JP3527866B2 - Vulcanized rubber composition preventing adhesion of marine organisms and method of preventing adhesion of marine organisms - Google Patents
Vulcanized rubber composition preventing adhesion of marine organisms and method of preventing adhesion of marine organismsInfo
- Publication number
- JP3527866B2 JP3527866B2 JP31431899A JP31431899A JP3527866B2 JP 3527866 B2 JP3527866 B2 JP 3527866B2 JP 31431899 A JP31431899 A JP 31431899A JP 31431899 A JP31431899 A JP 31431899A JP 3527866 B2 JP3527866 B2 JP 3527866B2
- Authority
- JP
- Japan
- Prior art keywords
- marine
- rubber
- sheet
- marine organisms
- chain
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 55
- 239000004636 vulcanized rubber Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 37
- 239000005060 rubber Substances 0.000 claims description 37
- 229920002379 silicone rubber Polymers 0.000 claims description 30
- 239000004945 silicone rubber Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003607 modifier Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920000582 polyisocyanurate Polymers 0.000 claims 1
- 239000011495 polyisocyanurate Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 10
- 231100000331 toxic Toxicity 0.000 description 10
- 230000002588 toxic effect Effects 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 241000238586 Cirripedia Species 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 241001474374 Blennius Species 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005662 Paraffin oil Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 230000010071 organism adhesion Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、海洋生物の付着を
防止した加硫ゴム組成物及び海洋生物付着防止方法に関
するものである。更に詳しくは、海洋を汚染せず、環境
を破壊する虞れがなく、しかも、海洋生物の付着を確実
に防止できる海洋生物の付着を防止した加硫ゴム組成物
及び海洋生物付着防止方法に関するものである。TECHNICAL FIELD The present invention relates to the attachment of marine organisms.
The present invention relates to a vulcanized rubber composition which is prevented and a method for preventing adhesion of marine organisms. More specifically, a vulcanized rubber composition which does not pollute the ocean, has no risk of destroying the environment, and can surely prevent adhesion of marine organisms, and marine organism adhesion It relates to prevention methods.
【０００２】[0002]
【従来の技術】海洋における岸壁、桟橋、護岸、発電所
の取水口、養殖海苔網用支柱、ブイ、防舷材、輸送ホー
ス等（本明細書では、上記をまとめて海洋構造物とい
う）や船舶には、海水に浸漬している部分に、フジツ
ボ、イガイ、海藻類の海洋生物が付着する。特に、水温
が高い時期や場所には大量に付着する。海洋構造物等や
船舶に海洋生物が付着すると、機能や美観を損なうの
で、取り除く必要がある。しかし、その付着力は非常に
強く、取り除く作業が困難であり、また、取り除いたと
しても、その処分に困っていた。2. Description of the Related Art Quays, piers, revetments, water intakes of power stations, cultivated seaweed net columns, buoys, fenders, transportation hoses, etc. (in the present specification, the above are collectively referred to as marine structures) and Marine organisms such as barnacles, mussels, and seaweed adhere to the portion of the ship that is immersed in seawater. In particular, a large amount adheres when or where the water temperature is high. If marine organisms adhere to marine structures and ships, they will impair their function and aesthetics and must be removed. However, its adhesion is so strong that it is difficult to remove it, and even if it was removed, it was difficult to dispose of it.
【０００３】そこで、海洋構造物等や船舶への海洋生物
の付着を防止しようとして、例えば、ゴムまたはプラス
チック等の一般的な組成を有する低表面張力のポリマー
をシート状にして表面に貼着する方法や、または、亜酸
化銅や有機錫化合物、その他毒性イオンを分離する化合
物を添加した塗料等を表面に塗布する方法等が知られて
いる。Therefore, in order to prevent marine organisms from adhering to marine structures and ships, a low surface tension polymer having a general composition such as rubber or plastic is formed into a sheet and attached to the surface. Known methods include, for example, coating a surface with a paint containing a cuprous oxide, an organic tin compound, or a compound that separates toxic ions.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記したよう
な従来の方法には、次のような課題があった。即ち、一
般的な組成を有する低表面張力のポリマーをシート状に
して表面に貼着する方法は、海洋生物の生息が比較的少
ない海洋では付着防止効果が認められたが、生息し易い
環境の海洋では付着する場合が多かった。However, the above-mentioned conventional method has the following problems. That is, a method of sticking a low surface tension polymer having a general composition to the surface in a sheet form has been confirmed to have an anti-adhesion effect in the ocean where marine life is relatively small. It often adhered to the ocean.
【０００５】毒性イオンを分離する化合物を添加した塗
料等を表面に塗布する方法は、海洋構造物等や船舶へ付
着した海洋生物を、塗料から分離した毒性イオンによ
り、死滅させ、付着を防止することができるが、同時
に、当該毒性イオンにより海洋を汚染し、環境を破壊す
る虞れがあった。A method of applying a paint or the like to which a compound for separating toxic ions is applied to the surface is to kill marine organisms adhering to marine structures and ships by the toxic ions separated from the paint to prevent the adherence. However, at the same time, there is a risk that the toxic ions may pollute the ocean and destroy the environment.
【０００６】本発明は、上記課題を解消するもので、海
洋構造物や船舶への海洋生物の付着を確実に防止でき、
これによって海洋生物を取り除く作業や取り除いた後の
処分が不要であり、しかも、毒性イオンにより海洋を汚
染することがなく、環境を破壊する虞れがない、海洋生
物の付着を防止した加硫ゴム組成物及び海洋生物付着防
止方法を提供することを目的とする。The present invention solves the above problems, and can reliably prevent marine life from adhering to marine structures and ships.
