JPS5827756A - Curing agent for underwater paint - Google Patents
Curing agent for underwater paintInfo
- Publication number
- JPS5827756A JPS5827756A JP12692581A JP12692581A JPS5827756A JP S5827756 A JPS5827756 A JP S5827756A JP 12692581 A JP12692581 A JP 12692581A JP 12692581 A JP12692581 A JP 12692581A JP S5827756 A JPS5827756 A JP S5827756A
- Authority
- JP
- Japan
- Prior art keywords
- curing agent
- underwater
- bisphenol
- paints
- curing
- 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
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、エポキシ樹脂を主剤として用いる水中塗料の
硬化剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curing agent for underwater paints using an epoxy resin as a main ingredient.
従来、海洋における鋼鉄製構造物の防食は塗装や電気防
食の手段により行われて来た。通常仕様の塗装は海水の
作用を受ける場所では２〜３年の寿命を持つといわれて
おり、それ以上の長期間の防食を塗装にたよることはで
きない。また、電気防食を施すためには、巨大な設備と
冷顔の維持費を必要とするため、特殊な施設に対しての
み実施されて来た。飛沫帯や海中で鋼鉄製構造物を長期
間防食するためには、新しい技術の開発が望まれて来た
。海水中で鋼鉄製構造物に再塗装を施し、長期的に防食
を行うという考えは、こうした現状から生じ、その目的
に使用する塗料として米国人り曾−ド、Ｗ、ドリスコに
よってポリアミド系の、ζ。Conventionally, corrosion protection of steel structures in the ocean has been carried out by means of painting or cathodic protection. It is said that standard coatings have a lifespan of 2 to 3 years in areas exposed to seawater, and coatings cannot be relied upon to provide corrosion protection for longer than that. Furthermore, cathodic protection requires huge equipment and maintenance costs, so it has only been applied to special facilities. In order to provide long-term corrosion protection for steel structures in the splash zone and under the sea, it has been desired to develop new technologies. The idea of repainting steel structures in seawater to provide long-term corrosion protection arose from this current situation, and Americans Risode, W. and Drisco developed a polyamide-based paint for this purpose. ζ.
”硬化剤が開発された。しかし、この硬化剤は水中での
接着性に欠け、今日広く用いられているとはノ
言えないのが現状である。近年、こうした水中塗の内の
一件は、すでに特許権を取得した。（特許第９４２７２
１号、特公昭５６−２６２７１．特願昭５６−１１６１
６８）これらの硬化剤はいずれも水中で良好に接着し、
かつ、長期間の防錆能力を有しているが、それぞれ、改
良すべきわずかな欠点を有していた。すなわち、特許第
９４２７２１号の水中接着性基剤組成物は硬化せし゛む
るために紫外線の照射を要した。特本発明者らは、更に
容易に製造でき、海水中での作業性、硬化性、接着性が
すぐれ、かつ耐海水性の良好な水中硬化性塗料の開発研
究を進めて、多価アミン１モルに対してビスフェノ−／
Ｉ／Ａを０．２５モルから４モルの割合で添加し、溶解
させて製造する硬化剤である。本硬化剤は実施例に示す
ように、分離分析の手段である薄層クロマトグラフィー
および高速液体クロマトグラフィーでその成分を分離分
析することによって、反応生成物ではなく、ビスフェノ
ールＡと多価アミンの混合物であることが証明された。``A hardening agent has been developed. However, this hardening agent lacks adhesive properties underwater, and it cannot be said that it is widely used today.In recent years, one of these underwater coatings has been , has already obtained a patent right (Patent No. 94272)
No. 1, Special Publication No. 56-26271. Patent application 1161-1983
68) All of these hardeners adhere well in water;
Although they each have long-term rust prevention ability, they each have slight drawbacks that should be improved. That is, the underwater adhesive base composition of Patent No. 942721 required irradiation with ultraviolet rays in order to cure. In particular, the present inventors have carried out research and development to develop underwater curable paints that are easier to produce, have excellent workability, curing properties, and adhesion in seawater, and have good seawater resistance, and have developed polyvalent amine 1. bisphenol per mole
It is a curing agent produced by adding and dissolving I/A at a ratio of 0.25 mol to 4 mol. As shown in the examples, by separating and analyzing its components using thin layer chromatography and high performance liquid chromatography, which are means of separation analysis, we found that this curing agent is not a reaction product, but a mixture of bisphenol A and polyvalent amine. It was proven that.
