JPH0117507B2 - - Google Patents
Info
- Publication number
- JPH0117507B2 JPH0117507B2 JP1381781A JP1381781A JPH0117507B2 JP H0117507 B2 JPH0117507 B2 JP H0117507B2 JP 1381781 A JP1381781 A JP 1381781A JP 1381781 A JP1381781 A JP 1381781A JP H0117507 B2 JPH0117507 B2 JP H0117507B2
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- resin composition
- polybutylene terephthalate
- present
- coating
- 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
Links
- -1 polybutylene terephthalate copolymer Polymers 0.000 claims description 34
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002519 antifouling agent Substances 0.000 claims description 17
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 241000195493 Cryptophyta Species 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 5
- 230000002265 prevention Effects 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 description 34
- 239000011342 resin composition Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-M terephthalate(1-) Chemical compound OC(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-M 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical class CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- RNVJQUPAEIQUTC-UHFFFAOYSA-N tricyclohexyltin Chemical class C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 RNVJQUPAEIQUTC-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical class C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は防汚防藻用ポリエステル系樹脂組成物
に関するものである。
従来、漁網、魚礁などの海洋構造物、船舶の船
底などにフジツボ、セルプラ、カキ、ホヤ、カサ
ネカンザシなどの海洋生物および緑藻、褐藻、珪
藻など藻類が付着、生長し、各種の被害、たとえ
ば漁網の網目が閉塞して海水の流通が低下した
り、魚類の生長が悪化したり、付着生物にもとづ
く重量の増大により潮流抵抗が大きくなり、海洋
構造物の破壊が助長されたり、船舶の推進効率が
低下したりするなどの障害が起ることが知られて
いる。
この海洋生物や藻類による上記被害を防止する
ために、各種の防汚防藻剤を配合した樹脂組成物
を前記漁網、魚礁あるいは船底などに塗布し、防
汚性被膜を形成させる手段が広く行われている
が、これら防汚防藻用樹脂組成物には長期に亘つ
て安定した防汚防藻効果を示すことが要求され
る。このような効果を得るには、防汚薬剤の性能
にもよるが、塗膜の耐久性及び防汚薬剤の水中へ
の溶出を長期間にわたつて有効濃度が溶出し得る
ものが要求され、塗膜形成に関与するビヒクルと
しての樹脂の役割はきわめて大きい。
一方近年水中防汚化を必要とする対象物が多様
化しているが、漁網、海洋構造物、船舶なども大
半が合成樹脂でできており、合成樹脂類との良好
な接着性を有するビヒクルが要望されている。
しかし従来用いられている油性系、ビニル系あ
るいは塩化ゴム系などは処理物体への密着性が悪
くて剥離しやすく耐久性に乏しい欠点があつた。
またアクリル樹脂中に多量の水酸基を導入させた
り、水易溶性物質を混入させたりして防汚薬剤の
溶出を良好にしたものも合成樹脂製品への密着性
が劣り、耐久性が悪く、長期間にわたつて防汚薬
剤の溶出を持続し防汚効果を長期間保持する性能
面でも良くない。
