配合量を示す
数字は部を表す（以下同じ）。A pale yellow transparent copolymer solution V-2 was prepared from the organic solvent, the monomer and the reaction initiator shown in Table 1 in the same manner except that V-1 and the organic solvent after the polymerization were not added. ~
V-7 was obtained. The viscosity and solid content concentration of the obtained copolymer solution are as shown in Table 1. In addition, the numbers showing the compounding amounts in the table represent parts (the same applies hereinafter).
【００２５】[0025]
【表１】 実施例１〜１０、比較例１〜４ 以上のようにして得た共重合体溶液Ｖ−１〜Ｖ−７を用
いて、本発明の防汚性コーティング材を表２に示す配合
により調製した。[Table 1] Examples 1 to 10 and Comparative Examples 1 to 4 Using the copolymer solutions V-1 to V-7 obtained as described above, the antifouling coating material of the present invention was prepared according to the formulation shown in Table 2. .
【００２６】また、比較例１および２として、亜酸化銅
とトリブチルスズメタクリレートとメチルメタクリレー
トとの共重合体からなる表３に示すワニスＡおよびＢを
用いた防汚塗料を表４に示す配合により調製した。さら
に比較例３および４として、従来型の亜酸化銅を用いた
防汚塗料を表４に示す配合により調製した。Further, as Comparative Examples 1 and 2, antifouling paints using varnishes A and B shown in Table 3 which are composed of a copolymer of cuprous oxide, tributyltin methacrylate and methyl methacrylate were prepared with the formulations shown in Table 4. did. Further, as Comparative Examples 3 and 4, antifouling paints using conventional cuprous oxide were prepared with the formulations shown in Table 4.
【００２７】[0027]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 以上のように調製した各防汚性コーティング材と防汚塗
料とを用いて、下記の要領で塗膜の消耗度と水棲生物の
付着性の試験を行った。[Table 4] Using each of the antifouling coating materials and antifouling paints prepared as described above, the degree of wear of the coating film and the adhesion of aquatic organisms were tested in the following manner.
【００２８】（塗膜の消耗度）実施例１〜１０および比
較例１〜４の各防汚性コーティング材と防汚塗料を、そ
れぞれ70× 150× 2mmの硬質塩化ビニル板に、乾燥膜厚
が 100μm になるようにアプリケーターで塗布し、海水
中に設置した回転ドラムに取付け、周速10ノットで回転
させて、 1カ月間の消耗膜厚を測定した。その結果を表
５に示す。(Exhaust Degree of Coating Film) The antifouling coating material and the antifouling coating material of Examples 1 to 10 and Comparative Examples 1 to 4 were each applied to a hard vinyl chloride plate of 70 × 150 × 2 mm to obtain a dry film thickness. Was applied with an applicator so that it would be 100 μm, attached to a rotating drum installed in seawater, and rotated at a peripheral speed of 10 knots, and the consumed film thickness for one month was measured. The results are shown in Table 5.
【００２９】（水棲生物の付着性）実施例１〜１０お
よび比較例１〜４の各防汚性コーティング材と防汚塗料
を、それぞれ防錆塗料を塗布した 100× 300× 3mmの銅
板に、乾燥膜厚が 150〜 200μm になるように塗布して
試料を作製した。これらの試料と比較例５として無処理
の試料とをそれぞれ広島湾宮島沖の海中に沈め、 6カ月
ごとに水棲生物の付着面積を調べた。各々の試料の付着
面積を百分率で表６に示す。(Adhesion of Aquatic Organisms) Each of the antifouling coating materials and antifouling paints of Examples 1 to 10 and Comparative Examples 1 to 4 was applied to a copper plate of 100 × 300 × 3 mm coated with an anticorrosion paint. A sample was prepared by coating so that the dry film thickness was 150 to 200 μm. These samples and an untreated sample as Comparative Example 5 were each submerged in the sea off Miyajima, Hiroshima Bay, and the adhered area of aquatic organisms was examined every 6 months. The adhesion area of each sample is shown in Table 6 as a percentage.
【００３０】[0030]
【表５】 [Table 5]
【表６】 （水棲生物の付着性）実施例１および５と比較例１お
よび４の各防汚性コーティング材と防汚塗料を、それぞ
れ50×50cmのポリ塩化ビニル樹脂製フレームに取付け
た、網目の大きさが 7節のポリエステル製の漁網に浸漬
塗布して試料を作製した。これらの試料と比較例５とし
て無処理の試料とをそれぞれ富山湾の海中に沈め、 2カ
月ごとに水棲生物の付着状態を調べた。その結果を表７
に示す。[Table 6] (Adhesion of Aquatic Organisms) The sizes of the meshes obtained by attaching the antifouling coating materials and antifouling paints of Examples 1 and 5 and Comparative Examples 1 and 4 to a polyvinyl chloride resin frame of 50 × 50 cm, respectively. Samples were prepared by dipping and coating in a polyester fishing net of Section 7. Each of these samples and a non-treated sample as Comparative Example 5 were submerged in the sea of Toyama Bay, and the state of attachment of aquatic organisms was examined every two months. The results are shown in Table 7.