本発明で用いられる多価アミンは、例えばエチレンジア
ミン、ジエチレとトリアミン、ジメチルｊアミノプロピ
ルアミン等脂肪族アミンはじめｍ −フェニレンジアミ
ン等の芳香族アミンを挙げることができる。これらアミ
ンは単独であるいは混合して用いることができる０
混合物中の多価アミンの量が０．２５モルより少ないと
ビスフェノールＡが多すぎて硬化剤として使用できない
。また４モルより多いと水中での作業性が悪かった。Examples of the polyvalent amine used in the present invention include aliphatic amines such as ethylene diamine, diethyl triamine, and dimethyl j-aminopropylamine, as well as aromatic amines such as m-phenylene diamine. These amines can be used alone or in combination. If the amount of polyvalent amine in the mixture is less than 0.25 mol, the amount of bisphenol A is too large to be used as a curing agent. Moreover, when the amount was more than 4 moles, workability in water was poor.
このようにして製造された硬化剤はエポキシ樹脂を主成
分とする塗料に対してすぐれた水中硬イし性を示した。The curing agent thus produced showed excellent underwater curing properties for paints containing epoxy resin as a main component.
次に実施例により本発明を更に詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
（実施例１）
１ス
−
の
と
ＤＳ
（実施例２）Ｈ
同上の硬化剤を薄層クロマトグラフィー（ＴＬＯ）
を及び高速液体クロマトグラフィー（）］ＰＬ’Ｏ）
で分 しま析した結果を下図に示す。
（“ア
の
の
こ
（
ア
フェノール人とアミンのみが認められた。ＴＬＣ展開条
件は担体にアルミナＥを用い、展開溶媒してアセトンを
使用した。ＨＰＬＯではＺｏｒｂａｘカラムを用いてメ
タノールを溶媒として用いた。(Example 1) 1S - DS (Example 2) H Same curing agent as above was subjected to thin layer chromatography (TLO)
and high performance liquid chromatography ()] PL'O)
The results of the analysis are shown in the figure below.
(Only aphenols and amines were observed. The TLC development conditions used alumina E as a carrier and acetone as a developing solvent. In HPLO, a Zorbax column was used and methanol was used as a solvent. there was.
ＰＬＯにおける伸出は紫外部（２５４ｎｍ）の吸収利用
した。このため紫外部に吸収の無いアミン、ＨＰＬＯで
は検出されていない。The extension in PLO utilized absorption in the ultraviolet region (254 nm). Therefore, it is not detected by HPLO, which is an amine that has no absorption in the ultraviolet region.
実施例３）
ビスフェノールＡ１モルに対してジエチレントリジン１
．２モルを混合して硬化剤を合成した。こ硬化剤Ｌｏｇ
をエビ：７−） ８２８ Ｌｏｇと３ｇのＴｉｏ２混合
物である主剤と混合して水中で塗装した七ろ、３時間後
に水中で完全に硬化した。Example 3) 1 mole of bisphenol A to 1 mole of diethylenetridine
．． A curing agent was synthesized by mixing 2 moles. This hardening agent Log
Shrimp: 7-) Shichiro was mixed with 828 Log and 3g of Tio2 mixture as a main ingredient and painted in water, and was completely cured in water after 3 hours.
実施例４）
ビスフェノールＡ４．５モルに対しジエチレントリジ２
５．５モルを混合した硬化剤を合成し、この昭和５７年
２月９日
特許庁長官 島 １）春 樹 殿
１、事件の表示
昭和５６年特許願第１２６９２５ 号
２ 発明の名称
水中塗料用硬化剤
３ 補正をする者
事件との関係 特許出願人
住所 東京都千代田区霞が関１丁目３番１号（＋１４）
氏名 工業技術院長 石 坂 誠 −４指定代理人
住所 広島県呉市広町１５０００番地
明 細 書
１、発明の名称
水中塗料用硬化剤
特許請求の範囲
多価アミン１モルに対してビスフェノールＡを、０．２
５モルから４モルの割合で添加し、溶解させてなる水中
塗料用硬化剤。Example 4) Diethylene tridi 2 for 4.5 mol of bisphenol A
Synthesized a curing agent mixed with 5.5 moles, and this was published on February 9, 1980 by the Commissioner of the Patent Office Shima 1) Haruki Tono 1, Indication of the case 1982 Patent Application No. 126925 2 Name of the invention For underwater paints Hardening agent 3 Relationship with the case of the person making the amendment Patent applicant address 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (+14)
Name: Makoto Ishizaka, Director of the Agency of Industrial Science and Technology -4 Designated Agent Address: 15000 Hiromachi, Kure City, Hiroshima Prefecture Specifications: 1. Name of the invention: Curing agent for underwater paints Claims: Bisphenol A per mole of polyvalent amine; 0.2
A curing agent for underwater paints that is added and dissolved at a ratio of 5 to 4 moles.