特開昭53−114920号公報にはビヒクルとして低
結晶化度のエチレン単独重合体またはエチレン共
重合体を用いたものが開示されているが、このも
のも接着性が悪く、また防汚薬剤の溶出速度が遅
いためか防汚効果があまり良くない。特公昭54−
37008号公報にはビヒクルとしてアクリル酸エス
テル共重合体およびメタクリル酸エステル共重合
体が提案されているがこのものも合成樹脂類との
接着性が十分でなく、防汚効果も短期間の間は良
いが長期間防汚効果を持続する点で十分でない。
本発明者等はこれらの観点から鋭意研究を行つ
た結果、上記の欠点のないビヒクルとしての樹脂
を見い出し、本発明を提案するに到つたのであ
る。すなわち本発明はビヒクル、防汚薬剤および
その他の添加物から防汚被膜を形成させるにあた
り該ビヒクルの一部又は全部にポリテトラメチレ
ングリコールおよび／またはイソフタール酸を共
重合成分とするポリブチレンテレフタレート共重
合体を使用することを特徴とする水中防汚用樹脂
組成物である。
本発明のビヒクルとして用いられるポリブチレ
ンテレフタレート共重合体としては、
(1)ポリテトラメチレングリコール共重合ポリブ
チレンテレフタレート、(2)イソフタール酸共重合
ポリブチレンテレフタレート、(3)ポリテトラメチ
レングリコールとイソフタール酸とを共重合した
ポリブチレンテレフタレート共重合体がある。
(1)のポリテトラメチレングリコール共重合ポリ
ブチレンテレフタレートとしてはポリテトラメチ
レングリコールの共重合比率が10〜60重量％のも
のがよい。共重合比率が10重量％より少ないと被
膜の硬さがかたくなり、例えば漁網に使用すると
硬くなつて取り扱いにくく、剥離しやすくなり耐
久性が劣つてくる。共重合比率を60重量％より多
くすると被膜強度が低下しやはり耐久性が低下す
る。(2)のイソフタール酸共重合ポリブチレンテレ
フタレートとしてはイソフタール酸の共重合比率
が20〜60重量％の範囲内のものがよい。イソフタ
ール酸の共重合比率が20重量％より少ないと被膜
の硬さがかたくなり、共重合比率が60重量％より
多くなると被膜強度が低下しやはり耐久性が低下
する。同様にポリテトラメチレングリコールとイ
ソフタル酸とを共重合したポリブチレンテレフタ
レート共重合体としては柔軟性、被膜強度の点か
らポリテトラメチレングリコールの共重合比率が
15〜50重量％、イソフタール酸の共重合比率が10
〜25重量％の範囲内である三元共重合体が好まし
い。
本発明の防汚防藻用ポリエステル系樹脂組成物
としては上記の共重合ポリブチレンテレフタレー
トをビヒクルとしたものが良いが、これに従来公
知のポリエチレン、ロジン類、エチレン−酢酸ビ
ニル共重合体、アクリル酸エステル共重合体、メ
タクリル酸エステル共重合体などを本発明の趣旨
を変更しない範囲で混合してもさしつかえない。
本発明のビヒクルに含有させる防汚薬剤として
はいかなる種類の化合物でも良く、例えばトリフ
エニル錫化合物、トリブチル錫化合物、トリシク
ロヘキシル錫化合物などの有機錫化合物、酸化第
一銅、塩化第一銅、ナフテン酸第一銅などの銅化
合物、ジチオカーバメイト亜鉛、ビス（２−ピリ
ジルチオ−１−オキサイド）亜鉛などの亜鉛化合
物、テトラクロルイソフタロニトリル、イソシア
ヌル酸誘導体、チウラム化合物などの有機化合物
が使用される。このうち有機錫化合物、銅化合物
の使用が特に好ましい。また上記防汚薬剤を複数
組合せて使用しても良い。本発明のビヒクルに配
合する防汚薬剤の配合量は３重量％以上30重量％
以上が良い。防汚薬剤の配合量が３重量％より少
ないと防汚効果が小さく、配合量が30重量％より
多いと被膜の耐久性が低下するので好ましくな
い。
本発明の実施において任意に使用されるその他
の添加物としては酸化チタン、亜鉛華、弁柄、鉛
丹、カーボンブラツクなどの顔料、シアニングリ
ーンなどの染料、ベントナイト、タルク、ナフテ
ン酸コバルト、ナフテス酸マンガンなどの充填
剤、その他溶剤、改質剤などが挙げられる。
本発明のビヒクルはデイスパージヨン、エマル
ジヨンといつた溶液の状態で物体に塗布して使用
することも出来るが、好ましい使用法としては本
発明の組成物は耐熱性に優れるので乾式法が良
く、したがつて溶融させるか、溶融して塗布する
のが良い。
溶液による湿式法では溶融塗布する乾式法に比
べ合成樹脂類への接着性が劣るので耐久性の点で
不利である。
乾式法としては漁網などの糸状物の場合、糸状
物に溶融させた本発明の樹脂組成物をコーテイン
グし、その糸状物を編網して漁網にする方法、海
洋構造物の部材を成形する時にまだ熱した状態に
ある部材に本発明の防汚用樹脂組成物の粉末を噴
射して溶融コーテイングする方法、粘着剤を入れ
た防汚用樹脂組成物の粉末を噴射して物体の表面
に付着させた後、その物体を加熱して溶融させ耐
久性のある被覆をつくる方法などがある。これら
の方法のうち本発明の樹脂組成物を溶融塗布する
のに最も好ましい方法は糸状物に適用する場合で
あり、耐久性のある強固な被膜をつくることがで
きる。
本発明の防汚防藻用ポリエステル系樹脂組成物
