JPS6330569A - Underwater curing epoxy paint composition - Google Patents
Underwater curing epoxy paint compositionInfo
- Publication number
- JPS6330569A JPS6330569A JP17419786A JP17419786A JPS6330569A JP S6330569 A JPS6330569 A JP S6330569A JP 17419786 A JP17419786 A JP 17419786A JP 17419786 A JP17419786 A JP 17419786A JP S6330569 A JPS6330569 A JP S6330569A
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- resin
- epoxy resin
- epoxy
- acid
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 23
- 239000004593 Epoxy Substances 0.000 title abstract description 8
- 239000003973 paint Substances 0.000 title description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920000768 polyamine Polymers 0.000 claims abstract description 10
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 239000008199 coating composition Substances 0.000 claims description 10
- 229920006334 epoxy coating Polymers 0.000 claims description 7
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 11
- 239000000049 pigment Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 abstract 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 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 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl phosphate Chemical compound 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
技 術 分 野
本発明は水中硬化型エポキシ塗料組成物にががり、さら
に詳しくは海洋構造物、港湾、河川施設などの水中部お
よび干満帯の塗装に用いられるけ著作、耐水性に優れた
エポキシ樹脂を主剤とする塗料組成物に関するものであ
る。[Detailed Description of the Invention] Technical Field The present invention relates to an underwater curable epoxy coating composition, and more specifically, to a coating composition used for coating underwater parts and tidal zones of marine structures, ports, river facilities, etc. The present invention relates to a coating composition whose main ingredient is an epoxy resin with excellent water resistance.
従来技術
従来から水中硬化型塗料としては各種の塗料か知られて
いる。これらのうちエポキシ−ポリアミド樹脂系に顔料
などを加えた組成物はポリアミド樹脂の界面活性能を利
用し、水中での被塗面に濡れ易く工夫されたものである
がポリアミド樹脂が水に溶解しやすく、未硬１ヒ状憇で
水中へ溶出するため、それを防止するために顔料などで
塗料粘度を高くする必要がある。しがしながらこの粘性
が被塗面との濡れ性を低下させ、塗装作業性も著しく阻
害している。また硬ｆヒ膜の被塗面とのけ著作および耐
食性も充分とはいえず、長期間の実用は期待できない。BACKGROUND OF THE INVENTION Various types of paints have been known as underwater curable paints. Among these, compositions made by adding pigments to epoxy-polyamide resins take advantage of the polyamide resin's surfactant ability and are designed to easily wet the surface to be coated in water, but the polyamide resin dissolves in water. It easily dissolves into water in an unhardened, cast-like form, so in order to prevent this, it is necessary to increase the viscosity of the paint using pigments or the like. However, this viscosity reduces the wettability with the surface to be coated and significantly impairs coating workability. In addition, the hardness of the hard film on the coated surface and corrosion resistance are not sufficient, and long-term practical use cannot be expected.
一方、エポキシ−ポリアミン樹脂系に顔料などを加えた
組成物は一般に疎水性が強く、親水性である被塗面に対
し濡れ性が悪く、そのそのため数々の改良技術が提案さ
れている。たとえば界面活性剤などで親水性／疎水性の
バランスを調整し、被塗面との濡れ性を改良する方法が
あるが硬化膜の付着性を向上させるには至っていない。On the other hand, compositions prepared by adding pigments to epoxy-polyamine resins generally have strong hydrophobic properties and have poor wettability on the hydrophilic surface to be coated, and for this reason a number of improvement techniques have been proposed. For example, there are methods of adjusting the hydrophilicity/hydrophobicity balance using surfactants and the like to improve wettability with the coated surface, but this has not yet led to improved adhesion of the cured film.
また界面活性剤の使用は耐水性を低下させる問題を含ん
でいる。さらに別の技術としてエポキシ樹脂のリン酸に
よる変性の試みもなされているが、硬化膜の付着性に問
題がある。Furthermore, the use of surfactants has the problem of reducing water resistance. As another technique, attempts have been made to modify epoxy resins with phosphoric acid, but there are problems with the adhesion of the cured film.