This disposal after removing work and to remove the marine life by is unnecessary, moreover, without having to pollute the ocean by toxic ions, there is no possibility to destroy the environment, marine students
An object of the present invention is to provide a vulcanized rubber composition in which adhesion of substances is prevented and a method for preventing adhesion of marine organisms.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に講じた本発明の手段は次のとおりである。第１の発明
にあっては、海洋生物との接触面積を小さくして海洋生
物の付着を防止した加硫ゴム組成物であって、主鎖が鎖
状であるポリマーとシリコーンゴムとの混合物と、海洋
生物が付着するのを防止することができる表面改質剤
と、を含み、上記主鎖が鎖状であるポリマーは、天然ゴ
ム、ポリイソプレンゴム、スチレン−ブタジエン共重合
ゴム、アクリロニトリル−ブタジエン共重合ゴム、ポリ
クロロプレンゴム、エチレン−プロピレン共重合ゴム、
ポリエチレンまたはポリプロピレンであり、上記混合物
は、シリコーンゴム３０〜１００重量部、主鎖が鎖状で
あるポリマー７０重量部以下であり、上記表面改質剤
は、ポリエチレンワックス、塊状クレー、四フッ化エチ
レンパウダー、シリコーンパウダー、セラミックパウダ
ーまたはシランカップリング剤から選ばれた１または２
以上であり、上記表面改質剤は粒径が５〜５０ミクロン
のパウダーであり、当該表面改質剤によって主鎖が鎖状
であるポリマーとシリコーンゴムとの混合物の表面にミ
クロ的な凹凸面が形成され、水との接触角が１００°を
超え、かつ、剥離力が３０ｇ／ｃｍ未満であることを特
徴とする、海洋生物の付着を防止した加硫ゴム組成物で
ある。 [Means for Solving the Problems] The means of the present invention taken to achieve the above object are as follows. According to the first aspect of the invention, the contact area with marine life is reduced to reduce marine life.
A vulcanized rubber composition that prevents adhesion of substances, the main chain of which is a chain
A mixture of a polymer and the silicone rubber is Jo, anda Table Men'aratame modifying agent that Ru can be prevented from marine organisms adhered, the polymer the main chain is a chain, the natural rubber
Rubber, polyisoprene rubber, styrene-butadiene copolymer
Rubber, acrylonitrile-butadiene copolymer rubber, poly
Chloroprene rubber, ethylene-propylene copolymer rubber,
Polyethylene or polypropylene, a mixture of the above
Is 30 to 100 parts by weight of silicone rubber and has a chain main chain.
70 parts by weight or less of a certain polymer, and the above surface modifier
Is polyethylene wax, block clay, ethyl tetrafluoride
Ren powder, silicone powder, ceramic powder
Or 1 or 2 selected from silane coupling agents
Above, the surface modifier has a particle size of 5 to 50 microns.
The main chain is chain-like due to the surface modifier.
On the surface of the mixture of polymer and silicone rubber.
A black and white uneven surface is formed, and the contact angle with water is 100 °.
And the peel force is less than 30 g / cm.
A vulcanized rubber composition that prevents marine organisms from adhering
is there.
【０００８】第２の発明にあっては、第１の発明に係る
加硫ゴム組成物をシートにするステップ、上記シートを
海洋構造物または船舶に貼着するステップ、を含むこと
を特徴とする、海洋生物付着防止方法である。According to a second invention, the first invention is concerned.
A method for preventing adhesion of marine organisms, which comprises a step of forming a vulcanized rubber composition into a sheet and a step of attaching the sheet to a marine structure or a ship.
【０００９】第３の発明にあっては、海洋構造物または
船舶に貼着するシートが、海洋生物が付着しにくいシー
トと、当該海洋生物が付着しにくいシートと海洋構造物
や船舶に対して接着性がよいシートとが重ねられ複層に
なっていることを特徴とする、第２の発明に係る海洋生
物付着防止方法。According to the third aspect of the present invention, a sheet to be attached to a marine structure or a ship is a sheet to which marine life is unlikely to adhere, a sheet to which marine life is unlikely to adhere, and a marine structure or ship. A method for preventing adhesion of marine organisms according to the second aspect of the present invention, characterized in that sheets having good adhesiveness are stacked to form a multilayer.
【００１０】シリコーンゴムとしては、重合度５０００
〜１００００のミラブル型シリコーンゴムが主に用いら
れ、主鎖を構成しているシロキサン部分の関与により撥
水性を有している。その反面、他物体に対しては接着性
が悪くなる。The silicone rubber has a degree of polymerization of 5000.
The millable silicone rubber of 10,000 to 10000 is mainly used, and it has water repellency due to the participation of the siloxane moiety constituting the main chain. On the other hand, the adhesion to other objects is poor.
【００１１】主鎖が鎖状であるポリマーとしては、天然
ゴム、ポリイソプレンゴム、スチレン−ブタジエン共重
合ゴム、アクリロニトリル−ブタジエン共重合ゴム、ポ
リクロロプレンゴム、エチレン−プロピレン共重合ゴ
ム、ポリエチレン、ポリプロピレン等を挙げることがで
きる。接着性はシリコーンゴム比べると優れている。Examples of the polymer having a chain main chain include natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polychloroprene rubber, ethylene-propylene copolymer rubber, polyethylene and polypropylene. Can be mentioned. Adhesiveness is superior to silicone rubber.
【００１２】上記主鎖が鎖状であるポリマーはシリコー
ンゴムと混合することによって使用される。その混合割
合は、主鎖が鎖状であるポリマーが７０重量部以下、シ
リコーンゴムが３０〜１００重量部である。主鎖が鎖状
であるポリマーが７０重量部を超えると混合物の撥水性
と剥離性が低下し海洋生物が付着する虞れがある。尚、
撥水性が大きいと、経験的に海洋生物が付着しにくいこ
とが知られており、当該撥水性は水との接触角を測定す
ることにより表示される。The above-mentioned polymer in which the main chain is linear is used by mixing with a silicone rubber. The mixing ratio is 70 parts by weight or less for the polymer having a chain main chain and 30 to 100 parts by weight for the silicone rubber. If the polymer having a chain main chain exceeds 70 parts by weight, the water repellency and releasability of the mixture may be deteriorated and marine organisms may be attached. still,
It is empirically known that marine organisms are unlikely to adhere when the water repellency is large, and the water repellency is displayed by measuring the contact angle with water.
【００１３】滑剤としては、脂肪酸、パラフィンオイ
ル、フッ素オイルまたはシリコーンオイルから選ばれた
１または２以上の組み合わせであるもの（上記各滑剤単
独で使用される場合もあるし、二種以上を組合せて使用
する場合もある。以下の表面改質剤においても同じであ
る。）等を挙げることができる。しかしながら、上記に
は限定されない。上記滑剤はシリコーンゴムと主鎖が鎖
状であるポリマーとの混合物と相溶性が小さく、そし
て、時間が経つと、ブルームまたはブリードしてきて、
撥水性と剥離性を大きくする性質を有する。The lubricant is one or a combination of two or more selected from fatty acids, paraffin oil, fluorine oil and silicone oil (the above lubricants may be used alone or in combination of two or more kinds). In some cases, the same applies to the following surface modifiers.) And the like. However, it is not limited to the above. The above lubricant has a low compatibility with a mixture of silicone rubber and a polymer having a chain main chain, and blooms or bleeds with the passage of time.
It has the property of increasing water repellency and releasability.