をつくる場合、ビヒクルとしての共重合ポリブチ
レンテレフタレートを重合する時に防汚薬剤やそ
の他の添加剤を加えて作る方法、ビヒクルとして
の共重合ポリブチレンテレフタレートのチツプな
いし粉末に防汚薬剤やその他の添加剤をブレンド
後溶融成形して作る方法、低重合度のポリエチレ
ンなどに防汚薬剤やその他の添加剤を加えて溶融
後チツプ状に成形し、このものと共重合ポリブチ
レンテレフタレートとをブレンド後溶融成形して
つくる方法などがあるがいずれの方法でも良い。
本発明の防汚防藻用ポリエステル系樹脂組成物
は従来公知のものと比べ合成樹脂類への密着性
（接着性）が良く、この被膜の強度は強く、また
耐摩耗性も優れており、水中での耐加水分解性に
も優れもいるので水中防汚被覆として耐久性に優
れている。そのうえ、本発明の防汚防藻用ポリエ
ステル系樹脂組成物は従来公知のものと比べ長期
間の防汚効果を示す。本発明の樹脂組成物は柔軟
性に富んでおり、耐久性が良く、防汚効果も優れ
ているので糸状物に適用するのが最も好ましい。
この防汚防藻加工を行つた糸状物を漁網にし、定
置網および養殖用網などとして使用するのが好ま
しい。しかし魚礁、浮消波提などの海洋構造物、
FRP船などの船舶の船底などにも適用し得る。
本発明の樹脂組成物はビヒクルとしての共重合ポ
リブチレンテレフタレートに混ぜる防汚薬剤とし
ては被膜の耐久性を損なわすに長期間防汚効果を
発揮させるためトリブチル錫化合物、トリフエニ
ル錫化合物など有機錫化合物、酸化第一銅、塩化
第一銅、ナフテン酸第一銅などの銅化合物をそれ
ぞれ単独ないしは併用するのが好ましい。
以下、参考例および実施例により本発明をさら
に具体的に説明する。
参考例 １
ジメチルテレフタレート89ｇ（0.45モル）、テ
トラメチレングリコール45ｇ（0.50モル）、平均
分子量2000のポリテトラメチレングリコール100
ｇ（0.05モル）、触媒としてチタニウムテトラブ
トキサイド25％ブタノール溶液1.5ml、２・６−
ジ−ｔ−ブチル−４−メチルフエノール0.15ｇを
撹拌器付き反応器に仕込み窒素置換を行ない、加
熱昇温した。反応温度を210℃以下にし約２時間
を要してメタノールを留出させた。系内温度を
245℃に上げ系内圧力を徐々に減圧にし、0.5mm
Hg以下の圧力において約1.5時間重合させ、極限
粘度2.4のポリテトラメチレングリコール共重合
ポリブチレンテレフタレートを得た。
参考例 ２
ジメチルテレフタレート59ｇ（0.30モル）、テ
トラメチレングリコール45ｇ（0.50モル）、ジメ
チルイソフタレート40ｇ（0.20モル）、触媒とし
てチタニウムテトラブトキサイド25％ブタノール
溶液1.5ml、２・６−ジ−ｔ−ブチル−４−メチ
ルフエノール0.15ｇを撹拌器付き反応器に仕込み
窒素置換を行ない加熱昇温した。以後参考例−１
と同様の操作で極限粘度2.0のイソフタール酸共
重合ポリブチレンテレフタレートを得た。
参考例 ３
ジメチルテレフタレート59ｇ（0.30モル）、テ
トラメチレングリコール45ｇ（0.50モル）、平均
分子量2000のポリテトラメチレングリコール60ｇ
（0.03モル）、ジメチルイソフタレート34ｇ（0.17
モル）、触媒としてチタニウムテトラブトキサイ
ド25％ブタノール溶液1.5ml、２・６−ジ−ｔ−
グチル−４−メチルフエノール0.15ｇを撹拌器付
き反応器に仕込み、窒素置換を行ない加熱昇温し
た。以後参考例−１と同様の操作で極限粘度2.3
のポリテトラメチレングリコール、イソフタール
酸共重合ポリブチレンテレフタレートを得た。
実施例 １〜６
上記参考例により製造されたビヒクルとしての
共重合ポリブチレンテレフタレートに防汚薬剤お
よび各種充填剤を混入して加熱溶融し防汚用樹脂
組成物を得た。第１表に組成物の種類、組成割合
を示す。この防汚用樹脂組成物を加熱溶融し、ポ
リエチレンテレフタレート系（極限粘度0.7、単
糸10デニール、引張強度６ｇ／ｄ）を合糸、撚糸
してつくつたトワイン（２万デニール）に公知の
溶融コーテイング装置で被膜厚さ0.5mmに被覆し
た。糸状物に被覆した防汚用樹脂組成物の密着性
（接着性）、耐摩耗性などの耐久性を評価するには
公知の糸−糸摩耗試験機で糸−糸摩耗試験を行な
うのが良い。摩耗条件は被覆トワインを直交さ
せ、一方の被覆トワインには荷重１Kgかけ、スト
ローク長50mmで60回／分の速度で摩耗した。被膜
が破壊しトワインの表面が露出するまでの摩耗回
数を測定し、比較例のサンプルとの対比で良悪の
評価を行なつた。その評価結果を第２表に示す。
防汚性能試験は被覆トワインを間隔50cmのステ
ンレス枠に３本合糸して取りつけ三重県尾鷲湾の
海面下１ｍの所に浸漬し、付着生物量を測定し
た。評価結果を第２表に示す。
比較例 １〜３
従来公知の防汚用樹脂組成物のビヒクルとして
(1) 旭ダウ社製低密度ポリエチレン（グレード：
M6545 密度0.915ｇ／cm3、MI45ｇ／10分）
(2) 住友化学社製エチレン−酢酸ビニル共重合体
（グレード“スミテード”DB−10、密度0.93
ｇ／cm3、MI70ｇ／10分、軟化点65℃）
