JPH0458510B2 - - Google Patents
Info
- Publication number
- JPH0458510B2 JPH0458510B2 JP7290484A JP7290484A JPH0458510B2 JP H0458510 B2 JPH0458510 B2 JP H0458510B2 JP 7290484 A JP7290484 A JP 7290484A JP 7290484 A JP7290484 A JP 7290484A JP H0458510 B2 JPH0458510 B2 JP H0458510B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- weight
- acid
- scaly
- soluble
- 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
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 11
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000003373 anti-fouling effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- -1 alkenyl ether Chemical compound 0.000 description 7
- 239000013535 sea water Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 241000206607 Porphyra umbilicalis Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000196251 Ulva arasakii Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は水溶出性塗膜を与える塗料組成物に関
する。さらに詳しくは、水または水溶液中で徐々
に溶出する重合体組成物をバインダーとした防汚
塗料組成物に関する。
海水が接触する構造物や機器類、例えば船舶、
海洋構造物、発電所冷却水系等の海水接触面に
は、アオサ、アオノリ、フジツボ、ムラサキイガ
イ、セルプラ等の動植物が付着し（以下汚損とい
う）、構造物や機器類本来の機能をそこなうこと
がある。
これに対し、従来からこれら動植物の付着を防
ぐ方法（以下防汚という）が種々試みられてきた
が、現在主流をなすものは三有機錫化合物、亜酸
化銅、ロダン第一銅などの化学物質を配合した塗
料を機器、構造体に塗布するか、または塩素およ
びその化合物（例えば次亜塩素酸ソーダなど）を
海水に注入する方法（以下、薬剤形防汚方法とい
う）である。しかしながら薬剤形防汚方法は、塩
素の如く、管理をあやまると高濃度で放出されて
有用な海産生物を斃死させたり、銅化合物の如く
分解無毒化しないため、特定海域に徐々に蓄積し
て生物への転移を起すなど、環境汚染を完全には
さけられない。
汚損の本質は、植物の胞子または動物の幼生が
構造物・機器類の海水接触面に付着して生長する
ことであり、薬剤形防汚方法は、溶出または溶解
した薬剤が胞子や幼生を斃死または逃避せしめる
ことによつて達成されるものである。従つて薬剤
形防汚方法は本質的に環境汚染の可能性を秘めて
いるものである。
本発明者等は、上記の問題について考究し、薬
剤を用いずに防汚する方法を鋭意研究した結果、
水または水溶液中で表面から徐々に溶出し、汚損
生物の付着基盤である塗膜を消失せしめ、定着し
た汚損生物を脱落せしめる水溶出性塗料組成物を
完成した。
すなわち本発明は、水溶出性樹脂に、鱗片状顔
料を配合することを特徴とする水溶出性塗料組成
物である。
本発明で用いる水溶出性樹脂は、
(A)成分として一般式(1)で示される単量体を５〜
75重量％
式中、R1はＨ，CH3または
CH2COO（CmH2mO）nR2，R2はＨまたは炭素数
１〜28の炭化水素基、CmH2mOはオキシアルキ
レン基、ｍは２〜４の整数、ｎは１〜200の整数
である。
(B)成分として重合性不飽和カルボン酸またはそ
の塩３〜55重量％、
(C)成分として疎水性の重合性不飽和単量体15〜
80重量％の共重合体である。
水溶出性樹脂に用いる(A)成分は、水溶性の単量
体であるアクリル酸、メタクリル酸、またはイタ
コン酸に、炭素数２〜４のアルキレンオキシドで
あるエチレンオキシド、プロピレンオキシド、ブ
チレンオキシドまたはテトラヒドロフランがカル
ボキシル基当り１〜200モル、好ましくは１〜30
モル付加した化合物、またはこの化合物の炭素数
１〜28、好ましくは１〜22のアルキルエーテル、
アルケニルエーテルまたはアルキルフエニルエー
テルである。
アルキレンオキシドの付加モル数が200モルを
越えると共重合反応がおこりにくくなり、アルキ
ルエーテル、アルケニルエーテルまたはアルキル
フエニルエーテルの炭化水素基の炭素数が28を越
えると水溶性が低下する。
(B)成分は、水溶性の単量体であるアクリル酸、
メタクリル酸、クロトン酸等の一塩基酸あるいは
マレイン酸、フマル酸、イタコン酸等の二塩基酸
またはこの二塩基酸の炭素数１〜22のアルキルあ
るいはアルケニルモノエステルのほか、これらカ
ルボン酸類のリチウム塩、ナトリウム塩、カリウ
ム塩、アンモニウム塩、炭素数１〜４のアルキル
アミン塩、モノエタノールアミン塩、ジエタノー
ルアミン塩、トリエタノールアミン塩などであ
る。
(C)成分は、疎水性の単量体であるアクリル酸エ
ステル類、メタクリル酸エステル類、酢酸ビニ
ル、スチレン、α−メチルスチレン、アクリロニ
トリル、塩化ビニル、ブタジエン、クロロプレン
などである。
本発明で用いる水溶出性樹脂は、(A)成分５〜75
重量％、(B)成分３〜55重量％および(C)成分15〜80
重量％、好ましくは(A)成分10〜70重量％、(B)成分
５〜55重量％および(C)成分20〜75重量％の共重合
体である。水溶出性樹脂の水溶性、強度、柔軟性