【００１４】上記滑剤は、シリコーンゴムと主鎖が鎖状
であるポリマーとの混合物１００重量部に対して、０．
５〜１００重量部使用される。滑剤が０．５重量部未満
であると、海洋生物が付着し易く、剥離しにくくなり、
１００重量部を超えると、主鎖が鎖状であるポリマーと
シリコーンゴムとの混合物に添加するときにロール機上
で全体がべたつくようになり滑剤を添加できなくなる。The above-mentioned lubricant is 0.1 parts by weight based on 100 parts by weight of a mixture of silicone rubber and a polymer having a chain main chain.
5 to 100 parts by weight are used. If the amount of the lubricant is less than 0.5 parts by weight, marine organisms are likely to attach and become difficult to peel off,
When it exceeds 100 parts by weight, the whole becomes sticky on a roll machine when added to a mixture of a polymer having a chain main chain and a silicone rubber, and a lubricant cannot be added.
【００１５】表面改質剤としては、ポリエチレンワック
ス、塊状クレー、四フッ化エチレンパウダー、シリコー
ンパウダー、セラミックパウダーまたはシランカップリ
ング剤から選ばれた１種または２種以上組み合わせたも
の等を挙げることができる。しかしながら、上記には限
定されない。上記表面改質剤は、粒径が５〜５０ミクロ
ンのパウダーであり、これによって架橋または硬化後、
主鎖が鎖状であるポリマーとシリコーンゴムとの混合物
の表面にミクロ的な凹凸面が形成され、海洋生物が接触
してきても、その接触面積を小さくする。Examples of the surface modifier include one or a combination of two or more selected from polyethylene wax, block clay, tetrafluoroethylene powder, silicone powder, ceramic powder and silane coupling agent. it can. However, it is not limited to the above. The surface modifier is a powder having a particle size of 5 to 50 microns, and after cross-linking or curing with the powder,
Even if a marine organism comes into contact with the surface of a mixture of a polymer having a chain main chain and a silicone rubber, a micro uneven surface is formed to reduce the contact area.
【００１６】表面改質剤は、シリコーンゴムと主鎖が鎖
状であるポリマーとの混合物１００重量部に対して、
０．５〜１００重量部使用される。滑剤が０．５重量部
未満であると、海洋生物が付着し易く、剥離しにくくな
る。１００重量部を超えると、主鎖が鎖状であるポリマ
ーとシリコーンゴムとの混合物に添加するときにロール
機上で混合物が切断してばらばらになり、いわゆる、ロ
ール操作が不能となり、表面改質剤を添加できなくな
る。The surface modifier is based on 100 parts by weight of a mixture of silicone rubber and a polymer having a chain main chain.
0.5 to 100 parts by weight is used. When the amount of the lubricant is less than 0.5 part by weight, marine organisms are likely to adhere to it and it becomes difficult to peel it off. If it exceeds 100 parts by weight, the mixture is cut into pieces on a roll machine when added to a mixture of a polymer having a chain main chain and a silicone rubber, so-called roll operation becomes impossible, and surface modification is performed. The agent cannot be added.
【００１７】主鎖が鎖状であるポリマーとシリコーンゴ
ムとの混合物を加硫（架橋）または硬化させるために、
ジクミルパーオキサイド、ジターシャルブチルパーオキ
サイド、変性アミン複合体等の架橋剤や硬化剤が０．１
〜２０重量部添加される。０．１重量部未満であると上
記混合物を架橋または硬化させることができず、２０重
量部を超えると、いわゆる、オーバー加硫となり、引張
強さや伸びが低下し、その結果、クラックや割れが生じ
る。In order to vulcanize (crosslink) or cure a mixture of a polymer having a chain main chain and a silicone rubber,
Crosslinking agents such as dicumyl peroxide, ditertiary butyl peroxide, modified amine complex, etc.
~ 20 parts by weight are added. If the amount is less than 0.1 parts by weight, the above mixture cannot be crosslinked or cured, and if it exceeds 20 parts by weight, so-called over-vulcanization occurs and tensile strength and elongation decrease, resulting in cracks and cracks. Occurs.
【００１８】主鎖が鎖状であるポリマーとシリコーンゴ
ムとの混合物に、滑剤、表面改質剤、架橋剤または硬化
剤等が添加された未架橋または未硬化のゴム組成物は、
カレンダー機等によってシート状にして、海洋構造物等
や船舶の底部等に貼着され、加硫または硬化される。ま
た、溶剤に溶かして塗料状にし、塗布され加硫または硬
化される。尚、本明細書においては、「貼着」という用
語には、ライニング（接着法、ルーズライニング、融着
法等による）しライナーを形成する場合も含む用語とし
て用いている。An uncrosslinked or uncured rubber composition obtained by adding a lubricant, a surface modifier, a crosslinking agent or a curing agent to a mixture of a polymer having a chain main chain and a silicone rubber is
The sheet is made into a sheet by a calendar machine or the like and attached to a marine structure or the like or the bottom of a ship, and vulcanized or cured. Further, it is dissolved in a solvent to form a paint, which is applied and vulcanized or cured. In the present specification, the term "adhering" is used as a term including a case of forming a liner by lining (by an adhesive method, a loose lining, a fusion method, etc.).
【００１９】シート状にして、海洋構造物や船舶の底部
に貼着等するときは、単層または複層にして使用する。
単層で使用するときは、シリコーンゴムの混合割合の多
い組成物が使用される。また、上記場合において、シリ
コーンゴムの中でも、撥水性と剥離性が大きく、海洋生
物が付着しにくく、また、海洋構造物や船舶に対しては
接着性が良いシリコーンゴムを選択して使用するのが好
ましい。When it is made into a sheet and attached to the bottom of a marine structure or a ship, it is used as a single layer or multiple layers.
When used as a single layer, a composition containing a large proportion of silicone rubber is used. Further, in the above case, among the silicone rubbers, a silicone rubber having a large water repellency and releasability, hardly adhering to marine organisms, and having good adhesiveness to marine structures and ships is selected and used. Is preferred.
【００２０】複層で使用するときは、例えば次のような
場合である。即ち、海洋生物が非常に付着し易い環境
（例えば、海水の温度が高く、潮流が遅い場合等）にな
っている海洋で使用する場合、或いは、更に上記のよう
な環境に加えて海洋構造物や船舶が接着性の悪い材料で
製造されている場合等である。When it is used in multiple layers, for example, it is as follows. That is, when used in the ocean where the marine organisms are very likely to attach (for example, when the temperature of seawater is high and the tidal current is slow), or in addition to the above environment, marine structures Or when the ship is made of a material with poor adhesion.