(3) 協和ガス化学社製ポリメチルメタクリレート
（グレードGC−1000）
を用いて。以後実施例１と同様な方法でこれらの
ビヒクルに防汚薬剤を混入し加熱溶融して防汚用
樹脂組成物を得た。第１表に組成物の種類、組成
割合を示す。この防汚用樹脂組成物を加熱溶融
し、実施例１と同様な方法でポリエステル製トワ
インに溶融コーテイングした。この被覆トワイン
を実施例と同様な方法で耐久性の評価、防汚性能
試験を行ない第２表のような評価結果を得た。
第２表に示すように本発明の防汚用樹脂組成物
は従来公知の防汚用樹脂組成物に比べ耐久性が良
く、長期防汚性能を発揮するので優れたものとい
える。
The present invention relates to a polyester resin composition for stain and algae prevention. Traditionally, marine organisms such as barnacles, serpura, oysters, sea squirts, and algae such as green algae, brown algae, and diatoms adhere to and grow on marine structures such as fishing nets, fish reefs, and the bottoms of ships, causing various types of damage, such as fishing nets. Clogged nets can reduce the flow of seawater, impede the growth of fish, increase the weight of attached organisms, increase tidal current resistance, promote the destruction of marine structures, and reduce the propulsion efficiency of ships. It is known that problems such as a decrease in In order to prevent the damage caused by marine organisms and algae, a widely used method is to apply a resin composition containing various antifouling and algae agents to the fishing nets, fish reefs, ship bottoms, etc. to form an antifouling film. However, these anti-fouling and anti-algae resin compositions are required to exhibit stable anti-fouling and algae effects over a long period of time. In order to obtain such an effect, although it depends on the performance of the antifouling agent, the durability of the coating film and the ability to elute the antifouling agent into water at an effective concentration over a long period of time are required. The role of resin as a vehicle involved in coating film formation is extremely important. On the other hand, objects that require underwater antifouling have diversified in recent years, and most of them, such as fishing nets, marine structures, and ships, are made of synthetic resins, and vehicles that have good adhesive properties with synthetic resins are needed. It is requested. However, conventionally used oil-based, vinyl-based, or chlorinated rubber-based materials have the drawback of poor adhesion to the object being treated, and are easy to peel off and lack durability.
