JPS6241632B2 - - Google Patents
Info
- Publication number
- JPS6241632B2 JPS6241632B2 JP57161773A JP16177382A JPS6241632B2 JP S6241632 B2 JPS6241632 B2 JP S6241632B2 JP 57161773 A JP57161773 A JP 57161773A JP 16177382 A JP16177382 A JP 16177382A JP S6241632 B2 JPS6241632 B2 JP S6241632B2
- Authority
- JP
- Japan
- Prior art keywords
- paint
- composition
- alkali silicate
- silicate
- organic polymeric
- 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
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003973 paint Substances 0.000 claims description 15
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 235000010261 calcium sulphite Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 241000316887 Saissetia oleae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 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
- 150000007513 acids Chemical class 0.000 description 1
- 231100000215 acute (single dose) toxicity testing Toxicity 0.000 description 1
- 238000011047 acute toxicity test Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000007227 biological adhesion Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-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
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- -1 pulp Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
本発明は海洋構築物、船舶、漁業設備、水槽な
どの塗装に好適な水中塗料組成物に関する。
近年、沿岸域での海洋開発に伴い、大型海洋構
築物の建造が増加している。これらの構築物は海
水による腐食の他に海洋生物の付着による腐食や
幣害を免れない。船舶では船底への海洋生物の付
着による抵抗の増加のため多大なエネルギーの損
失が大きな問題である。漁業設備では定置網や養
殖網への付着による死滅が報告され、海水を冷却
水として用いる沿岸の各種工場では配管内面への
生物付着による有効面積の減少やスクリーンの目
詰りのおそれがある。淡水の場合にも下水処理場
の浄化槽などへの藻類の付着による弊害が起きて
いる。
海水による腐食に対しては重防食方法の進歩
で、ある程度の対策が可能であるが、海洋生物や
藻類の付着防止方法は現在では満足できるものは
見出されていない。現状では含塩素水の散布や有
毒物質を含んだ塗料の塗装により付着生物を死滅
させるか忌避させる方法が、一般的に用いられて
いる。これらはいずれも有害物質が流出し、広い
水域に分散するため周囲の環境に及ぼす影響が無
視できない。たとえば船底塗料に使用を許可され
ている防汚剤は亜酸化銅や有機錫化合物などいず
れも毒性の高いものである。
本発明者らはこのような問題点を解決する水中
防汚塗料組成物を提供することを目的として種々
研究を重ねた結果次のような塗料組成物がきわめ
て高い安全性を有し、生物付着防止能を持つこと
を見出し本発明を完成した。
本発明はすなわち有機高分子物質をビヒクルと
した塗料基剤に、ケイ酸アルカリ水溶液を硬化剤
にて硬化させた粉度150メツシユ以下の組成物粉
末を上記有機高分子物質に対し10〜300重量％分
散させてなる水中塗料組成物である。
本発明に使用されるケイ酸アルカリは一般式
M2O・nSiO2、mH2Oで示され式中Ｍはカリウ
ム、ナトリウム、リチウムまたは四級アンモニウ
ムでありｎ＝0.5〜８である。この水溶液に加え
られる硬化剤としては各種鉱酸、多価金属の酸化
物、水酸化物、硫酸塩、亜硫酸塩、塩化物、硝酸
塩、炭酸塩、ケイフツ化物、リン酸塩、縮合リン
酸塩、金属等が挙げれる。特にケイ酸アルカリと
反応して硬化度の高い硬化剤が望ましく、このよ
うな例として酸化マグネシウム、酸化カルシウ
ム、硫酸カルシウム、亜流酸カルシウム、ケイフ
ツ化ナトリウム、金属亜鉛等が適当である。この
ような硬化剤を加え常温もしくは加熱して硬化、
乾燥させた後、粉砕して使用する。粉末の粒径は
150メツシユ以下が適当であり、250メツシユ以下
が特に望ましい。150メツシユより大いければ分
散不良を起しやすく、塗膜中のブツの混入やピン
ホールが生じやすくなる。ビヒクルとなる有機高
分子物質としてはエポキシ樹脂、ポリウレタン樹
脂、ケイ素樹脂などの熱硬化性樹脂や塩化ビニル
樹脂、酢酸ビニル樹脂、アクリル樹脂などの熱可
塑性樹脂の単独または混合物、共重合体が挙げら
れる。これらを有機溶剤溶液とし、または水系エ
マルジヨンとして塗料基剤を製造する。
本発明の目的である防汚効果またはケイ酸アル
カリ硬化物粉体の分散性を良好ならしめるために
は有機溶剤溶液が好ましい。このような塗料基剤
に上記のケイ酸アルカリ硬化物の粉末を配合分散
させるのであるが、粉末の配合量は有機高分子物
質に対し10〜300重量％の範囲が適当である。10
重量％未満では防汚効果が不十分であり、また、
300重量％をこえると塗膜形成が不完全であり、
密着性や耐水性等が低下する。本発明組成物に必
要に応じ添加される他の成分は充填剤、分散剤、
顔料、増粘剤、消泡剤、沈降防止剤などであり、
充填剤としてはタルク、カオリン、炭酸カルシウ
ム等の無機質粉末、アスベスト、パルプ、ガラス
等の繊維状物、顔料としては酸化チタン、酸化ク
ロム、ベンガラ等の無機顔料やフタロシアニン等
の有機顔料が挙げられる。このようにして得られ
た製品はケイ酸アルカリの硬化組成物を含むこと
により淡水中、海水中において顕著な防汚性を有
する。またケイ酸アルカリの硬化組成物はほぼ無
毒に近く（マウス経口投与急性毒性試験のLD50
値は約50000mg／Kgである）従来用いられている
防汚剤のごとく環境安全上の問題を考慮する必要
がない。またケイ酸アルカリと種々の有機高分子
エマルジヨンとよりなる塗料組成物は公知である
が、これらは一般に相溶性が悪くゲル化や分離が
生じやすい。さらに皮膜の形成能が十分でない等