発明が解決しようとする問題点
そこで水中で被塗面に容易に被膜でき、硬化膜の付着力
に優れ、且つ長期の防食に耐えうる水中硬化型エポキシ
塗料組成物が要望されており、かかる塗料組成物を提供
することが本発明目的である。Problems to be Solved by the Invention Therefore, there is a need for an underwater-curable epoxy coating composition that can be easily coated on the surface to be coated in water, has excellent adhesion of the cured film, and can withstand long-term corrosion protection. It is an object of the present invention to provide a composition.
問題点を解決するための手段
本発明にしたがえば上記目的を達成するため、エポキシ
樹脂とカルボン酸とを反応させて得られるカルボン酸変
性エポキシ樹脂と、ポリアミド樹脂またはポリアミン樹
脂とを樹脂成分として含むことを特徴とする二液型組成
物である水中硬化型エポキシ塗料組成物が提供せられる
。Means for Solving the Problems According to the present invention, in order to achieve the above object, a carboxylic acid-modified epoxy resin obtained by reacting an epoxy resin with a carboxylic acid, and a polyamide resin or a polyamine resin are used as resin components. Provided is an underwater curable epoxy coating composition that is a two-component composition comprising:
本発明においてはエポキシ樹脂の有する優れた塗膜性能
と硬化性を失うことなくカルボン酸とエポキシ樹脂の一
部を反応させることにより、分子内に極性基が導入され
、付着力の向上が達成せられる。In the present invention, a polar group is introduced into the molecule by reacting a portion of the epoxy resin with carboxylic acid without losing the excellent coating performance and curability of the epoxy resin, thereby achieving improved adhesion. It will be done.
本発明で使用するカルボン酸変性エポキシ樹脂はカルボ
ン酸とエポキシ樹脂とから製造することができ、通常こ
れら両者をエポキシ樹脂中のエポキシ基１当量に対し、
カルボン酸のカルボキシル基が０．０１〜０．５当量、
好ましくは０．０１〜０．３当量の割合となる如く反応
させる。カルボキシル基が０．０１当量未満であると塗
料作業性および硬化膜の付着性が悪くなる傾向を示し、
また０、５当量を越えると粘度が上昇し、共に好ましく
ない０反応温度は通常５０〜１５０″Ｃ程度で行う。ま
た反応促進剤として必要により第３級アミンを０．１％
以下添加してもよい。この反応においては溶剤は必ずし
も必要ではないが、溶剤の共存下で反応を行ってもよい
。この際の溶剤としては、芳香族系溶剤、ケトン系溶剤
、エーテル系溶剤などが挙げられ、これら溶剤の使用量
は目的とするカルボン酸変性エポキシ樹脂１００重量部
当たり、通常５〜５０重量部程度である。このようにし
て得られるカルボン酸変性エポキシ樹脂は通常液状であ
るが固体の場合は希釈剤などで溶解して使用することが
好ましい。エポキシ当量は４０００以下、好ましくは１
９０〜５００程度である。The carboxylic acid-modified epoxy resin used in the present invention can be produced from a carboxylic acid and an epoxy resin.
The carboxyl group of the carboxylic acid is 0.01 to 0.5 equivalent,
The reaction is preferably carried out at a ratio of 0.01 to 0.3 equivalents. If the carboxyl group is less than 0.01 equivalent, paint workability and cured film adhesion tend to deteriorate,
In addition, if the amount exceeds 0.5 equivalents, the viscosity will increase, which is not preferable.The reaction temperature is usually about 50 to 150"C. If necessary, 0.1% tertiary amine may be added as a reaction accelerator.