発明の詳細な説明
本発明は、エポキシ樹脂を主剤として用いる水中塗料の
硬化剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curing agent for underwater paints that uses an epoxy resin as a main ingredient.
従来、海洋における鋼鉄製構造物の防食は塗装や電気防
食の手段により行われて来た。通常仕様の塗装は海水の
作用を受ける場所では２〜３年の寿命を持つといわれて
おり、それ以上の長期間の防食を塗装にたよることはで
きない。また、電気防食を施すためには、巨大な設備と
多額の維持費を必要とするため、特殊な施設に対しての
み実施されて来た。飛沫帯や海中で鋼鉄製構造物を長期
間防食するためには、新しい技術の開発が望まれて来た
。海水中で鋼鉄製構造物に再塗装を施し、長期的に防食
を行うという考えは、こうした現状から生じ、その口約
に使用する塗料として米国人言えないのが現状である。Conventionally, corrosion protection of steel structures in the ocean has been carried out by means of painting or cathodic protection. It is said that standard coatings have a lifespan of 2 to 3 years in areas exposed to seawater, and coatings cannot be relied upon to provide corrosion protection for longer than that. In addition, cathodic protection requires huge equipment and a large amount of maintenance costs, so it has only been applied to special facilities. In order to provide long-term corrosion protection for steel structures in the splash zone and under the sea, it has been desired to develop new technologies. The idea of repainting steel structures in seawater to provide long-term corrosion protection arose out of this current situation, and the current situation is that Americans cannot say what paints they should use.
近年、こうした水中塗料の開発に対する要請は、水中溶
接後の防錆が水中溶接の発展と共に重要となるに伴って
、大きくなって来た。In recent years, the demand for the development of such underwater paints has increased as rust prevention after underwater welding has become important with the development of underwater welding.
本発明者は、こうした産業界の要請に答えるため、昭和
５０年度から、水中塗料の開発研究を進め、過去におい
て３件の水中塗料の特許を出願し、その内の一件はすで
に特許権を取得した。（特許第９４２７２１号特公昭５
６−２６２７］□１、桔願昭５５−１１６１６８ ）こ
れらの硬化剤はいずれも水中で良好に接着し、かつ、長
期間の防錆能力を有しているが、それぞれ、改良すべき
わずかな欠点を有していた。すなわち、特許第９４２７
２１号の水中接着性基剤組成物は硬化せしむるために紫
外線の照射を要した。持分・昭５６−２６２７１は着色
性に欠けていた。特願昭５５−１１６１６８は先の特許
の欠点は改良していたものの、合成原料が三成分系で合
成操作が、やや複雑であった。In order to respond to these industrial demands, the present inventor has been conducting research and development of underwater paints since 1975, and has applied for three patents for underwater paints in the past, one of which has already been patented. Obtained. (Patent No. 942721 Special Publication Showa 5
6-2627] □1, Kigansho 55-116168) All of these hardening agents have good adhesion in water and long-term rust prevention ability, but each has a few points that should be improved. It had drawbacks. That is, Patent No. 9427
The underwater adhesive base composition of No. 21 required irradiation with ultraviolet light to cure. Equity・Sho 56-26271 lacked coloring properties. Although Japanese Patent Application No. 116,168/1987 improved upon the drawbacks of the previous patent, the synthetic raw materials were a three-component system and the synthesis operations were somewhat complicated.