の理由で水中塗料として使用するには適当でな
い。本発明の水中塗料組成物は有機質塗料中にケ
イ酸アルカリと硬化剤との反応生成物が均一に分
散された独特の構成を有し、有機質塗料の皮膜形
成能は損われることなく、またケイ酸アルカリお
よびその硬化剤成分との相互作用により水中にお
ける防汚効果が発揮されるものと考えられる。本
発明の塗料組成物を基材に塗布するにはスプレ
ー、ローラー、刷毛等各種の塗布方法が可能であ
る。基材としてはスレート、モルタル、コンクリ
ート、ケイ酸カルシウム等の無機材料またはアル
ミニウム板、鉄板、ステンレス板等の各種金属板
が挙げられる。
以下、実施例、比較例により本発明の効果を具
体的に説明する。なお組成についてはいずれも重
量基準である。
実施例、比較例
ケイ酸アルカリの硬化物は次のようにして作製
した。
配合１ ケイ酸ソーダ水溶液（固形分40％）15部
金属亜鉛 70部
亜流酸カルシウム 15部
配合２ ケイ酸ソーダ水溶液（固形分40％）15部
酸化マグネシウム 20部
炭酸カルシウム 65部
配合３ ケイ酸カリ水溶液（固形分30％） 20部
ケイフツ化ナトリウム 40部
酸化亜鉛 40部
配合４ ケイ酸ソーダ水溶液を150℃で乾燥硬化
させたもの
配合１〜４を十分に硬化、乾燥させた後、ベブ
ルミルで粉砕し、粒径150メツシユ以下のものを
用いる。次に第１表に示される有機高分子物質の
有機溶剤（キシロール／メチルイソブチルケトン
＝1/1）溶液またはエマルジヨンに充填剤、顔料
および上記配合例のケイ酸アルカリ硬化物粉末を
十分に攪拌混合して塗料組成物を調整した。基材
としてシヨツトブラストにより黒皮、錆、油分を
完全に除去した後、塩化ゴム系紡錆塗料を塗布し
た２×50×150mmの軟鋼板（JIS G3141）と５×
50×150mmのフレキシブル板（JIS A5403）を用
い、各塗料の乾燥膜厚みがほぼ50ミクロンになる
ようにスプレー塗装したものを試験板とした。
試験方法は次のとおりであり、その結果を第１
表に示す。
(i) 耐水性：試験板を水に720時間浸漬し表面を
目視観察する。
(ii) 防汚性：大阪湾の海面下１ｍおよび下水処理
場の浄化槽の水面下30cmに試験板を吊下げ１年
毎に海洋生物や藻類の付着の様子を観察する。
評価 ◎生物類の付着面積が ５％以下
〇 〃 ５〜10％
△ 〃 10〜30％
× 〃 30％以上
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an underwater coating composition suitable for coating marine structures, ships, fishing equipment, aquariums, and the like. In recent years, the construction of large marine structures has increased due to marine development in coastal areas. These structures are subject to not only corrosion by seawater but also corrosion and damage due to the attachment of marine organisms. A major problem with ships is the loss of a large amount of energy due to increased resistance due to the adhesion of marine organisms to the bottom of the ship. In fishing equipment, there have been reports of death due to adhesion to fixed nets and aquaculture nets, and in various coastal factories that use seawater as cooling water, there is a risk of a reduction in the effective surface area and clogging of screens due to organisms adhering to the inner surface of pipes. In the case of fresh water, harmful effects are also occurring due to algae adhering to septic tanks at sewage treatment plants. Advances in heavy-duty anti-corrosion methods have made it possible to take some measures against corrosion caused by seawater, but no satisfactory method has yet been found to prevent the adhesion of marine organisms and algae. Currently, methods commonly used include spraying chlorinated water or painting with paint containing toxic substances to kill or repel attached organisms. In all of these cases, harmful substances flow out and are dispersed over a wide area of water, so the impact they have on the surrounding environment cannot be ignored. For example, the antifouling agents permitted for use in ship bottom paints are highly toxic, such as cuprous oxide and organotin compounds. The present inventors have conducted various studies with the aim of providing an underwater antifouling paint composition that solves these problems, and as a result, the following paint composition has an extremely high level of safety and is resistant to biofouling. The present invention was completed by discovering that it has a preventive ability. In other words, the present invention involves adding a composition powder having a fineness of 150 mesh or less, which is obtained by curing an aqueous alkali silicate solution with a curing agent to a coating base containing an organic polymeric substance as a vehicle, to a paint base containing an organic polymeric substance in an amount of 10 to 300% by weight based on the organic polymeric substance. This is an underwater paint composition made by dispersing %. The alkali silicate used in the present invention has the general formula