は、それら(A)，(B)，(C)各成分の種類、割合および
共重合体の分子量を適当に選ぶことにより調整す
ることができる。
(A)、(B)両成分は水溶出性樹脂に適度な水溶性を
付与するのに必要であり、また該組成物が水に均
一に溶出するためには両成分がそれぞれ一定の割
合で存在することが必である。(A)、(B)両成分がと
もに前記の範囲より大きいと、水に対する溶解度
が大きくなり過ぎるため好ましくなく、前記の範
囲より小さいと溶解度が小さすぎて防汚効果が弱
くなる。
(C)成分は強度や柔軟性を与え、また該樹脂組成
物の水に対する溶解度を調節するために必要であ
る。配合割合が前記の範囲より大きいと溶解度が
低下し、小さいと強度や柔軟性が低下するととも
に、水に対する溶解度が大きくなりすぎる。
水溶出性樹脂は(A)、(B)および(C)の各成分の混合
物を、ラジカル触媒の存在下で、溶液重合、乳化
重合あるいは懸独重合を行うことによつて容易に
得られる。
水溶出性樹脂の分子量は小さいほど水に対する
溶解度は大きいが、適度な溶解度を保つためには
重量平均分子量が5000〜500000、好ましくは
10000〜300000に調整することが望ましい。
本水溶出性樹脂は塗料中に５〜60重量％の範囲
で配合して使用するが、５重量％未満では連続塗
膜になりにくく、60重量％を越えると稠度が高く
なりすぎて、塗料として扱いにくくなる。
また本発明の塗料組成物に使用する鱗片状顔料
は、タルク、マイカ、鱗片状酸化鉄、ガラスフレ
ークであり、これらは塗料組成物を物体に塗布し
た後塗膜中で重なり合つて存在し、樹脂が溶解す
るにともなつて脱落して、付着した汚損生物のふ
るい落し効果をより大ならしめる。鱗片状顔料の
粒子径は50μ以上のものがより効果的であるが
50μ以下でも無効ではない。
鱗片状顔料は、塗料組成物中に１ないし40重量
％の範囲で１種または２種以上混合して使用す
る。鱗片状顔料の含有量が１重量％以内ではふる
い落し効果が十分でなく40重量％を超えると塗膜
の消耗速度が大きくなり、耐用年数が短くなる。
鱗片状顔料の他にチタン白、リトポン、バライ
タ、弁柄等の通常の顔料を塗料本来の性能を損わ
ない範囲であれば必要に応じて常法により混練し
て使用しても良い。
本塗料組成物はスプレー塗り、刷毛塗り、流し
塗り等の通常の方法で被塗装物に塗布することが
できる。
得られた塗膜は適当な強度と柔難性を有し、汚
損生物が付着しない程度の適度な速度で溶出し、
毒性のある薬剤を使用することなく水と接触する
材料への汚損生物の付着を防止すると共に、被覆
表面を常に均一な表面状態に維持することができ
る。
以下、製造例、実施例、比較例により本発明を
詳述する。文中特に断わらない限り、部、％は重
量部、重量％を示す。
水溶出性樹脂の製造
製造例 Ａ
撹拌機、窒素吹込みライン、コンデンサーおよ
び排気ラインを付設した４ツ口フラスコ内に、前
記一般式〔）で示される化合物(A)としてポリオ
キシプロピレン（ｎ＝５）グリコールモノメタク
リレート50部、重合性不飽和酸(B)としてメタクリ
ル酸5.0部、その他の重合性不飽和単量体(C)とし
てメチルメタクリレート45部、重合開始剤として
Ｎ，N′−アゾビスイソブチロニトリル（以下
AIBNと略す）0.5部、イソプロパノール（以下
1PAと略す）400部を仕込み、窒素ガス流通下に
1PAの還流温度まで昇温し、引続き同温度で16時
間撹拌して重合反応を行つた。得られた重合体溶
液は透明液体であつた。重合体溶液を固形分50％
まで濃縮して重合体溶液Ａとした。重合体溶液Ａ
の粘度は気泡粘度計でχであり、ゲルパーミエー
シヨンクロマトグラフによる平均分子量は数平均
で13500、重量平均で52900であつた。
以下同様にして、第１表の(A)、(B)、(C)各成分を
第１表に示す割合で反応させ、水溶出性樹脂Ｂ〜
Ｋを得た。
得られた水溶出性樹脂Ａ〜Ｋを100mm×50mmの
ステンレス板の片面に膜厚300〜700μに塗布し、
このステンレス板を円筒状の固定枠に塗面が中心
に向くよう固定して海水を満した容器内に浸漬し
た。次いで容器中央に設置した撹拌機により水の
撹拌を行い、塗膜表面が常に水流で洗われる状態
にして30日間にわたつて溶出試験を行つた。この
時の水の流速は塗膜近傍で10cm／秒である。この
ステンレス板を１日後、５日後、30日後に取り出
して十分に乾燥したのち重量を測定し、塗膜比重
を１と仮定して、塗膜の重量減少量と塗布面積か
ら次の式により塗膜厚の減少量を求めた。
塗膜厚の減少量（μ）＝（初期重量（ｇ）−
重量（ｇ））×104／表面積（cm2）×密度（ｇ／cm3）
得られた結果を第３表に示す。なお水溶出性樹
脂の他の特性を第３表に示した。
The present invention relates to coating compositions that provide water-soluble coatings. More specifically, the present invention relates to an antifouling paint composition using a polymer composition that gradually dissolves in water or an aqueous solution as a binder. Structures and equipment that come into contact with seawater, such as ships,