本発明者らは、更に容易に製造でき、海水中ての作業性
、硬化性、接着性がすぐれ、かつ耐海水性の良好な水中
硬化性塗料の開発研究を進めて、鋭意研究を重ねた結果
、水中で強力に付着し、製法が極めて容易な硬化剤を見
出し、この知見に基づいて本発明を成すに至った。すな
わち、本発明は多価アミン１モルに対してビスフェノー
ルＡを０．２５モルから４モルの割合で添加し、溶解さ
せて製造する硬化剤である。本硬化剤は実施例に示すよ
うに、分離分析の手段である薄層クロマトグラフィーお
よび高速液体クロマトグラフィーでその成分を分離分析
することによって、反応生成物ではなく、ヒスフェノー
ルＡと多価アミンの混合物であることが証明された。The inventors of the present invention have carried out extensive research to develop underwater curable paints that are easier to manufacture, have excellent workability, curing properties, and adhesion in seawater, and have good seawater resistance. As a result, a curing agent that adheres strongly in water and is extremely easy to manufacture was discovered, and based on this knowledge, the present invention was accomplished. That is, the present invention is a curing agent produced by adding and dissolving bisphenol A in a ratio of 0.25 to 4 moles per mole of polyvalent amine. As shown in the examples, this curing agent was obtained by separating and analyzing its components using thin layer chromatography and high performance liquid chromatography, which are means of separation analysis. proved to be a mixture.
とができる。これらアミンは単独であるいは混合して用
いることができる。I can do that. These amines can be used alone or in combination.
混合物中の多価アミンの量が０．２５モルより少ないと
ビスフェノールＡが多すぎて硬化剤として使用できない
。また４モルより多いと水中での作業性が悪かった。If the amount of polyvalent amine in the mixture is less than 0.25 mole, there will be too much bisphenol A to be used as a curing agent. Moreover, when the amount was more than 4 moles, workability in water was poor.
このようにして製造された硬化剤はエポキシ樹脂を主成
分とする塗料に対してすぐれた水中硬化性を示した。The curing agent thus produced showed excellent underwater curing properties for paints containing epoxy resin as a main component.
次に実施例により本発明を更に詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
（実施例１）
ビスフェノールＡ１モルに対してジエチレントリアミン
１モルを混合して硬化剤を合成した。この硬化剤１０
ａをエピコート８２８．１０ ａと混合して水中で塗装
した。塗膜は水中で３時間後、完全硬化した。(Example 1) A curing agent was synthesized by mixing 1 mol of diethylenetriamine with 1 mol of bisphenol A. This curing agent 10
a was mixed with Epicote 828.10 a and painted in water. The coating was completely cured after 3 hours in water.
（実施例２）
同上の硬化剤を薄層クロマトグラフィー（ＴＬＣ）及び
高速液体クロマトグラフィー（ＨＰＬＣ）で分析した結
果を第１図及び第２図に示す。(Example 2) The results of analyzing the above curing agent by thin layer chromatography (TLC) and high performance liquid chromatography (HPLC) are shown in FIGS. 1 and 2.
第１図及び第２図に示すように、硬化剤中にはビスフェ
ノールＡとアミンの反応物は見らレス、モノマーである
ビスフェノールＡとアミンのみがみとめられた。Ｔ’Ｌ
Ｃの展開条件は担体にアルミナＥを用い、展開溶媒と
してアセトンを使用した。As shown in FIGS. 1 and 2, no reaction product of bisphenol A and amine was found in the curing agent, and only bisphenol A and amine, which are monomers, were observed. T'L
The developing conditions for C were that alumina E was used as a carrier and acetone was used as a developing solvent.
ＨＰＬＣではゾルパックスＯＤＳカラム−を用いてメタ
ノールを溶媒として用いた。ＨＰＬＣにおける検出は紫
外部（２５４ｍｍ）の吸収を利用した。このため紫外部
に吸収の無いアミンは、１１１） Ｌ Ｃでは検出され
ていない。In HPLC, methanol was used as a solvent using a Solpax ODS column. Detection in HPLC utilized absorption in the ultraviolet region (254 mm). Therefore, amines that have no absorption in the ultraviolet region are not detected by 111) LC.
（実施例３）
ビスフェノールＡ１モルに対してジエチレントリアミン
１２モルを混合して硬化剤を合成した。(Example 3) A curing agent was synthesized by mixing 12 moles of diethylenetriamine with 1 mole of bisphenol A.
この硬化剤１０ｇのエピコート８２８．１０ Ｇと３ｇ
のＦＯ□の混合物である主剤と混合して水中で塗装した
ところ、３時間後に水中で完全に硬化した。10g of this curing agent, Epicoat 828.10G and 3g
When the mixture was mixed with a main agent which is a mixture of FO□ and painted in water, it was completely cured in water after 3 hours.
（実施例４） して水中塗装した。(Example 4) and painted underwater.
その結果を次の表に示す。The results are shown in the table below.