It is represented by M2O.nSiO2 , mH2O , where M is potassium, sodium, lithium or quaternary ammonium, and n=0.5-8. Hardening agents added to this aqueous solution include various mineral acids, polyvalent metal oxides, hydroxides, sulfates, sulfites, chlorides, nitrates, carbonates, silicate, phosphates, condensed phosphates, Examples include metals. In particular, a curing agent that reacts with an alkali silicate and has a high degree of curing is desirable, and suitable examples include magnesium oxide, calcium oxide, calcium sulfate, calcium sulfite, sodium silicate, and metallic zinc. Add such a hardening agent and harden at room temperature or by heating.
After drying, crush and use. The particle size of the powder is
A value of 150 meshes or less is appropriate, and a value of 250 meshes or less is particularly desirable. If the mesh size is larger than 150, poor dispersion is likely to occur, and particles and pinholes are likely to occur in the coating film. Examples of organic polymeric substances that serve as vehicles include thermosetting resins such as epoxy resins, polyurethane resins, and silicone resins, and thermoplastic resins such as vinyl chloride resins, vinyl acetate resins, and acrylic resins, singly or in mixtures, and copolymers. . A paint base is prepared from these as a solution in an organic solvent or as an aqueous emulsion. An organic solvent solution is preferable in order to improve the antifouling effect or the dispersibility of the alkali silicate cured powder, which is the object of the present invention. The above-mentioned powder of the alkali silicate cured product is mixed and dispersed in such a paint base, and the amount of the powder blended is suitably in the range of 10 to 300% by weight based on the organic polymeric substance. Ten
If it is less than % by weight, the antifouling effect is insufficient, and
If it exceeds 300% by weight, the coating film formation will be incomplete.
Adhesion, water resistance, etc. decrease. Other components that may be added to the composition of the present invention as necessary include fillers, dispersants,
Pigments, thickeners, antifoaming agents, antisettling agents, etc.
Examples of fillers include inorganic powders such as talc, kaolin, and calcium carbonate, and fibrous materials such as asbestos, pulp, and glass. Examples of pigments include inorganic pigments such as titanium oxide, chromium oxide, and red iron oxide, and organic pigments such as phthalocyanine. The product thus obtained has remarkable antifouling properties in freshwater and seawater because it contains an alkali silicate hardening composition. In addition, the cured composition of alkali silicate is almost non-toxic (LD 50 in acute toxicity test for oral administration to mice).