【００２１】上記複層の具体例としては、上層（海洋生
物と接する層）は撥水性と剥離性を大きくするために、
シリコーンゴムの混合割合が大きい組成物を使用し、海
洋生物が付着しにくいようにする。下層（海洋構造物や
船舶と接する層）は、上層と海洋構造物や船舶との間に
あって、両者の接着を確実にするために、主鎖が鎖状で
あるポリマーの混合割合の大きい組成物を使用する。As a specific example of the above-mentioned multi-layer, an upper layer (a layer in contact with marine organisms) has a large water repellency and peeling property,
Use a composition with a high proportion of silicone rubber to keep marine organisms from adhering. The lower layer (the layer in contact with the marine structure or ship) is between the upper layer and the marine structure or ship, and is a composition with a large mixing ratio of the polymer having a chain main chain in order to ensure adhesion between the two. To use.
【００２２】（作用）
本発明に係る海洋生物の付着を防止した加硫ゴム組成物
は、主鎖が鎖状であるポリマーとシリコーンゴムとの混
合物と、海洋生物が付着するのを防止することができる
表面改質剤とを含んでいる。(Function) The vulcanized rubber composition according to the present invention, which prevents the adhesion of marine organisms, comprises a mixture of a polymer having a chain main chain and a silicone rubber.
And compound, and a surface modifier marine organisms can be prevented from adhering.
【００２３】また、表面改質剤は、表面にミクロ的な凹
凸面を形成し、海洋生物が接触してきても、その接触面
積を小さくし、剥離性を大きくする。従って、海洋生物
の付着を防止した加硫ゴム組成物は、海洋生物が付着し
にくく、また、たとえ、付着したとしても、直ちに剥離
して海中に落ち、実質上、付着するのを防止することが
できる。また、毒性イオンを出す化合物を使用していな
いので、海洋を汚染し、環境を破壊する虞れもない。Further, the surface modifier forms a microscopic uneven surface on the surface and reduces the contact area and enhances the releasability even when marine organisms come into contact with it. Therefore, marine life
The vulcanized rubber composition in which the adherence is prevented hardly adheres to marine organisms, and even if adhered, it can be immediately peeled off and dropped into the sea, and substantially adhered. Moreover, since no compound that produces toxic ions is used, there is no risk of polluting the ocean and destroying the environment.
【００２４】海洋生物の付着を防止した加硫ゴム組成物
をシートとし、海洋構造物または船舶に貼着する海洋生
物付着防止方法によると、当該シートは塗膜に比べて厚
いため、表面改質剤の添加量が多く、十分な撥水性や剥
離性を有するので、海中に長期間にわたって浸漬する海
洋構造物や船舶に対して、海洋生物が付着するのを十分
に防止することができる。According to the method for preventing adhesion of marine organisms, which is a sheet made of a vulcanized rubber composition which prevents marine organisms from adhering, the sheet is thicker than a coating film. Since a large amount of surface modifier is added and it has sufficient water repellency and releasability, it is necessary to sufficiently prevent marine organisms from adhering to marine structures and ships that are immersed in the sea for a long time. You can
【００２５】海洋構造物または船舶に貼着するシートが
複層であり、上層（海洋生物と接する層）として海洋生
物が付着しにくいシートを使用し、下層（海洋構造物等
や船舶と接する層）として上記上層と海洋構造物や船舶
に対して接着性がよいシートを使用したものは、海洋生
物が非常に付着し易い環境になっている海洋において
も、上層シートにより海洋生物が付着するのを確実に防
ぐことができる。また、下層シートにより上層シート自
体が海洋構造物や船舶に対する接着が悪くても、上層シ
ートを海洋構造物や船舶に確実に接着できる。The sheet to be attached to the marine structure or the vessel is a multi-layered sheet, and the sheet (the layer in contact with the marine life) is used as the upper layer (the layer in contact with the marine life), and the lower layer (the layer in contact with the marine structure or the vessel) As a sheet using a sheet having good adhesion to the above upper layer and a marine structure or a ship as the above), the marine organisms will adhere to the upper sheet even in the ocean where the marine organisms are very likely to attach. Can be reliably prevented. Further, even if the upper layer sheet itself has poor adhesion to the marine structure or the vessel, the lower layer sheet can surely adhere the upper layer sheet to the marine structure or the vessel.
【００２６】[0026]
【実施例１】下記の５種の割合でロール機で素練し素練
物を作製した。シリコーンゴム（東芝シリコーン株式会
社製）のみのもの（素練物１という）、 シリコーンゴ
ム（信越化学工業株式会社製）のみのもの（素練物２と
いう）、 シリコーンゴム７０重量部とエチレン−プロ
ピレン共重合ゴム（住友化学工業株式会社製）３０重量
部のもの（素練物３という）、シリコーンゴム５０重量
部とエチレン−プロピレン共重合ゴム５０重量部のもの
（素練物４という）、シリコーンゴム３０重量部とエチ
レン−プロピレン共重合ゴム７０重量部のもの（素練物
５という）。Example 1 A masticated product was prepared by masticating with a roll machine at the following five ratios. Silicone rubber (Toshiba Silicone Co., Ltd.) only (Mixed product 1) Silicone rubber (Shin-Etsu Chemical Co., Ltd.) only (Mixed product 2) Silicone rubber 70 parts by weight ethylene-propylene copolymer Rubber (manufactured by Sumitomo Chemical Co., Ltd.) 30 parts by weight (referred to as masticate 3), silicone rubber 50 parts by weight and ethylene-propylene copolymer rubber 50 parts by weight (referred to as masticate 4), silicone rubber 30 parts by weight And 70 parts by weight of ethylene-propylene copolymer rubber (referred to as masticated product 5).
【００２７】上記素練物１〜５に、架橋剤であるジクミ
ルパーオキサイド２重量部、滑剤であるパラフィンオイ
ル１０重量部、表面改質剤であるシリコーンパウダー１
０重量部を、ロール機で添加しつつ混練し、混練物１〜
５を得た。上記混練物１〜５を常温で２４時間熟成し、
カレンダー機にて厚さ５ｍｍにシーティングし、シート
を得た。このシートを、表面をトルエンで清浄した縦１
２０ｍｍ、横１２０ｍｍの鉄板に貼着し、１６０℃、６
〜２０分の条件でプレス加硫して試料を作製し、本発明
の試料１〜５とした。尚、本発明の試料１と２は、接着
性を考慮して、予め、鉄板をブチルゴム系のプライマー
を塗布し前処理を行った。2 parts by weight of dicumyl peroxide as a cross-linking agent, 10 parts by weight of paraffin oil as a lubricant, and silicone powder 1 as a surface modifier were added to the above-mentioned masticated products 1 to 5.