Plants and animals such as sea lettuce, green laver, barnacles, mussels, and cellupa adhere to seawater contact surfaces such as marine structures and power plant cooling water systems (hereinafter referred to as contamination), which can impair the original functions of structures and equipment. . To deal with this, various methods have been tried to prevent the adhesion of these animals and plants (hereinafter referred to as antifouling), but the current mainstream methods are chemical substances such as triorganotin compounds, cuprous oxide, and cuprous Rodan. This method involves applying a paint containing the following to equipment and structures, or injecting chlorine and its compounds (for example, sodium hypochlorite) into seawater (hereinafter referred to as a drug-based antifouling method). However, chemical antifouling methods, like chlorine, can be released in high concentrations and kill useful marine life if not managed properly, and unlike copper compounds, which cannot be decomposed and detoxified, they can gradually accumulate in specific sea areas and cause the death of useful marine life. It is not possible to completely avoid environmental pollution, such as metastasis. The essence of fouling is that plant spores or animal larvae attach to and grow on the seawater contact surfaces of structures and equipment, and chemical antifouling methods kill the spores and larvae with eluted or dissolved drugs. Or, it can be achieved through escape. Therefore, pharmaceutical antifouling methods inherently have the potential for environmental pollution. The inventors of the present invention have considered the above-mentioned problems, and as a result of intensive research into antifouling methods without using chemicals,
We have completed a water-soluble paint composition that gradually dissolves from the surface in water or an aqueous solution, causes the paint film that is the base for the attachment of fouling organisms to disappear, and causes the fixed fouling organisms to fall off. That is, the present invention is a water-soluble coating composition characterized in that a scale-like pigment is blended into a water-soluble resin. The water-soluble resin used in the present invention contains 5 to 5 monomers represented by general formula (1) as component (A).
75% by weight In the formula, R 1 is H, CH 3 or CH 2 COO (CmH 2 mO) nR 2 , R 2 is H or a hydrocarbon group having 1 to 28 carbon atoms, CmH 2 mO is an oxyalkylene group, and m is 2 to 4 n is an integer from 1 to 200. 3 to 55% by weight of a polymerizable unsaturated carboxylic acid or its salt as component (B), 15 to 55% by weight of a hydrophobic polymerizable unsaturated monomer as component (C)
80% by weight copolymer. Component (A) used in the water-soluble resin is a water-soluble monomer such as acrylic acid, methacrylic acid, or itaconic acid, and an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran. is 1 to 200 mol, preferably 1 to 30 mol per carboxyl group.