In addition, acrylic resins that have been introduced with a large amount of hydroxyl groups or mixed with easily water-soluble substances to improve the elution of antifouling agents have poor adhesion to synthetic resin products, poor durability, and long-lasting properties. It is also not good in terms of performance in maintaining the antifouling effect for a long period of time by sustaining the elution of the antifouling agent over a period of time. JP-A-53-114920 discloses a vehicle using an ethylene homopolymer or ethylene copolymer with a low degree of crystallinity, but this also has poor adhesion and is difficult to use as an antifouling agent. The antifouling effect is not very good, probably because the elution rate is slow. Tokuko Showa 54-
Publication No. 37008 proposes acrylic ester copolymers and methacrylic ester copolymers as vehicles, but these also do not have sufficient adhesion to synthetic resins, and their antifouling effects only last for a short period of time. Although it is good, it is not sufficient in terms of maintaining the antifouling effect for a long period of time. As a result of intensive research from these viewpoints, the present inventors have discovered a resin as a vehicle that does not have the above-mentioned drawbacks, and have come to propose the present invention. That is, the present invention provides a polybutylene terephthalate copolymer containing polytetramethylene glycol and/or isophthalic acid as a copolymer component in part or all of the vehicle to form an antifouling film from a vehicle, an antifouling agent, and other additives. This is an underwater antifouling resin composition characterized by using a combination. The polybutylene terephthalate copolymers used as the vehicle of the present invention include (1) polytetramethylene glycol copolymerized polybutylene terephthalate, (2) isophthalic acid copolymerized polybutylene terephthalate, and (3) polytetramethylene glycol and isophthalic acid. There is a polybutylene terephthalate copolymer copolymerized with The polytetramethylene glycol copolymerized polybutylene terephthalate (1) preferably has a polytetramethylene glycol copolymerization ratio of 10 to 60% by weight. If the copolymerization ratio is less than 10% by weight, the hardness of the coating will become hard, and when used for fishing nets, for example, it will become hard and difficult to handle, and will easily peel off, resulting in poor durability. If the copolymerization ratio exceeds 60% by weight, the strength of the coating will decrease and the durability will also decrease. The isophthalic acid copolymerized polybutylene terephthalate (2) is preferably one in which the copolymerization ratio of isophthalic acid is within the range of 20 to 60% by weight. If the copolymerization ratio of isophthalic acid is less than 20% by weight, the hardness of the film becomes hard, and if the copolymerization ratio exceeds 60% by weight, the strength of the film decreases and the durability also decreases. Similarly, as a polybutylene terephthalate copolymer made by copolymerizing polytetramethylene glycol and isophthalic acid, the copolymerization ratio of polytetramethylene glycol is
15-50% by weight, copolymerization ratio of isophthalic acid is 10
Terpolymers in the range ˜25% by weight are preferred. The antifouling and algae-preventing polyester resin composition of the present invention preferably uses the above-mentioned copolymerized polybutylene terephthalate as a vehicle. Acid ester copolymers, methacrylic ester copolymers, etc. may be mixed as long as the gist of the present invention is not changed. Any kind of compound may be used as the antifouling agent to be contained in the vehicle of the present invention, such as organotin compounds such as triphenyltin compounds, tributyltin compounds, and tricyclohexyltin compounds, cuprous oxide, cuprous chloride, and naphthenic acid. Copper compounds such as cuprous, zinc compounds such as zinc dithiocarbamate and zinc bis(2-pyridylthio-1-oxide), and organic compounds such as tetrachloroisophthalonitrile, isocyanuric acid derivatives, and thiuram compounds are used. Among these, use of organic tin compounds and copper compounds is particularly preferred. Further, a plurality of the above antifouling agents may be used in combination. The amount of the antifouling agent added to the vehicle of the present invention is 3% by weight or more and 30% by weight.