(The value is approximately 50,000 mg/Kg) There is no need to consider environmental safety issues like conventionally used antifouling agents. Furthermore, coating compositions comprising alkali silicate and various organic polymer emulsions are known, but these generally have poor compatibility and are prone to gelation and separation. Furthermore, it is not suitable for use as an underwater paint because of its insufficient ability to form a film. The underwater paint composition of the present invention has a unique structure in which a reaction product of an alkali silicate and a hardening agent is uniformly dispersed in the organic paint, and the film-forming ability of the organic paint is not impaired. It is thought that the antifouling effect in water is exerted by the interaction with the acid alkali and its curing agent component. The coating composition of the present invention can be applied to a substrate by various methods such as spray, roller, brush, etc. Examples of the base material include inorganic materials such as slate, mortar, concrete, and calcium silicate, and various metal plates such as aluminum plates, iron plates, and stainless steel plates. Hereinafter, the effects of the present invention will be specifically explained using Examples and Comparative Examples. Note that all compositions are based on weight. Examples and Comparative Examples A cured product of alkali silicate was produced as follows. Formulation 1 Sodium silicate aqueous solution (solid content 40%) 15 parts Metallic zinc 70 parts Calcium sulfite 15 parts Formulation 2 Sodium silicate aqueous solution (solid content 40%) 15 parts Magnesium oxide 20 parts Calcium carbonate 65 parts Combination 3 Potassium silicate Aqueous solution (solid content 30%) 20 parts Sodium silicate 40 parts Zinc oxide 40 parts Blend 4 Sodium silicate aqueous solution dried and hardened at 150°C After thoroughly hardening and drying Blends 1 to 4, pulverize with a bevel mill. However, use particles with a particle size of 150 mesh or less. Next, fillers, pigments, and the alkali silicate hardened powder of the above formulation example are thoroughly stirred and mixed into an organic solvent (xylol/methyl isobutyl ketone = 1/1) solution or emulsion of the organic polymer substances shown in Table 1. A coating composition was prepared. As a base material, after completely removing black scale, rust, and oil by shot blasting, a 2 x 50 x 150 mm mild steel plate (JIS G3141) and 5 x
The test board was a 50 x 150 mm flexible board (JIS A5403) that was spray-painted with each paint so that the dry film thickness was approximately 50 microns. The test method is as follows, and the results are
Shown in the table. (i) Water resistance: The test plate is immersed in water for 720 hours and the surface is visually observed. (ii) Fouling resistance: Test plates are hung 1 m below the sea surface in Osaka Bay and 30 cm below the water surface in septic tanks at sewage treatment plants, and the state of adhesion of marine organisms and algae is observed every year. Evaluation ◎Biological adhesion area is 5% or less 〃 〃 5-10% △ 〃 10-30% × 〃 30% or more [Table]
Claims (1)
に、ケイ酸アルカリ溶液を硬化剤により硬化させ
た粒度150メツシユ以下の組成物粉末を上記有機
高分子物質に対し10〜300重量％分散してなる水
中塗料組成物。1. Composition powder with a particle size of 150 mesh or less, which is obtained by curing an alkali silicate solution with a curing agent, is dispersed in a paint base material containing an organic polymeric substance as a vehicle in an amount of 10 to 300% by weight based on the organic polymeric substance. Underwater paint composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16177382A JPS5951955A (en) | 1982-09-16 | 1982-09-16 | Underwater paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16177382A JPS5951955A (en) | 1982-09-16 | 1982-09-16 | Underwater paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5951955A JPS5951955A (en) | 1984-03-26 |
| JPS6241632B2 true JPS6241632B2 (en) | 1987-09-03 |
Family
ID=15741625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16177382A Granted JPS5951955A (en) | 1982-09-16 | 1982-09-16 | Underwater paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5951955A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014527563A (en) * | 2011-12-28 | 2014-10-16 | 上海墻特節能材料有限公司 | Inorganic dry powder architectural paint and production method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072697C (en) * | 1997-11-28 | 2001-10-10 | 化学工业部海洋化工研究院 | Non-toxic anti-pollution paint for sea |
| CN105925160B (en) * | 2014-11-05 | 2018-04-17 | 河北晨阳工贸集团有限公司 | A kind of high adhesion force wear-resistant engineering machinery water-repellent paint |
| CN110527362B (en) * | 2019-09-09 | 2021-08-31 | 王学芳 | Chemical reaction color system material, preparation method thereof and coating material prepared from chemical reaction color system material |
| CN111909595A (en) * | 2020-08-14 | 2020-11-10 | 常州市武进晨光金属涂料有限公司 | Water-based anticorrosive paint for metal protection and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49114637A (en) * | 1973-03-06 | 1974-11-01 |
-
1982
- 1982-09-16 JP JP16177382A patent/JPS5951955A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49114637A (en) * | 1973-03-06 | 1974-11-01 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014527563A (en) * | 2011-12-28 | 2014-10-16 | 上海墻特節能材料有限公司 | Inorganic dry powder architectural paint and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5951955A (en) | 1984-03-26 |
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