a molar addition compound, or an alkyl ether of this compound having 1 to 28 carbon atoms, preferably 1 to 22 carbon atoms,
It is an alkenyl ether or an alkylphenyl ether. If the number of moles of alkylene oxide added exceeds 200 moles, the copolymerization reaction will be difficult to occur, and if the number of carbon atoms in the hydrocarbon group of the alkyl ether, alkenyl ether or alkylphenyl ether exceeds 28, water solubility will decrease. Component (B) is acrylic acid, which is a water-soluble monomer;
Monobasic acids such as methacrylic acid and crotonic acid, dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and alkyl or alkenyl monoesters having 1 to 22 carbon atoms of these dibasic acids, as well as lithium salts of these carboxylic acids. , sodium salt, potassium salt, ammonium salt, alkylamine salt having 1 to 4 carbon atoms, monoethanolamine salt, diethanolamine salt, triethanolamine salt, and the like. Component (C) includes hydrophobic monomers such as acrylic esters, methacrylic esters, vinyl acetate, styrene, α-methylstyrene, acrylonitrile, vinyl chloride, butadiene, and chloroprene. The water-soluble resin used in the present invention includes component (A) 5 to 75
Weight%, component (B) 3-55% by weight and component (C) 15-80
It is a copolymer of 10 to 70% by weight of component (A), 5 to 55% by weight of component (B), and 20 to 75% by weight of component (C). The water solubility, strength, and flexibility of the water-soluble resin can be adjusted by appropriately selecting the types and proportions of each component (A), (B), and (C) and the molecular weight of the copolymer. Both components (A) and (B) are necessary to impart appropriate water solubility to the water-soluble resin, and in order for the composition to dissolve uniformly in water, both components must be present at a certain ratio. It is necessary to exist. If both components (A) and (B) are larger than the above range, the solubility in water will be too high, which is undesirable. If it is smaller than the above range, the solubility will be too low and the antifouling effect will be weakened. Component (C) is necessary to impart strength and flexibility and to adjust the solubility of the resin composition in water. If the blending ratio is larger than the above range, the solubility will decrease, and if it is smaller, the strength and flexibility will decrease and the solubility in water will become too high. The water-soluble resin can be easily obtained by subjecting a mixture of components (A), (B), and (C) to solution polymerization, emulsion polymerization, or suspension polymerization in the presence of a radical catalyst. The smaller the molecular weight of the water-soluble resin, the greater its solubility in water; however, in order to maintain appropriate solubility, the weight average molecular weight should be between 5,000 and 500,000, preferably
It is desirable to adjust it to 10000-300000. This water-eluting resin is used by blending it into the paint in a range of 5 to 60% by weight, but if it is less than 5% by weight, it will be difficult to form a continuous coating, and if it exceeds 60% by weight, the consistency will become too high and the paint will become thicker. becomes difficult to handle. Further, the scaly pigments used in the coating composition of the present invention are talc, mica, scaly iron oxide, and glass flakes, which are present in an overlapping manner in the coating film after the coating composition is applied to the object, As the resin dissolves, it falls off, making the effect of sieving off attached fouling organisms even greater. It is more effective if the particle size of the scaly pigment is 50μ or more.
It is not invalid even if it is less than 50μ. The scaly pigments are used alone or in a mixture of two or more in the range of 1 to 40% by weight in the coating composition. If the content of the scaly pigment is less than 1% by weight, the sieving effect will not be sufficient, and if it exceeds 40% by weight, the rate of wear of the coating film will increase and the service life will be shortened.
In addition to the scaly pigments, ordinary pigments such as titanium white, lithopone, baryta, and Bengara may be used by kneading them in a conventional manner as required, as long as they do not impair the original performance of the paint. The present coating composition can be applied to the object to be coated by a conventional method such as spraying, brushing, flow coating, etc. The resulting coating film has appropriate strength and flexibility, and dissolves at an appropriate rate to prevent fouling organisms from adhering to it.
It is possible to prevent fouling organisms from adhering to materials that come into contact with water without using toxic chemicals, and to maintain the coated surface in a uniform surface condition at all times. The present invention will be explained in detail below using production examples, examples, and comparative examples. Unless otherwise specified in the text, parts and % indicate parts by weight and % by weight. Production example of water-eluting resin A: In a four-necked flask equipped with a stirrer, nitrogen blowing line, condenser and exhaust line, polyoxypropylene (n= 5) 50 parts of glycol monomethacrylate, 5.0 parts of methacrylic acid as the polymerizable unsaturated acid (B), 45 parts of methyl methacrylate as the other polymerizable unsaturated monomer (C), and N,N'-azo as the polymerization initiator. Bisisobutyronitrile (hereinafter
(abbreviated as AIBN) 0.5 part, isopropanol (hereinafter referred to as
Pour 400 parts (abbreviated as 1PA) and place under nitrogen gas flow.