The following may be added. Although a solvent is not necessarily required in this reaction, the reaction may be carried out in the presence of a solvent. Examples of the solvent in this case include aromatic solvents, ketone solvents, ether solvents, etc. The amount of these solvents used is usually about 5 to 50 parts by weight per 100 parts by weight of the target carboxylic acid-modified epoxy resin. It is. The carboxylic acid-modified epoxy resin thus obtained is usually liquid, but if it is solid, it is preferably used after being dissolved with a diluent. Epoxy equivalent is 4000 or less, preferably 1
It is about 90-500.
本発明で原料として用いられるエポキシ樹脂は下記式、
Ｚ
Ｃ８２ＣＣＨ２０
○
（式中２は −Ｈｌ−Ｃ１ｆ、、−Ｃ２Ｈ５テある）で
示されるグリシジルエーテル基を分子内に少なくとも１
コ有するものであり、その代表的なものとしては、例え
ばビスフェノールＡのジグリシジルエーテル、ビスフェ
ノールＦのジグリシジルエーテル、フェノールノボラッ
クエポキシ樹脂、ビスフェノール類のアルキレンオキシ
ド付加物のジグリシジルエーテルなどが好適に用いられ
る。The epoxy resin used as a raw material in the present invention has the following formula:
Z C82CCH20 ○ At least one glycidyl ether group represented by (in the formula, 2 is -Hl-C1f, -C2H5) in the molecule.
Typical examples include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, phenol novolac epoxy resin, and diglycidyl ether of alkylene oxide adducts of bisphenols. It will be done.
本発明においてエポキシ樹脂の変性に用いられるカルボ
ン酸としては少なくとも１コのカルボキシル基を有する
カルボン酸であり、例えばギ酸、酢酸、プロピオン酸、
乳酸等のモノカルボン酸、蓚酸、マロン酸、コハク酸、
リンゴ酸、酒石酸、セバシン酸、マレイン酸、フタル酸
、グルタミン酸などのジカルボン酸、またクエン酸など
のトリカルボン酸などが挙げられ、特にリンゴ酸、酒石
酸、クエン酸のような分子内に少なくとも１コの水酸基
を有するジカルボン酸、トリカルボン酸が好ましい。The carboxylic acid used for modifying the epoxy resin in the present invention is a carboxylic acid having at least one carboxyl group, such as formic acid, acetic acid, propionic acid,
Monocarboxylic acids such as lactic acid, oxalic acid, malonic acid, succinic acid,
Examples include dicarboxylic acids such as malic acid, tartaric acid, sebacic acid, maleic acid, phthalic acid, and glutamic acid, and tricarboxylic acids such as citric acid. Dicarboxylic acids and tricarboxylic acids having a hydroxyl group are preferred.
本発明では上記のカルボン酸変性エポキシ樹脂の硬化剤
として通常のエポキシ樹脂用の硬化剤が用いられ、それ
らは例えば脂肪族系ポリアミン、芳香族系ポリアミン、
指環族系ポリアミン、ポリアミド、ポリメルカプタン等
でありうるが、就中ポリアミド樹脂、ポリアミン樹脂が
好ましい。これら硬Ｃヒ剤の使用量も通常の硬化剤とし
ての使用量であり、通常エポキシ基１当量に対しポリア
ミンの場合はアミン当量、ポリメルカプタンの場合はメ
ルカプタンの活性水素当量を０．５〜２．０当量程度使
用すればよい。In the present invention, ordinary curing agents for epoxy resins are used as curing agents for the above-mentioned carboxylic acid-modified epoxy resins, such as aliphatic polyamines, aromatic polyamines,
It may be a ring type polyamine, a polyamide, a polymercaptan, etc., but polyamide resins and polyamine resins are particularly preferred. The amount of these hardening agents used is also the amount used as a normal curing agent, and usually 0.5 to 2 amine equivalents for polyamines and 0.5 to 2 active hydrogen equivalents of mercaptans for polymercaptans are used for 1 equivalent of epoxy group. It is sufficient to use about .0 equivalent.