0 part by weight is kneaded while being added by a roll machine, and kneaded product 1 to
Got 5. Aging the above kneaded products 1 to 5 at room temperature for 24 hours,
Sheets were obtained by sheeting to a thickness of 5 mm with a calendar machine. This sheet has a vertical surface 1
Stick it on an iron plate with a width of 20 mm and a width of 120 mm.
Samples were prepared by press vulcanization under the condition of ˜20 minutes to prepare Samples 1 to 5 of the present invention. Samples 1 and 2 of the present invention were pretreated by previously coating an iron plate with a butyl rubber-based primer in consideration of adhesiveness.
【００２８】比較例として、エチレン−プロピレン共重
合ゴム、ポリクロロプレンゴム、天然ゴム、フッソゴム
をそれぞれ単独で素練し、各素練物により、一般的な組
成のの混練物を得た。これらの混練物を常温で２４時間
熟成し、カレンダー機にて厚さ５ｍｍにシーティング
し、シートを得た。これらのシートを、表面をトルエン
で清浄した縦１２０ｍｍ、横１２０ｍｍの鉄板に貼着
し、１６０℃、６〜２０分の条件でプレス加硫して試料
を作製し、比較例の試料１〜４とした。As a comparative example, ethylene-propylene copolymer rubber, polychloroprene rubber, natural rubber and fluorine rubber were individually masticated, and each masticated material gave a kneaded material having a general composition. These kneaded materials were aged at room temperature for 24 hours and sheeted to a thickness of 5 mm with a calender to obtain a sheet. These sheets were attached to an iron plate having a length of 120 mm and a width of 120 mm whose surface was cleaned with toluene, and press-vulcanized under the conditions of 160 ° C. for 6 to 20 minutes to prepare samples. And
【００２９】上記本発明の試料１〜５と上記比較例の試
料１〜４の加硫ゴム面の水との接触角及び剥離力を測定
後、ロープに吊し、海苔養殖場内の観測塔より海中に浸
漬し、フジツボの付着程度を調べた。After measuring the contact angle and peeling force between water on the vulcanized rubber surfaces of Samples 1 to 5 of the present invention and Samples 1 to 4 of the above Comparative Example, they were hung on a rope and observed from an observation tower in a seaweed farm. It was immersed in the sea, and the degree of adhesion of barnacles was examined.
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１中において、硬さはＪＩＳ Ｋ６３０
１ 加硫ゴム試験法に規定されているスプリング硬さ試
験法にて測定した。水との接触角は、協和界面科学
（株）製「ウエハー処理評価装置」ＣＡ−Ｓ１５０によ
り測定した。液適は蒸留水を使用した。In Table 1, the hardness is JIS K630.
1 Measured by the spring hardness test method specified in the vulcanized rubber test method. The contact angle with water was measured by "Wafer processing evaluation device" CA-S150 manufactured by Kyowa Interface Science Co., Ltd. Distilled water was used as the solution.
【００３２】剥離力は下記のようにして測定した。先
ず、試料の表面をイソプロピルアルコールで洗浄し、常
温で５時間乾燥させた。乾燥後の試料と日東電工（株）
製粘着テープ（品番３１Ｂ）とを重ね合せ、１ｋｇｆの
重さの金属ロールで押えて付けて貼着した。この貼着し
た試料に２０ｋｇ／ｃｍ2の荷重をかけ、２５℃で２５
時間保持し調整した。調整後の試料を、新東科学（株）
製トライボキアＨＥＩＤＯＮタイプ１４ＤＲを使用し剥
離力を測定した。また、色調の欄において、透明という
記載は無色透明、白という記載は白色不透明、黒という
記載は黒色不透明であることを示す。尚、硬さと色調は
おおよその物性を知るための参考として記した。The peeling force was measured as follows. First, the surface of the sample was washed with isopropyl alcohol and dried at room temperature for 5 hours. Samples after drying and Nitto Denko Corporation
The pressure-sensitive adhesive tape (product number 31B) was superposed and pressed by a metal roll having a weight of 1 kgf to be stuck and stuck. A load of 20 kg / cm 2 is applied to the attached sample, and the sample is kept at 25 ° C for 25
Hold and adjust for time. Adjusted sample, Shinto Kagaku Co., Ltd.
The peeling force was measured using TRIBOKIA HEIDON type 14DR manufactured by KK. Further, in the column of color tone, the description transparent is colorless and transparent, the description white is opaque white, and the description black is opaque black. The hardness and color tone are shown as a reference for knowing the approximate physical properties.
【００３３】（考察）
本発明の試料１〜５は１〜３年の浸漬期間において、フ
ジツボが付着していない。しかしながら、比較例の試料
１〜４は１年の浸漬期間において、フジツボが付着して
いる。このことから、水との接触角が１００°を超え、
そして、剥離力が３０ｇ／ｃｍ未満であれば、海洋生物
の付着を防止できることが分かる。ゴム組成物には、毒
性イオンを出す化合物を使用していないので、当然、海
洋を汚染し、環境を破壊することはない。(Discussion) The samples 1 to 5 of the present invention have no barnacle attached during the immersion period of 1 to 3 years. However, the barnacles adhere to the samples 1 to 4 of the comparative example during the one-year immersion period. From this, the contact angle with water exceeds 100 °,
And, it can be seen that if the peeling force is less than 30 g / cm, the adhesion of marine organisms can be prevented. Since the rubber composition does not use any compound that produces toxic ions, it naturally does not pollute the ocean and destroy the environment.
【００３４】[0034]
【実施例２】上記混練物３をカレンダー機にて厚さ２．
５ｍｍにシーティングし、シートを得た。また、上記混
練物５において、シリコーンパウダーの代わりに四フッ
化エチレンパウダーを使用し、この混練物をカレンダー
機にて厚さ２．５ｍｍにシーティングした。前者のシー
トは撥水性と剥離性がよく、後者のシートは前者のシー
トと後記ＦＲＰとに対する接着性が比較的よい。[Example 2] Thickness of the kneaded product 3 was 2.
Sheeting was performed by sheeting to 5 mm. Further, in the above kneaded material 5, tetrafluoroethylene powder was used in place of the silicone powder, and this kneaded material was sheeted to a thickness of 2.5 mm with a calender machine. The former sheet has good water repellency and releasability, and the latter sheet has relatively good adhesion to the former sheet and the FRP described later.