The above is good. If the amount of the antifouling agent is less than 3% by weight, the antifouling effect will be small, and if the amount is more than 30% by weight, the durability of the coating will be reduced, which is not preferable. Other additives that may be optionally used in the practice of the present invention include pigments such as titanium oxide, zinc white, Bengara, red lead, and carbon black, dyes such as cyanine green, bentonite, talc, cobalt naphthenate, and naphthenic acid. Examples include fillers such as manganese, other solvents, and modifiers. The vehicle of the present invention can be applied to an object in the form of a solution such as a dispersion or emulsion, but the preferred method of use is a dry method since the composition of the present invention has excellent heat resistance. Therefore, it is better to melt it or to apply it after melting it. The wet method using a solution has poorer adhesion to synthetic resins than the dry method using melt coating, so it is disadvantageous in terms of durability. As a dry method, in the case of filamentous objects such as fishing nets, the filamentous substance is coated with the molten resin composition of the present invention, and the filamentous substance is knitted into fishing nets, and when molding members of marine structures. A method of melt-coating by spraying the powder of the antifouling resin composition of the present invention on a still heated member, and a method of spraying the powder of the antifouling resin composition containing an adhesive to adhere to the surface of the object. After that, the object is heated to melt it and create a durable coating. Among these methods, the most preferred method for melt-coating the resin composition of the present invention is when it is applied to filamentous materials, and a durable and strong coating can be produced. When making the antifouling and algae polyester resin composition of the present invention, there is a method in which an antifouling agent and other additives are added during polymerization of copolymerized polybutylene terephthalate as a vehicle; This method is made by blending terephthalate chips or powder with antifouling agents and other additives and then melt-molding, or by adding antifouling agents and other additives to low polymerization degree polyethylene, melting it, and then forming it into chips. There is a method in which this material is blended with copolymerized polybutylene terephthalate and then melt-molded, but any method may be used. The antifouling and algae-preventing polyester resin composition of the present invention has better adhesion (adhesiveness) to synthetic resins than conventionally known compositions, has strong coating strength, and has excellent abrasion resistance. It also has excellent hydrolysis resistance in water, making it highly durable as an underwater antifouling coating. Moreover, the antifouling and antialgae polyester resin composition of the present invention exhibits a long-term antifouling effect compared to conventionally known compositions. The resin composition of the present invention is highly flexible, has good durability, and has an excellent antifouling effect, so it is most preferably applied to filamentous materials.
It is preferable to make the filamentous material subjected to this antifouling and algae treatment into a fishing net and use it as a fixed net, aquaculture net, etc. However, marine structures such as fish reefs and floating waves,
It can also be applied to the bottom of ships such as FRP ships.
In the resin composition of the present invention, the antifouling agent to be mixed with the copolymerized polybutylene terephthalate as a vehicle is an organic tin compound such as a tributyltin compound or a triphenyltin compound in order to exhibit a long-term antifouling effect without impairing the durability of the coating. It is preferable to use copper compounds such as cuprous oxide, cuprous chloride, cuprous naphthenate, etc. alone or in combination. Hereinafter, the present invention will be explained in more detail using Reference Examples and Examples. Reference example 1 89 g (0.45 mol) of dimethyl terephthalate, 45 g (0.50 mol) of tetramethylene glycol, 100 polytetramethylene glycol with an average molecular weight of 2000
g (0.05 mol), 1.5 ml of 25% butanol solution of titanium tetrabutoxide as a catalyst, 2.6-
0.15 g of di-t-butyl-4-methylphenol was charged into a reactor equipped with a stirrer, purged with nitrogen, and heated to raise the temperature. The reaction temperature was lowered to 210°C or less, and methanol was distilled off over about 2 hours. system temperature
Raise the temperature to 245℃ and gradually reduce the internal pressure to 0.5mm.
Polymerization was carried out for about 1.5 hours at a pressure below Hg to obtain polytetramethylene glycol copolymerized polybutylene terephthalate with an intrinsic viscosity of 2.4. Reference Example 2 59 g (0.30 mol) of dimethyl terephthalate, 45 g (0.50 mol) of tetramethylene glycol, 40 g (0.20 mol) of dimethyl isophthalate, 1.5 ml of 25% butanol solution of titanium tetrabutoxide as a catalyst, 2,6-di-t- 0.15 g of butyl-4-methylphenol was charged into a reactor equipped with a stirrer, purged with nitrogen, and heated to raise the temperature. Hereafter reference example-1
Isophthalic acid copolymerized polybutylene terephthalate with an intrinsic viscosity of 2.0 was obtained in the same manner as above. Reference example 3 59 g (0.30 mol) of dimethyl terephthalate, 45 g (0.50 mol) of tetramethylene glycol, 60 g of polytetramethylene glycol with an average molecular weight of 2000
(0.03 mol), dimethyl isophthalate 34 g (0.17
mol), 1.5 ml of titanium tetrabutoxide 25% butanol solution as catalyst, 2,6-di-t-
0.15 g of gutyl-4-methylphenol was placed in a reactor equipped with a stirrer, and the reactor was purged with nitrogen and heated to raise the temperature. Thereafter, the same operation as in Reference Example-1 was performed to obtain a limiting viscosity of 2.3.