また本発明による水中硬化型エポキシ塗料組成物は従来
の水中硬化型塗料に用いられる顔料、骨材を必要に応じ
て適宜含有してもよい。用いられる顔料および骨材は着
色機能のほか、水中で塗装する際に被覆材料が水との比
重差により浮遊することを防止するためのものであり、
比重が大きくかつ耐食性に優れたものが好ましい。たと
えば、酸１ヒチタン、酸化亜鉛、酸化鉄、酸化アルミニ
ウム、アルミニウム粉、硫酸バリウム、硫酸カルシウム
、炭酸カルシウム、炭酸マグネシウム、タルク、クレー
、カオリン、マイカ、グラファイト、シリカ、珪藻土、
アスベストなどが挙げられる。Further, the underwater curable epoxy coating composition according to the present invention may optionally contain pigments and aggregates used in conventional underwater curable coatings. In addition to the coloring function, the pigments and aggregates used are used to prevent the coating material from floating due to the difference in specific gravity with water when painting underwater.
It is preferable that the material has a large specific gravity and excellent corrosion resistance. For example, titanium acid, zinc oxide, iron oxide, aluminum oxide, aluminum powder, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, talc, clay, kaolin, mica, graphite, silica, diatomaceous earth,
Examples include asbestos.
骨材としては、硼砂、ガラスフレーク、ガラス繊維、合
成繊維、天然または人造マイカジアスアイアンオキサイ
ドなどが挙げられる。顔料および骨材の配合量は全組成
物中の顔料、骨材の容積濃度として６０％以下が好才し
い。さらに所望によりこの塗料組成物中に界面活性剤、
揺変剤、シランカップリング剤、インヒビターなどの改
質剤、粘度調整のための非反応性希釈剤、溶剤などを加
えることも可能である。Examples of the aggregate include borax, glass flakes, glass fibers, synthetic fibers, natural or artificial mica diaceous iron oxide, and the like. The content of the pigment and aggregate is preferably 60% or less as a volume concentration of the pigment and aggregate in the entire composition. Furthermore, if desired, a surfactant may be added to this coating composition.
It is also possible to add modifiers such as thixotropic agents, silane coupling agents, and inhibitors, non-reactive diluents for viscosity adjustment, solvents, and the like.
本発明にかかる水中硬化型エポキシ塗料組成物は水中に
おいて容易に鋼材、コンクリートなどに刷毛、ローラー
、コテなどで施工分行うことができ、従来のエポキシ系
水中硬化塗料と比較して次の利点を有する。The underwater curable epoxy paint composition according to the present invention can be easily applied underwater to steel materials, concrete, etc. with a brush, roller, trowel, etc., and has the following advantages compared to conventional epoxy underwater curable paints. have
■被塗面との濡れ性が良く、塗装作業性が優れている。■Good wettability with the surface to be coated and excellent painting workability.
■硬化膜の付着性が優れている。■Excellent adhesion of cured film.
■電気的に高抵抗膜であり、耐食性が優れている。■It is an electrically high resistance film and has excellent corrosion resistance.
上記のとおり本発明の水中硬化型エポキシ塗料組成物は
水中塗装作業性に優れ、形成された塗膜は長期にわたっ
て防食効果が大きく、海洋構造物などの飛沫帯や没水部
などの塗装用材料として好適である。As mentioned above, the underwater curable epoxy coating composition of the present invention has excellent underwater coating workability, and the formed coating film has a large anticorrosion effect over a long period of time, and is a material for coating spray zones and submerged areas of marine structures. It is suitable as
以下に実施例、比較例を示して本発明をより具体的に説
明する。実施例および比較例において、部はすべて重量
による。尚、実施例および比較例における評価方法は次
のとおりである。EXAMPLES The present invention will be explained in more detail by showing Examples and Comparative Examples below. In the Examples and Comparative Examples, all parts are by weight. The evaluation method in Examples and Comparative Examples is as follows.