The temperature was raised to a reflux temperature of 1 PA, and the polymerization reaction was subsequently carried out by stirring at the same temperature for 16 hours. The resulting polymer solution was a transparent liquid. Polymer solution with solid content of 50%
Polymer solution A was obtained by concentrating the solution to 100%. Polymer solution A
The viscosity was χ as determined by a bubble viscometer, and the average molecular weight determined by gel permeation chromatography was 13,500 on the number average and 52,900 on the weight average. In the same manner, components (A), (B), and (C) in Table 1 were reacted in the proportions shown in Table 1, and water-soluble resins B to
I got K. The obtained water-eluting resins A to K were applied to one side of a 100 mm x 50 mm stainless steel plate to a film thickness of 300 to 700 μ.
This stainless steel plate was fixed to a cylindrical fixed frame with the painted surface facing the center, and immersed in a container filled with seawater. Next, the water was stirred using a stirrer placed in the center of the container, and an elution test was conducted for 30 days with the surface of the coating constantly being washed with a stream of water. The flow rate of water at this time was 10 cm/sec near the coating film. The stainless steel plate was taken out after 1 day, 5 days, and 30 days, and after sufficiently drying, its weight was measured. Assuming that the specific gravity of the coating film was 1, the following formula was used based on the weight loss of the coating film and the coated area. The amount of decrease in film thickness was determined. Amount of decrease in coating film thickness (μ) = (Initial weight (g) -
Weight (g) x 10 4 /Surface area (cm 2 ) x Density (g/cm 3 ) The results obtained are shown in Table 3. Table 3 shows other properties of the water-soluble resin.
【表】
実施例 １〜40，比較例 １〜６
水溶出性樹脂Ａ〜Ｋのうち、比較的高溶出量で
あるＡ、Ｂ、中程度であるＦ、低溶出量である
Ｅ、Ｉの５水溶出性樹脂を用いて、第２表に示す
配合で実施例１〜40の塗料組成物を調製し、あら
かじめタールエポキシ塗料（JIS−K5664−１種）
を塗布した10×20cmの軟鋼板（JIS−Ｇ−3310）
に刷毛を用いて塗膜厚が1000μになるように塗
布、乾燥した後、兵庫県州本市在由良湾で筏から
水面下1.5ｍの所に浸漬し、汚損生物の付着状態
を観察した。また比較例１としてタールエポキシ
塗料を塗布したのみ試験板を同時に浸漬し、汚損
生物の付着状態を観察した。さらに比較例２〜６
として、鱗片状顔料を使用せず、チタン白のみを
配合して塗料組成物を調整し、実施例と同様に作
成した試験板を浸漬して、汚損生物の付着状態を
観察した。[Table] Examples 1 to 40, Comparative Examples 1 to 6 Among the water-soluble resins A to K, A and B have a relatively high elution amount, F has a medium elution amount, and E and I have a low elution amount. 5 Using a water-eluting resin, the coating compositions of Examples 1 to 40 were prepared according to the formulations shown in Table 2, and tar epoxy coatings (JIS-K5664-1 class) were prepared in advance.
10×20cm mild steel plate coated with (JIS-G-3310)
After coating with a brush to a coating thickness of 1000 μm and drying, the coating was immersed 1.5 m below the water surface from a raft in Zaiyura Bay, Shumoto City, Hyogo Prefecture, and the state of adhesion of fouling organisms was observed. Further, as Comparative Example 1, a test plate coated with tar epoxy paint was immersed at the same time, and the state of adhesion of fouling organisms was observed. Furthermore, comparative examples 2 to 6
A paint composition was prepared by blending only titanium white without using any scaly pigment, and a test plate prepared in the same manner as in the example was immersed to observe the state of adhesion of fouling organisms.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
第３表の浸漬試験結果から、海水に対する溶解
性が大きいほど付着生物が少なく、また鱗片状顔
料が防汚に効果的であることを示している。すな
わち実施例１〜８と比較例２、実施例９〜16と比
較例３、実施例17〜24と比較例４、実施例25〜32
と比較例５、実施例33〜40と比較例６がそれぞれ
対応するものであるが、いずれも鱗片状顔料を含
有する塗膜が、チタン白のみの塗膜より防汚力が
大きく、また、実施例33〜36と実施例37〜40の試
験結果に示されるように、樹脂が低溶出性の場合
には、鱗片状顔料が多い塗膜が、少ない塗膜より
防汚力が大きい。
本組成物は防汚剤を用いておらず、したがつて
海産生物に対する生理的影響がなく、環境汚染が
全くない、すぐれた防汚塗料である。[Table] The immersion test results in Table 3 show that the greater the solubility in seawater, the fewer attached organisms, and that the scaly pigment is effective in antifouling. That is, Examples 1 to 8 and Comparative Example 2, Examples 9 to 16 and Comparative Example 3, Examples 17 to 24 and Comparative Example 4, and Examples 25 to 32.