Polytetramethylene glycol and isophthalic acid copolymerized polybutylene terephthalate was obtained. Examples 1 to 6 An antifouling agent and various fillers were mixed into the copolymerized polybutylene terephthalate as a vehicle produced in the above reference example, and the mixture was heated and melted to obtain an antifouling resin composition. Table 1 shows the types and composition ratios of the compositions. This antifouling resin composition is heated and melted, and polyethylene terephthalate (intrinsic viscosity 0.7, single yarn 10 denier, tensile strength 6 g/d) is doubled and twisted into twine (20,000 denier) yarn. A coating was applied to a thickness of 0.5 mm using a coating device. In order to evaluate the durability such as adhesion (adhesiveness) and abrasion resistance of the antifouling resin composition coated on a thread-like material, it is recommended to perform a thread-thread abrasion test using a known thread-thread abrasion tester. . The abrasion conditions were such that the coated twines were crossed at right angles, a load of 1 kg was applied to one coated twine, and the wear was carried out at a rate of 60 times/min with a stroke length of 50 mm. The number of wears until the coating was destroyed and the twine surface was exposed was measured, and the quality was evaluated by comparing it with a sample of a comparative example. The evaluation results are shown in Table 2. In the antifouling performance test, three coated twine threads were attached to a stainless steel frame with a spacing of 50 cm, and the coated twine threads were immersed 1 m below the sea surface in Owase Bay, Mie Prefecture, and the amount of attached biomass was measured. The evaluation results are shown in Table 2. Comparative Examples 1 to 3 As a vehicle for a conventionally known antifouling resin composition (1) Low density polyethylene manufactured by Asahi Dow Co., Ltd. (grade:
M6545 Density 0.915g/ cm3 , MI45g/10min) (2) Ethylene-vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (Grade "Sumitade" DB-10, density 0.93)
g/cm 3 , MI70 g/10 minutes, softening point 65°C) (3) Using polymethyl methacrylate (grade GC-1000) manufactured by Kyowa Gas Chemical Co., Ltd. Thereafter, an antifouling agent was mixed into these vehicles in the same manner as in Example 1, and the mixture was heated and melted to obtain an antifouling resin composition. Table 1 shows the types and composition ratios of the compositions. This antifouling resin composition was heated and melted, and melt-coated on a polyester twine in the same manner as in Example 1. The coated twine was evaluated for durability and tested for antifouling performance in the same manner as in the examples, and the evaluation results shown in Table 2 were obtained. As shown in Table 2, the antifouling resin composition of the present invention has better durability than conventionally known antifouling resin compositions and exhibits long-term antifouling performance, so it can be said to be excellent.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
はイソフタル酸を共重合成分とするポリブチレン
テレフタレート共重合体に防汚剤を配合してなる
防汚防藻用ポリエステル系樹脂組成物。1. A polyester resin composition for stain and algae prevention, which is prepared by adding an antifouling agent to a polybutylene terephthalate copolymer containing polytetramethylene glycol and/or isophthalic acid as a copolymerization component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1381781A JPS57128742A (en) | 1981-02-03 | 1981-02-03 | Antifouling and algae-proofing polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1381781A JPS57128742A (en) | 1981-02-03 | 1981-02-03 | Antifouling and algae-proofing polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57128742A JPS57128742A (en) | 1982-08-10 |
| JPH0117507B2 true JPH0117507B2 (en) | 1989-03-30 |
Family
ID=11843825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1381781A Granted JPS57128742A (en) | 1981-02-03 | 1981-02-03 | Antifouling and algae-proofing polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57128742A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090119276A (en) * | 2008-05-15 | 2009-11-19 | 엘에스산전 주식회사 | Electromagnetic switch and making method thereof |
| BRPI0923651A2 (en) | 2008-12-24 | 2019-09-24 | Chugoku Marine Paints | antifouling coating composition, antifouling coating film and base fouling prevention method |
| CN103608416B (en) | 2011-06-23 | 2015-12-02 | 中国涂料株式会社 | The manufacture method of binary liquid shape hydrolysis-type antifouling paint compositions, antifouling coat and antifouling base material |
-
1981
- 1981-02-03 JP JP1381781A patent/JPS57128742A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57128742A (en) | 1982-08-10 |
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