源も１ｌｉ１１
◎・・・ヘラによる１回のしごき塗りで被塗面を１００
％被覆できる状態
○・・・ヘラによる２回のしごき塗りで被塗面を１００
％被覆できる状態
Δ・・・ヘラによる３〜５回のしごき塗りで被塗面を１
００％被覆できる状態
×・・・ヘラによる６回以上のしごき塗りで被塗面を被
覆できる状態
゛ への゛れ
ヘラ塗装した硬化膜の被塗面との接触角を目視で観察。The source is also 1li11 ◎...100% of the surface to be coated with one stroke with a spatula
Condition where % can be covered ○...The surface to be coated can be coated with 100% by applying it twice with a spatula.
%Coverable condition Δ: Apply 3 to 5 times with a spatula to coat the surface to be coated.
00% coverage condition x: Condition where the coated surface can be coated by 6 or more strokes with a spatula The contact angle of the spatula-applied cured film with the coated surface was visually observed.
Ｏ・・・ ４５°より小
△・・・ ４５°〜９０゜
×・・・ ９０°より大
付−」１−」１
１０！ｌ■間隔のゴバン目試験による残存塗膜面積◎・
・・９５％以上
Ｏ・・・９４〜８０％
Δ・・・７９〜５０％
×・・・４９％以下
１１へｌ髭１に
塗膜の交流電気抵抗値
測定条件：電極面ｆｆ５０ｃｍ２、周波数１ ｋＨｚ測
定器 ：ＣＪＡ−３型剤食塗膜試験器（親電子工業社製
）
実施例１〜１７
第１表に示したエポキシ樹脂とカルボン酸を混合し、さ
らに反応促進剤としてＮ、Ｎ−ジメチルベンジルアミン
を０．０５％添加し、１３０°Ｃで３時間反応を行いカ
ルボン酸変性エポキシ樹脂を得た。該樹脂１００部に酸
化チタン１０部、タルク５０部、ガラスフレーク３０部
を混合し、硬ｆヒ剤を第１表に示した配合割合で配合し
、粘度調整剤として適当量の非反応性希釈剤（ハイゾー
ル５ＡＳ２９６、日本石油化学社製）を加えた塗料を水
中硬化型エポキシ塗料組成物とした。但し、実施例１７
では上記顔料を加えずクリヤーとして使用した。O... Smaller than 45° △... 45° ~ 90° ×... Larger than 90° -"1-"1 10! Remaining paint film area by cross-cut test at l ■ interval ◎・
...95% or more O...94 to 80% Δ...79 to 50% ×...49% or less To 11 l AC electrical resistance value of the coating on whisker 1 Measurement conditions: electrode surface ff50cm2, frequency 1 kHz measuring device: CJA-3 type agent food coating tester (manufactured by Shindenshi Kogyo Co., Ltd.) Examples 1 to 17 The epoxy resin and carboxylic acid shown in Table 1 were mixed, and N and N- were added as reaction accelerators. Dimethylbenzylamine was added in an amount of 0.05%, and the reaction was carried out at 130°C for 3 hours to obtain a carboxylic acid-modified epoxy resin. 10 parts of titanium oxide, 50 parts of talc, and 30 parts of glass flakes were mixed with 100 parts of the resin, and a hardening agent was added in the proportions shown in Table 1, and an appropriate amount of non-reactive diluent was added as a viscosity modifier. The paint containing the agent (Hysol 5AS296, manufactured by Nippon Petrochemical Co., Ltd.) was used as a water-curable epoxy paint composition. However, Example 17
In this case, the above pigment was not added and used as a clear.
予め１年間海水中で発錆させた厚さ３．２１１１ｍの鋼
板をワイヤーブラシでＳ ｔ −３（ＳＩＳ ０５−５
９００による）処理した鋼板を被塗基材とし、上記水中
硬化型エポキシ塗料組成物を海水中において、ヘラで約
３龍の厚さに塗布し、水中塗装牢業性、被塗面への濡れ
性を評価した。さらに浸漬１年後の硬化膜の付着性、電
気抵抗を測定した。以上の結果を第１表に示す。A 3.2111m thick steel plate that had been rusted in seawater for one year was polished with a wire brush.