Comparative Example 5, Examples 33 to 40, and Comparative Example 6 correspond to each other, but in each case, the coating film containing the scaly pigment had greater antifouling power than the coating film containing only titanium white, and As shown in the test results of Examples 33 to 36 and Examples 37 to 40, when the resin has a low elution property, a coating film containing a large amount of scaly pigment has a greater antifouling power than a coating film containing a small amount of scaly pigment. This composition does not use an antifouling agent, so it is an excellent antifouling paint that has no physiological effects on marine organisms and does not cause any environmental pollution.
Claims (1)
％、 式中、R1はＨ，CH3または CH2COO（CmH2mO）nR2，R2はＨまたは炭素
数１〜28の炭化水素基、CmH2mOはオキシア
ルキレン基、ｍは２〜４の整数、ｎは１〜200
の整数である。 (B)： 重合性不飽和カルボン酸またはその塩３〜
55重量％、および (C)： 疎水性の重合性不飽和単量体15〜80重量％ の共重合体である水溶出性樹脂と、鱗片状顔料を
含有することを特徴とする水溶出性塗料組成物。 ２ (B)成分がマレイン酸、イタコン酸、これら二
塩基酸の半エステル化物、アクリル酸またはメタ
クリル酸である特許請求の範囲第１項記載の水溶
出性塗料組成物。 ３ 水溶出性樹脂を５〜60重量％、鱗片状顔料を
１〜40重量％含むものである特許請求の範囲第１
項または第２項記載の水溶出性塗料組成物。 ４ 鱗片状顔料がタルク、マイカ、鱗片状酸化鉄
またはガラスフレークである特許請求の範囲第１
項ないし第３項のいづれかに記載の水溶出性塗料
組成物。[Claims] 1 (A): 5 to 75% by weight of the monomer represented by general formula (1), In the formula, R 1 is H, CH 3 or CH 2 COO (CmH 2 mO) nR 2 , R 2 is H or a hydrocarbon group having 1 to 28 carbon atoms, CmH 2 mO is an oxyalkylene group, and m is 2 to 4 integer, n is 1 to 200
is an integer. (B): Polymerizable unsaturated carboxylic acid or its salt 3~
55% by weight, and (C): a water-eluting resin that is a copolymer of 15 to 80% by weight of a hydrophobic polymerizable unsaturated monomer, and a water-eluting resin characterized by containing a scaly pigment. Paint composition. 2. The water-soluble coating composition according to claim 1, wherein component (B) is maleic acid, itaconic acid, a half ester of these dibasic acids, acrylic acid or methacrylic acid. 3. Claim 1, which contains 5 to 60% by weight of water-soluble resin and 1 to 40% by weight of scaly pigment.
The water-soluble coating composition according to item 1 or 2. 4 Claim 1 in which the scaly pigment is talc, mica, scaly iron oxide, or glass flakes
The water-soluble coating composition according to any one of Items 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7290484A JPS60217277A (en) | 1984-04-13 | 1984-04-13 | Paint composition soluble in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7290484A JPS60217277A (en) | 1984-04-13 | 1984-04-13 | Paint composition soluble in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60217277A JPS60217277A (en) | 1985-10-30 |
| JPH0458510B2 true JPH0458510B2 (en) | 1992-09-17 |
Family
ID=13502799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7290484A Granted JPS60217277A (en) | 1984-04-13 | 1984-04-13 | Paint composition soluble in water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60217277A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808641A (en) * | 1986-07-31 | 1989-02-28 | Fujisawa Pharmaceutical Co., Ltd. | Concrete admixture |
-
1984
- 1984-04-13 JP JP7290484A patent/JPS60217277A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60217277A (en) | 1985-10-30 |
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