【００３５】先ず、後者のシートを、表面をトルエンで
清浄した縦１２０ｍｍ、横１２０ｍｍのＦＲＰ（ガラス
繊維強化不飽和ポリエステル）に貼着し、次いで、貼着
した後者のシートの表面に前者のシートを貼着した。こ
れを、１６０℃、６〜２０分の条件でプレス加硫して試
料を作製し、本発明の試料６とした。First, the latter sheet was attached to FRP (glass fiber reinforced unsaturated polyester) having a length of 120 mm and a width of 120 mm, the surface of which was cleaned with toluene, and then the former sheet was attached to the surface of the attached latter sheet. I stuck it. This was press-vulcanized at 160 ° C. for 6 to 20 minutes to prepare a sample, which was designated as Sample 6 of the present invention.
【００３６】本発明の試料６の加硫ゴム面の水との接触
角及び剥離力を測定後、ロープに吊し、排水によって海
水の温度が高くなっている発電所内の岸壁の近くの海中
に浸漬し、フジツボの付着程度を調べた。After measuring the contact angle with water and the peeling force of the vulcanized rubber surface of Sample 6 of the present invention, it was hung on a rope and placed in the sea near the quay in the power plant where the temperature of seawater is high due to drainage. After immersion, the degree of adhesion of barnacles was examined.
【００３７】[0037]
【表２】 [Table 2]
【００３８】（考察）
上層は実施例１における本発明の試料３と同一の組成物
であるから、本発明の試料３の場合と同一の結果が得ら
れている。尚、接着性が悪いＦＲＰに貼着されているに
も拘らず、下層における混練物５、即ち主鎖が鎖状であ
るポリマーの混合割合が多い混練物を使用することによ
り上層のシート（上記前者のシート）とＦＲＰとの間の
接着力が十分であることが分かった。また、ゴム組成物
には、毒性イオンを出す化合物を使用していないので、
当然、海洋を汚染し、環境を破壊することはない。(Discussion) Since the upper layer has the same composition as the sample 3 of the present invention in Example 1, the same result as that of the sample 3 of the present invention is obtained. It should be noted that, even though the kneaded product 5 in the lower layer, that is, the kneaded product in which the polymer having a chain-like main chain is mixed in a large proportion is used, even though it is adhered to the FRP having poor adhesion, the upper layer sheet (the above It was found that the adhesive strength between the former sheet) and the FRP was sufficient. In addition, since the rubber composition does not use any compound that produces toxic ions,
Naturally, it does not pollute the ocean and destroy the environment.
【００３９】[0039]
【実施例３】実施例１における素練物３〜５において、
エチレン−プロピレン共重合ゴムの代わりにスチレン−
ブタジエン共重合ゴムを使用し、同様の操作を行い、得
られた素練物を素練物７〜９とした。更に、混練物３〜
５において、パラフィンオイルの代わりにフッ素オイル
とシリコーンオイルとの混合物を、シリコーンパウダー
の代わりにセラミックパウダーとポリエチレンワックス
との混合物を使用し、同様の操作を行い、得られた混練
物を混練物７〜９とした。混練物７〜９の２０重量部
を、トルエン８０重量部に溶かし、本発明の塗料１〜３
とした。[Example 3] In the masticated products 3 to 5 in Example 1,
Styrene instead of ethylene-propylene copolymer rubber
A butadiene copolymer rubber was used and the same operation was carried out to obtain masticates 7 to 9. Furthermore, kneaded product 3 ~
5, a mixture of fluorine oil and silicone oil was used in place of paraffin oil, and a mixture of ceramic powder and polyethylene wax was used in place of silicone powder, and the same operation was performed to obtain a kneaded product. It was set to ~ 9. 20 parts by weight of the kneaded materials 7 to 9 are dissolved in 80 parts by weight of toluene, and the coating materials 1 to 3 of the present invention are dissolved.
And
【００４０】比較例として、エチレン−プロピレン共重
合ゴム、ポリクロロプレンゴム、天然ゴム、フッ素ゴム
をそれぞれ単独に素練し、各素練物により一般的な組成
の混練物を得た。それらの２０重量部を、トルエン８０
重量部に溶かし、比較例の塗料１〜４とした。As a comparative example, ethylene-propylene copolymer rubber, polychloroprene rubber, natural rubber and fluororubber were individually masticated, and each masticated product yielded a kneaded product having a general composition. 20 parts by weight of them are mixed with 80 parts of toluene.
It was dissolved in parts by weight to obtain coatings 1 to 4 of Comparative Example.
【００４１】本発明の塗料１〜３と比較例の塗料１〜４
とを、トルエンで清浄しブチルゴム系のプライマーを塗
布し前処理を行った縦１２０ｍｍ、横１２０ｍｍの鉄板
に塗布する。次いで、乾燥し、常温〜１００℃、５分〜
７日の条件で間接加硫させ、厚さ１ｍｍの塗膜を形成
し、本発明の試料７〜９と比較例の試料５〜８とを作製
した。本発明の試料７〜９と比較例の試料５〜８との加
硫ゴム面の水との接触角及び剥離力を測定後、ロープに
吊し、排水によって海水の温度が高くなっている発電所
内の岸壁の近くの海中に１年間浸漬し、フジツボの付着
程度を調べた。Paints 1 to 3 of the present invention and paints 1 to 4 of Comparative Example
And are cleaned with toluene, applied with a butyl rubber-based primer, and applied on a pretreated iron plate having a length of 120 mm and a width of 120 mm. Next, it is dried and then at room temperature to 100 ° C for 5 minutes.
Indirect vulcanization was performed under the conditions of 7 days to form a coating film having a thickness of 1 mm, and Samples 7 to 9 of the present invention and Samples 5 to 8 of Comparative Examples were produced. Power generation in which the contact angle of water between the vulcanized rubber surfaces of Samples 7 to 9 of the present invention and Samples 5 to 8 of Comparative Example and the peeling force were measured, and then suspended on a rope and the temperature of seawater was increased by drainage. It was immersed in the sea near the quay inside the plant for one year, and the degree of adhesion of barnacles was examined.