900) treated steel plate as the base material to be coated, the above-mentioned underwater-curing epoxy coating composition was applied to a thickness of approximately 3 mm in seawater using a spatula, and the underwater coating durability and wettability of the coated surface were determined. The gender was evaluated. Furthermore, the adhesiveness and electrical resistance of the cured film after one year of immersion were measured. The above results are shown in Table 1.
実施例１８
実施例６の組成物にアルキルリン酸塩（エレクトロスト
リッパーＮ、花王アトラス社製）を０．５重量％添加し
、実施例６と同様の評価を行った。Example 18 0.5% by weight of an alkyl phosphate (Electrostripper N, manufactured by Kao Atlas Co., Ltd.) was added to the composition of Example 6, and the same evaluation as in Example 6 was performed.
結果を第１表に示す。The results are shown in Table 1.
比較例Ｉ
ＭＩ Ｌ−Ｐ−２８５７９（ＹＤ）の配合に従って塗料
を製造し、その塗料を用いて実施例と同様の評価を行っ
た。結果を第２表に示す。Comparative Example I A paint was manufactured according to the formulation of MI LP-28579 (YD), and the paint was evaluated in the same manner as in the examples. The results are shown in Table 2.
比較例２
ビスフェノールＡジグリシジルエーテル（エポキシ当量
１９０）１００部に実施例同様の顔料配合を同割合で混
合し、硬化剤を第２表に示した配合割合で配合して、比
較組成物を得た。この組成物を用いて実施例と同様の評
価を行った結果を第２表に示す。Comparative Example 2 A comparative composition was obtained by mixing 100 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190) with the same pigment formulation as in the example in the same proportion, and adding a curing agent in the proportion shown in Table 2. Ta. Table 2 shows the results of the same evaluation as in Examples using this composition.
比較例３
ビスフェノールＡジグリシジルエーテル（エポキシ当量
１９０）１００部とオルトリン酸２部を混合し、８０”
Ｃで５時間反応を行い、リン酸変性エポキシ樹脂を得た
。該樹脂１００部に実施例同様の顔料配合を同割合で混
合し、硬化剤を第２表に示した配合割合で配合して比較
組成物を得た。Comparative Example 3 100 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190) and 2 parts of orthophosphoric acid were mixed, and 80"
The reaction was carried out at C for 5 hours to obtain a phosphoric acid-modified epoxy resin. Comparative compositions were obtained by mixing 100 parts of the resin with the same pigment formulations as in the examples in the same proportions, and blending curing agents in the proportions shown in Table 2.
この組成物を用いて実施例と同様の評価を行った結果を
第２表に示す。Table 2 shows the results of the same evaluation as in Examples using this composition.
比較例４
比較例２にアルキルベンゼンスルホン酸塩を２部混合し
、比較組成物を得た。この組成物を用ｂ）で実施例と同
様の評価を行った結果を第２表に示す。Comparative Example 4 Two parts of an alkylbenzene sulfonate were mixed with Comparative Example 2 to obtain a comparative composition. This composition was evaluated in b) in the same manner as in Example, and the results are shown in Table 2.
比較例５
比較例２にオレイン酸を２部混合し、比較組成物を得た
。この組成物を用いて実施例と同様の評価を行った結果
を第２表に示す。Comparative Example 5 Two parts of oleic acid were mixed with Comparative Example 2 to obtain a comparative composition. Table 2 shows the results of the same evaluation as in Examples using this composition.
（以下余白）(Margin below)
Claims (4)
るカルボン酸変性エポキシ樹脂と、ポリアミド樹脂また
はポリアミン樹脂を樹脂成分として含むことを特徴とす
る水中硬化型エポキシ塗料組成物。(1) An underwater curable epoxy coating composition characterized by containing a carboxylic acid-modified epoxy resin obtained by reacting an epoxy resin and a carboxylic acid, and a polyamide resin or a polyamine resin as resin components.