Shown in.
【００３１】[0031]
【表７】 各試験結果が示すように、本発明の防汚性コーティング
材は、長期間において安定した防汚性を発揮する。[Table 7] As each test result shows, the antifouling coating material of the present invention exhibits stable antifouling property for a long period of time.
【００３２】[0032]
【発明の効果】以上説明したように、本発明で得られる
防汚性コーティング材は、共重合体の側鎖のトリオルガ
ノシリル基が加水分解して親水性を増し、水中で制御さ
れた溶解性、すなわち自己研磨性を示すので、環境に影
響を及ぼす有機スズ化合物や有機スズ含有共重合体を用
いることなく優れた防汚効果を発揮することができる。
本発明の防汚性コーティング材は、水中構築物、漁網、
船底等の水棲生物の付着による汚染を防止するのに有効
である。As described above, the antifouling coating material obtained by the present invention has a controlled solubility in water because the triorganosilyl group of the side chain of the copolymer is hydrolyzed to increase hydrophilicity. Since it exhibits the property, that is, the self-polishing property, it is possible to exert an excellent antifouling effect without using an organic tin compound or an organic tin-containing copolymer that affects the environment.
The antifouling coating material of the present invention is an underwater structure, a fishing net,
It is effective in preventing pollution due to the attachment of aquatic organisms such as ship bottoms.
【００３３】[0033]
フロントページの続き (72)発明者 斉藤 信宏 群馬県太田市西新町133番地 東芝シリコ ーン株式会社内 (72)発明者 栗田 明嗣 群馬県太田市西新町133番地 東芝シリコ ーン株式会社内 (72)発明者 畑中 正行 群馬県太田市西新町133番地 東芝シリコ ーン株式会社内Front page continued (72) Inventor Nobuhiro Saito 133 Nishishinmachi, Ota City, Gunma Prefecture, Toshiba Silicon Corporation (72) Inventor Akitsu Kurita 133 Nishishinmachi, Ota City, Gunma Prefecture, Toshiba Silicon Corporation (72) ) Inventor Masayuki Hatanaka 133 Nishinishimachi, Ota City, Gunma Prefecture Toshiba Toshiba Corporation
Claims (4)
Ｒ4 はそれぞれ炭素数 1〜18のアルキル基、シクロアル
キル基およびフェニル基からなる群より選ばれる1価の
炭化水素基で、うち少なくとも 1個は炭素数 4以上の 1
価の炭化水素基を示す）で表される少なくとも 1種の不
飽和トリオルガノシリル単量体と、（メタ）アクリル系
およびビニル系化合物から選ばれる少なくとも 1種の有
機単量体とを重合させて得られる共重合体と、海水反応
性顔料とを含有することを特徴とする防汚性コーティン
グ材。Claims: (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 , R 3 ,
R 4 is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and a phenyl group, at least one of which is a C 4 or more 1
(Which represents a valent hydrocarbon group) and at least one unsaturated triorganosilyl monomer represented by (1) and at least one organic monomer selected from (meth) acrylic and vinyl compounds are polymerized. An antifouling coating material comprising the copolymer obtained as described above and a seawater-reactive pigment.
ある請求項１記載の防汚性コーティング材。2. The antifouling coating material according to claim 1, wherein R 2 , R 3 and R 4 are all butyl groups.
で、残余が炭素数 6以上のアルキル基である請求項１記
載の防汚性コーティング材。3. The antifouling coating material according to claim 1, wherein two of R 2 , R 3 and R 4 are methyl groups and the rest are alkyl groups having 6 or more carbon atoms.