【００４２】（考察）
本発明の試料７〜９のゴム組成物は実施例１における本
発明の試料３〜５のゴム組成物とほぼ同一であり、比較
例の試料５〜８のゴム組成物は比較例の試料１〜４のゴ
ム組成物とほぼ同一である。表示は省いたが、本発明の
試料７〜９の加硫ゴム面の水との接触角、剥離力及びフ
ジツボが付着しない点についても、実施例１における本
発明の試料３〜５ほぼ同一であった。従って、本発明の
試料７〜９のゴム組成物は、そのまま、塗料としても適
用できることが分かる。(Discussion) The rubber compositions of Samples 7 to 9 of the present invention are almost the same as the rubber compositions of Samples 3 to 5 of the present invention in Example 1, and the rubber compositions of Samples 5 to 8 of Comparative Example. Are almost the same as the rubber compositions of Samples 1 to 4 of Comparative Example. Although not shown, Samples 3 to 5 of the present invention in Example 1 are almost the same in terms of the contact angle of water on the vulcanized rubber surface of Samples 7 to 9 of the present invention, the peeling force, and the point that no barnacles are attached. there were. Therefore, it is understood that the rubber compositions of Samples 7 to 9 of the present invention can be directly applied as a coating material.
【００４３】一方、比較例の試料５〜８は比較例の試料
１〜４と加硫ゴム面の水との接触角、剥離力及びフジツ
ボの付着等ほぼ同一であった。従って、比較例の試料５
〜８のゴム組成物は、塗料としても使用できないことが
分かる。本発明の試料７〜９のゴム組成物は、毒性イオ
ンを出す化合物を使用していないので、当然、海洋を汚
染し、環境を破壊することはない。On the other hand, the samples 5 to 8 of the comparative example were almost the same as the samples 1 to 4 of the comparative example in terms of contact angle with water on the surface of the vulcanized rubber, peeling force and adhesion of barnacles. Therefore, sample 5 of the comparative example
It can be seen that the rubber compositions of ~ 8 cannot be used as a paint. Since the rubber compositions of Samples 7 to 9 of the present invention do not use a compound that produces toxic ions, naturally, they do not pollute the ocean and destroy the environment.
【００４４】なお、本明細書で使用している用語と表現
はあくまで説明上のものであって、限定的なものではな
く、上記用語、表現と等価の用語、表現を除外するもの
ではない。また、本発明は図示の実施の形態に限定され
るものではなく、特許請求の範囲の記載内において種々
の変形が可能である。It should be noted that the terms and expressions used in the present specification are merely for explanation, they are not limiting, and the terms and expressions equivalent to the above terms and expressions are not excluded. The present invention is not limited to the illustrated embodiments, and various modifications can be made within the scope of the claims.
【００４５】[0045]
【発明の効果】本発明は上記構成を備え、次の効果を有
する。
（ａ）本発明に係る海洋生物の付着を防止した加硫ゴム
組成物は、主鎖が鎖状であるポリマーとシリコーンゴム
との混合物と、海洋生物が付着するのを防止することが
できる表面改質剤とを含んでいる。従って、表面改質剤
は、表面にミクロ的な凹凸面を形成し、接触面積を小さ
くし、剥離性を大きくする。その結果、加硫ゴム組成物
は、海洋生物が付着しにくく、また、たとえ、付着した
としても、直ちに剥離して海中に落ち、実質上付着する
のを防止することができる。また、毒性イオンを出す化
合物を使用していないので、海洋を汚染し、環境を破壊
する虞れもない。The present invention having the above-mentioned structure has the following effects. (A) Vulcanized rubber that prevents marine organisms from adhering to the present invention
The composition comprises a mixture of a polymer having a chain main chain and a silicone rubber, and a surface modifier capable of preventing marine organisms from adhering thereto. Therefore, the surface modifier forms a micro uneven surface on the surface, reduces the contact area, and increases the peeling property. As a result, the vulcanized rubber composition is unlikely to have marine organisms attached thereto , and even if attached, it can be immediately peeled off and fall into the sea to prevent substantial attachment. Moreover, since no compound that produces toxic ions is used, there is no risk of polluting the ocean and destroying the environment.
【００４６】（ｂ）海洋生物の付着を防止した加硫ゴム
組成物でシートを形成し、海洋構造物または船舶に貼着
する海洋生物付着防止方法によると、当該シートは塗膜
に比べて厚いため、表面改質剤の添加量が多く、十分な
撥水性や剥離性を有するので、海中に長期間にわたって
浸漬する海洋構造物や船舶に対して、海洋生物が付着す
るのを十分に防止することができる。(B) Vulcanized rubber that prevents marine organisms from adhering
According to the method for preventing the attachment of marine organisms, which forms a sheet from the composition and attaches it to a marine structure or a ship, since the sheet is thicker than the coating film, the amount of the surface modifier added is large and the water repellency is sufficient. Since it has a peeling property and a peeling property, it is possible to sufficiently prevent marine organisms from adhering to marine structures and ships that are immersed in the sea for a long time.