ルボン酸とをエポキシ基１当量に対し、カルボキシル基
が０．０１〜０．５当量の割合となる量で反応させて得
られる樹脂である特許請求の範囲第１項記載の組成物。(2) A patent claim in which the carboxylic acid-modified epoxy resin is a resin obtained by reacting an epoxy resin and a carboxylic acid in an amount such that the ratio of carboxyl groups to 1 equivalent of epoxy group is 0.01 to 0.5 equivalents. The composition according to item 1.
囲第１項記載の組成物。(3) The composition according to claim 1, wherein the carboxylic acid is a polyhydric carboxylic acid.
−ＯＨ）を有するカルボン酸である特許請求の範囲第２
項記載の組成物。(4) Carboxylic acid has at least one hydroxyl group in the molecule (
-OH) Claim 2
Compositions as described in Section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17419786A JPS6330569A (en) | 1986-07-24 | 1986-07-24 | Underwater curing epoxy paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17419786A JPS6330569A (en) | 1986-07-24 | 1986-07-24 | Underwater curing epoxy paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6330569A true JPS6330569A (en) | 1988-02-09 |
| JPH0521949B2 JPH0521949B2 (en) | 1993-03-26 |
Family
ID=15974420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17419786A Granted JPS6330569A (en) | 1986-07-24 | 1986-07-24 | Underwater curing epoxy paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6330569A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234469A (en) * | 1988-03-16 | 1989-09-19 | Chugoku Marine Paints Ltd | Underwater curable resin composition |
| WO1998014488A1 (en) * | 1996-10-04 | 1998-04-09 | Ppg Industries, Inc. | Coating compositions with citric acid containing polymers for enhanced adhesion to substrates |
| EP0796903A3 (en) * | 1996-03-21 | 1998-05-06 | Dai Nippon Toryo Co., Ltd. | Underwater curable coating composition |
| US6169150B1 (en) | 1998-12-02 | 2001-01-02 | Ppg Industries Ohio, Inc. | Coating compositions with dicarboxylic half ester containing polymers and polyanhydride curing agents |
| CN106047048A (en) * | 2016-05-24 | 2016-10-26 | 杭州萧山临江化工制品有限公司 | Salt spray resistant coating for marine steel structures |
| WO2019198378A1 (en) * | 2018-04-13 | 2019-10-17 | 株式会社Moresco | Compound and use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5430248A (en) * | 1977-08-12 | 1979-03-06 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
| JPS5523143A (en) * | 1978-08-07 | 1980-02-19 | Asahi Chem Ind Co Ltd | Cold-setting resin composition |
| JPS5634765A (en) * | 1979-08-31 | 1981-04-07 | Kansai Paint Co Ltd | Cold curable coating composition |
| JPS5637077A (en) * | 1979-08-31 | 1981-04-10 | Kansai Paint Co Ltd | Anticorrosive method for steel structure |
| JPS58215463A (en) * | 1982-06-07 | 1983-12-14 | Harima Kasei Kogyo Kk | Epoxy resin composition for paint |
| JPS59221367A (en) * | 1983-05-31 | 1984-12-12 | Yokohama Rubber Co Ltd:The | Adhesive composition |
-
1986
- 1986-07-24 JP JP17419786A patent/JPS6330569A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5430248A (en) * | 1977-08-12 | 1979-03-06 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
| JPS5523143A (en) * | 1978-08-07 | 1980-02-19 | Asahi Chem Ind Co Ltd | Cold-setting resin composition |
| JPS5634765A (en) * | 1979-08-31 | 1981-04-07 | Kansai Paint Co Ltd | Cold curable coating composition |
| JPS5637077A (en) * | 1979-08-31 | 1981-04-10 | Kansai Paint Co Ltd | Anticorrosive method for steel structure |
| JPS58215463A (en) * | 1982-06-07 | 1983-12-14 | Harima Kasei Kogyo Kk | Epoxy resin composition for paint |
| JPS59221367A (en) * | 1983-05-31 | 1984-12-12 | Yokohama Rubber Co Ltd:The | Adhesive composition |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234469A (en) * | 1988-03-16 | 1989-09-19 | Chugoku Marine Paints Ltd | Underwater curable resin composition |