ガノシリル単量体の量が10〜95重量％である請求項１な
いし請求項３のいずれか１項記載の防汚性コーティング
材。4. The antifouling coating according to any one of claims 1 to 3, wherein the amount of unsaturated triorganosilyl monomer among the monomers of the copolymer is 10 to 95% by weight. Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6258168A JP2833493B2 (en) | 1994-10-24 | 1994-10-24 | Antifouling coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6258168A JP2833493B2 (en) | 1994-10-24 | 1994-10-24 | Antifouling coating material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20251486A Division JPS6357675A (en) | 1986-08-28 | 1986-08-28 | Antifouling coating material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10116616A Division JP3053081B2 (en) | 1998-04-27 | 1998-04-27 | Copolymer for antifouling coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07150076A true JPH07150076A (en) | 1995-06-13 |
| JP2833493B2 JP2833493B2 (en) | 1998-12-09 |
Family
ID=17316479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6258168A Expired - Lifetime JP2833493B2 (en) | 1994-10-24 | 1994-10-24 | Antifouling coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2833493B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1016681A2 (en) * | 1998-12-28 | 2000-07-05 | Chugoku Marine Paints, Ltd. | Silyl (meth)acrylate copolymers, processes for preparing the same, antifouling paint compositions containing the silyl (meth)acrylate copolymers, antifouling coating films formed from the antifouling paint compositions, antifouling methods using the antifouling paint compositions, and hulls or underwater structures coated with the antifouling coating films |
| EP1127902A1 (en) * | 2000-02-25 | 2001-08-29 | Sigma Coatings B.V. | Metal-free binders for self-polishing anti-fouling paints |
| FR2836473A1 (en) * | 2002-02-26 | 2003-08-29 | Atofina | Preparation of organoacyloxysilane derivatives used for synthesis of pharmaceutical products and reactive intermediates comprises reacting silane precursors and carboxylic anhydrides |
| SG106113A1 (en) * | 2001-11-13 | 2004-09-30 | Atofina Chem Inc | Coating compositions |
| WO2019203182A1 (en) * | 2018-04-20 | 2019-10-24 | 日東化成株式会社 | Copolymer for antifouling coating composition and antifouling coating composition containing said copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60500452A (en) * | 1983-01-17 | 1985-04-04 | エム・アンド・テイ・ケミカルス・インコ−ポレイテツド | Erosive ship bottom paint to control ship pollution |
| JPS6357675A (en) * | 1986-08-28 | 1988-03-12 | Chugoku Toryo Kk | Antifouling coating material |
-
1994
- 1994-10-24 JP JP6258168A patent/JP2833493B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60500452A (en) * | 1983-01-17 | 1985-04-04 | エム・アンド・テイ・ケミカルス・インコ−ポレイテツド | Erosive ship bottom paint to control ship pollution |
| JPS6357675A (en) * | 1986-08-28 | 1988-03-12 | Chugoku Toryo Kk | Antifouling coating material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1016681A2 (en) * | 1998-12-28 | 2000-07-05 | Chugoku Marine Paints, Ltd. | Silyl (meth)acrylate copolymers, processes for preparing the same, antifouling paint compositions containing the silyl (meth)acrylate copolymers, antifouling coating films formed from the antifouling paint compositions, antifouling methods using the antifouling paint compositions, and hulls or underwater structures coated with the antifouling coating films |
| EP1016681A3 (en) * | 1998-12-28 | 2000-12-27 | Chugoku Marine Paints, Ltd. | Silyl (meth)acrylate copolymers, processes for preparing the same, antifouling paint compositions containing the silyl (meth)acrylate copolymers, antifouling coating films formed from the antifouling paint compositions, antifouling methods using the antifouling paint compositions, and hulls or underwater structures coated with the antifouling coating films |
| SG85690A1 (en) * | 1998-12-28 | 2002-01-15 | Chugoku Marine Paints | Silyl (meth)acrylate copolymers, processes for preparing the same, antifouling paint compositions containing the silyl (meth)acrylate copolymers, antifouling coating films formed |
| EP1127902A1 (en) * | 2000-02-25 | 2001-08-29 | Sigma Coatings B.V. | Metal-free binders for self-polishing anti-fouling paints |
| WO2001062811A1 (en) * | 2000-02-25 | 2001-08-30 | Sigma Coatings B.V. | Metal-free binders for self-polishing antifouling paints |
| SG106113A1 (en) * | 2001-11-13 | 2004-09-30 | Atofina Chem Inc | Coating compositions |
| FR2836473A1 (en) * | 2002-02-26 | 2003-08-29 | Atofina | Preparation of organoacyloxysilane derivatives used for synthesis of pharmaceutical products and reactive intermediates comprises reacting silane precursors and carboxylic anhydrides |
| WO2019203182A1 (en) * | 2018-04-20 | 2019-10-24 | 日東化成株式会社 | Copolymer for antifouling coating composition and antifouling coating composition containing said copolymer |
| JP6624664B1 (en) * | 2018-04-20 | 2019-12-25 | 日東化成株式会社 | Copolymer for antifouling paint composition, antifouling paint composition containing the copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2833493B2 (en) | 1998-12-09 |
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