【００４７】（ｃ）海洋構造物または船舶に貼着するシ
ートが複層であり、上層（海洋生物と接する層）として
海洋生物が付着しにくいシートを使用し、下層（海洋構
造物等や船舶と接する層）として上記上層と海洋構造物
や船舶に対して接着性がよいシートを使用したものは、
海洋生物が非常に付着し易い環境になっている海洋にお
いても、上層シートにより海洋生物が付着するのを確実
に防ぐことができる。また、下層シートにより上層シー
ト自体が海洋構造物や船舶に対する接着が悪くても、上
層シートを海洋構造物や船舶に確実に接着できる。(C) The sheet to be attached to the marine structure or the vessel is a multi-layered sheet, and the upper layer (the layer in contact with the marine life) is a sheet to which marine life is unlikely to adhere, and the lower layer (the marine structure or the ship) A layer that uses a sheet with good adhesion to the above upper layer and marine structures or ships
Even in the ocean where the marine organisms are very likely to attach, the upper sheet can reliably prevent the marine organisms from attaching. Further, even if the upper layer sheet itself has poor adhesion to the marine structure or the vessel, the lower layer sheet can surely adhere the upper layer sheet to the marine structure or the vessel.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉野 憲司 福岡県浮羽郡浮羽町大字高見215番地 株式会社 ユニ・スター 内 (72)発明者 原口 武人 福岡県浮羽郡田主丸町大字野田601 有 限会社 田主丸化成 内 (56)参考文献 特開 昭58−13673（ＪＰ，Ａ) 特開 昭61−118429（ＪＰ，Ａ) 特開 平４−370173（ＪＰ，Ａ) 特開 平８−165455（ＪＰ，Ａ) 特開 平10−7988（ＪＰ，Ａ) 特開 平10−330688（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 83/00 - 83/16 C08K 3/00 - 13/08 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Yoshino, 215 Takami, Ukiha-cho, Ukiha-gun, Fukuoka Prefecture Uni Star Co., Ltd. Kasei (56) Reference JP 58-13673 (JP, A) JP 61-118429 (JP, A) JP 4-370173 (JP, A) JP 8-165455 (JP, A) ) JP-A-10-7988 (JP, A) JP-A-10-330688 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08L 83/00-83/16 C08K 3 / 00-13/08
Claims (3)
生物の付着を防止した加硫ゴム組成物であって、 主鎖が鎖状であるポリマーとシリコーンゴムとの混合物
と、 海洋生物が付着するのを防止することができる表面改質
剤と、 を含み、上記主鎖が鎖状であるポリマーは、天然ゴム、ポリイソ
プレンゴム、スチレン−ブタジエン共重合ゴム、アクリ
ロニトリル−ブタジエン共重合ゴム、ポリクロロプレン
ゴム、エチレン−プロピレン共重合ゴム、ポリエチレン
またはポリプロピレンであり、 上記混合物は、シリコーンゴム３０〜１００重量部、主
鎖が鎖状であるポリマー７０重量部以下であり、 上記表面改質剤は、ポリエチレンワックス、塊状クレ
ー、四フッ化エチレンパウダー、シリコーンパウダー、
セラミックパウダーまたはシランカップリング剤から選
ばれた１または２以上であり、 上記表面改質剤は粒径が５〜５０ミクロンのパウダーで
あり、当該表面改質剤によって主鎖が鎖状であるポリマ
ーとシリコーンゴムとの混合物の表面にミクロ的な凹凸
面が形成され、 水との接触角が１００°を超え、かつ、剥離力が３０ｇ
／ｃｍ未満であることを特徴とする、 海洋生物の付着を防止した加硫ゴム組成物。 1. A method for reducing the contact area with marine life to reduce the ocean
A vulcanized rubber composition that prevents organisms from adhering, and a mixture of a polymer having a chain main chain and a silicone rubber
If, anda Table Men'aratame modifying agent that Ru can be prevented from adhering marine organisms, the polymer the main chain is a chain, the natural rubber, polyiso
Plane rubber, styrene-butadiene copolymer rubber, acrylic
Ronitrile-butadiene copolymer rubber, polychloroprene
Rubber, ethylene-propylene copolymer rubber, polyethylene
Or polypropylene, and the mixture is mainly composed of 30 to 100 parts by weight of silicone rubber,
The amount of the chain-like polymer is 70 parts by weight or less, and the surface modifier is polyethylene wax or lumpy clay.
ー, tetrafluoroethylene powder, silicone powder,
Select from ceramic powder or silane coupling agent
1 or 2 or more, and the surface modifier is a powder having a particle size of 5 to 50 microns.
A polymer whose main chain is chain-like due to the surface modifier.
-Like unevenness on the surface of the mixture of silicone and silicone rubber
Surface is formed , the contact angle with water exceeds 100 °, and the peeling force is 30g
It is less than / cm, The vulcanized rubber composition which prevented the adhesion of marine life.
にするステップ、 上記シートを海洋構造物または船舶に貼着するステッ
プ、 を含むことを特徴とする、 海洋生物付着防止方法。2. A method for preventing adhesion of marine organisms, which comprises the step of forming the vulcanized rubber composition according to claim 1 into a sheet, and the step of attaching the sheet to a marine structure or a ship.
が、海洋生物が付着しにくいシートと、当該海洋生物が
付着しにくいシートと海洋構造物や船舶に対して接着性
がよいシートとが重ねられ複層になっていることを特徴
とする、 請求項２記載の海洋生物付着防止方法。3. A sheet to be attached to a marine structure or a ship, a sheet to which marine life is unlikely to adhere, a sheet to which the marine life is unlikely to adhere, and a sheet having good adhesion to the marine structure or ship. The method for preventing adhesion of marine organisms according to claim 2, characterized in that they are stacked to form a multilayer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31431899A JP3527866B2 (en) | 1999-11-04 | 1999-11-04 | Vulcanized rubber composition preventing adhesion of marine organisms and method of preventing adhesion of marine organisms |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31431899A JP3527866B2 (en) | 1999-11-04 | 1999-11-04 | Vulcanized rubber composition preventing adhesion of marine organisms and method of preventing adhesion of marine organisms |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001131413A JP2001131413A (en) | 2001-05-15 |
| JP3527866B2 true JP3527866B2 (en) | 2004-05-17 |
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ID=18051913
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31431899A Expired - Fee Related JP3527866B2 (en) | 1999-11-04 | 1999-11-04 | Vulcanized rubber composition preventing adhesion of marine organisms and method of preventing adhesion of marine organisms |
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| CN103649240B (en) | 2011-01-19 | 2016-09-14 | 哈佛学院院长等 | There is high-voltage stability, optical transparence and the smooth surface of selfreparing feature |
| US9932484B2 (en) | 2011-01-19 | 2018-04-03 | President And Fellows Of Harvard College | Slippery liquid-infused porous surfaces and biological applications thereof |
| WO2013094412A1 (en) * | 2011-12-21 | 2013-06-27 | 日東電工株式会社 | Pressure sensitive adhesive tape with attached antifouling layer |
| JP2013227476A (en) * | 2012-01-06 | 2013-11-07 | Nitto Denko Corp | Adhesive tape for preventing deposition of aquatic organism |
| US9963597B2 (en) | 2012-07-12 | 2018-05-08 | President And Fellows Of Harvard College | Slippery self-lubricating polymer surfaces |
| JP2014062215A (en) * | 2012-09-03 | 2014-04-10 | Nitto Denko Corp | Aquatic organism adhesion prevention adhesive tape |
| JP2015007201A (en) * | 2013-06-26 | 2015-01-15 | 日東電工株式会社 | Aquatic anti-biofouling pressure-sensitive adhesive tape |
| JP6503170B2 (en) * | 2014-09-05 | 2019-04-17 | 日東電工株式会社 | Resin composition, antifouling material, antifouling layer, and laminated film |
| WO2020077160A1 (en) | 2018-10-11 | 2020-04-16 | Freeflow Medical Devices Llc | Fluoropolymer based anti-thrombotic coatings |
| WO2020077161A1 (en) | 2018-10-11 | 2020-04-16 | Freeflow Medical Devices Llc | Packaging for medical devices coated with perfluorinated liquids or dispersions thereof |
| JP7672753B1 (en) | 2024-04-19 | 2025-05-08 | バッセル化学株式会社 | Chemical-free antifouling paint composition and method for forming antifouling film using the same |
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