| EP0796903A3 (en) * | 1996-03-21 | 1998-05-06 | Dai Nippon Toryo Co., Ltd. | Underwater curable coating composition |
| WO1998014488A1 (en) * | 1996-10-04 | 1998-04-09 | Ppg Industries, Inc. | Coating compositions with citric acid containing polymers for enhanced adhesion to substrates |
| US5891960A (en) * | 1996-10-04 | 1999-04-06 | Ppg Industries, Inc. | Coating compositions with citric acid containing polymers for enhanced adhesion to substrates |
| US6169150B1 (en) | 1998-12-02 | 2001-01-02 | Ppg Industries Ohio, Inc. | Coating compositions with dicarboxylic half ester containing polymers and polyanhydride curing agents |
| CN106047048A (en) * | 2016-05-24 | 2016-10-26 | 杭州萧山临江化工制品有限公司 | Salt spray resistant coating for marine steel structures |
| WO2019198378A1 (en) * | 2018-04-13 | 2019-10-17 | 株式会社Moresco | Compound and use thereof |
| CN111971322A (en) * | 2018-04-13 | 2020-11-20 | 株式会社Moresco | Compound and use thereof |
| JPWO2019198378A1 (en) * | 2018-04-13 | 2021-02-12 | 株式会社Moresco | Compounds and their uses |
| JP2022159286A (en) * | 2018-04-13 | 2022-10-17 | 株式会社Moresco | Compound and use thereof |
| CN111971322B (en) * | 2018-04-13 | 2023-08-08 | 株式会社Moresco | Compounds and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0521949B2 (en) | 1993-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5005675B2 (en) | High solid type anticorrosion paint composition | |
| JP6153132B2 (en) | Epoxy resin composition | |
| JP5913762B1 (en) | Anticorrosion paint composition, paint film, ship and marine structure | |
| JPS61192372A (en) | Method for submerged painting of steel structure | |
| JPS6330569A (en) | Underwater curing epoxy paint composition | |
| JP6629539B2 (en) | Anticorrosion coating composition, anticorrosion coating, substrate with anticorrosion coating, and method for producing the same | |
| KR101553120B1 (en) | A manufacturing method of a fatty acid and a silane coupling agent modified epoxy resin, and coating composition for ship containing the modified epoxy resin | |
| JP2017025159A (en) | Anticorrosive coating material composition, anticorrosive coating film, and base material with anticorrosive coating film and method for producing the same | |
| JP5760740B2 (en) | Amine-based curing agent, epoxy resin composition containing amine-based curing agent, and cured product thereof | |
| JPS6333479A (en) | Coating material composition for underwater coating | |
| JPS63179973A (en) | Underwater curable paint composition | |
| KR20220023295A (en) | Solvent-free Coating Composition | |
| KR950006073B1 (en) | Silicon modified epoxy paint composition | |
| JPS62270668A (en) | Method of imparting corrosion-proofness to steel structure under water | |
| JP2896102B2 (en) | Paint composition | |
| JPS6330568A (en) | Underwater curing amine-modified epoxy paint composition | |
| JPH0229479A (en) | Underwater coating epoxy resin composition | |
| JP2783416B2 (en) | Underwater paintable underwater curable resin composition and underwater paint method for forming a coating film with the composition | |
| JP4445064B2 (en) | Heavy anticorrosion micro solvent type epoxy resin coating composition | |
| JPS62135519A (en) | Underwater-curable epoxy resin composition | |
| JPS63371A (en) | Underwater curing corrosion-resistant material composition | |
| JPS6191217A (en) | Protection of underwater structure | |
| JPH021774A (en) | Antifouling coating composition to be applied to wet surface | |
| JPH01129054A (en) | Epoxy resin composition for application to wet surface | |
| JPH03199229A (en) | Epoxy resin composition of under water coating type |