第１図は、硬化剤の薄層クロマトグラフィによる分析例
、第２図は、硬化剤の液体クロマトグラフィによる分析
例を示すものである。
１・・・・・・・・・ビスフェノールＡのスポット２・
・・・・・・・・アミンのスポット３・・・・・・・・
・ビスフェノールＡのピーク第１１！１
第２−図FIG. 1 shows an example of analysis of a curing agent by thin layer chromatography, and FIG. 2 shows an example of analysis of a curing agent by liquid chromatography. 1...Bisphenol A spot 2.
・・・・・・・・・Amine spot 3・・・・・・・・・
・Bisphenol A peak No. 11!1 Fig. 2
Claims (1)
５モルから４モルの割合で添加し、溶解させてなる水中
塗料用硬化剤。0.2 bisphenol A per mole of polyvalent amine
A curing agent for underwater paints that is added and dissolved at a ratio of 5 to 4 moles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12692581A JPS5856587B2 (en) | 1981-08-12 | 1981-08-12 | Curing agent for underwater paints |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12692581A JPS5856587B2 (en) | 1981-08-12 | 1981-08-12 | Curing agent for underwater paints |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5827756A true JPS5827756A (en) | 1983-02-18 |
| JPS5856587B2 JPS5856587B2 (en) | 1983-12-15 |
Family
ID=14947288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12692581A Expired JPS5856587B2 (en) | 1981-08-12 | 1981-08-12 | Curing agent for underwater paints |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5856587B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191217A (en) * | 1984-10-12 | 1986-05-09 | Nitto Electric Ind Co Ltd | Protection of underwater structure |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5981650U (en) * | 1982-11-25 | 1984-06-01 | 富士通テン株式会社 | Automotive power circuit |
| JPS59162720A (en) * | 1983-03-03 | 1984-09-13 | 神鋼電機株式会社 | Power source circuit of electronic part for vehicle |
-
1981
- 1981-08-12 JP JP12692581A patent/JPS5856587B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191217A (en) * | 1984-10-12 | 1986-05-09 | Nitto Electric Ind Co Ltd | Protection of underwater structure |
| JPH0572403B2 (en) * | 1984-10-12 | 1993-10-12 | Nitto Denko Corp |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5856587B2 (en) | 1983-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2357992C2 (en) | Anticorrosive coating compound with high content of non-volatile components, quick-set anticorrosive coating compound with high content of non-volatile components, ship or similar coating process, anticorrosive film with high content of non-volatile components and quick-set anticorrosive film with high content of nonvolatile components after coating, filmy ship and submarine construction | |
| US5707702A (en) | Epoxy pipelining composition and method of manufacture | |
| CN101643615B (en) | Polyaniline modified glass flake heavy-duty anti-corrosive coating and preparation method thereof | |
| KR910012056A (en) | 2-component epoxy resin composition | |
| US5059640A (en) | Epoxy corrosion-resistant coating | |
| RU2007146142A (en) | METHOD FOR THE FORMATION OF CRACK-RESISTANT RESISTANT EPOXY COATING AND THE PAINT COMPOSITION SUITABLE FOR SUCH METHOD | |
| JP2008543533A5 (en) | ||
| CN105008471A (en) | Anti-corrosion paint composition, anti-corrosion coating, and method for preventing corrosion of base material | |
| ATE182353T1 (en) | CATIONIC RESIN AND CAPED POLYISOCYANATE AS A CROSS-LINKING AGENT SUITABLE FOR USE IN ELECTROCOATING | |
| JP2001002986A (en) | Coating material composition | |
| JPS6411830A (en) | Organic composite plated steel plate excellent in press formability, weldability, electrocoating property and corrosion resistance | |
| US4728544A (en) | Method for coating steel structures in water | |
| NO20002863D0 (en) | Dispersed resins for use in coating compositions | |
| CN103952060A (en) | Epoxy anticorrosive paint modified by polymer containing chlorine and preparation method of epoxy anticorrosive paint | |
| GB2075022A (en) | Water-reducible epoxy coating compositions | |
| JPS5827756A (en) | Curing agent for underwater paint | |
| KR20220117346A (en) | Low-voc coating composition, anticorrosive coating film, base with coating film, and production method for base with coating film | |
| CN105694662A (en) | Solvent-free epoxy coal tar anticorrosion paint and its preparation method and use | |
| CN109233532A (en) | A kind of high solid anti-corrosion antifouling environment-friendly type coating of thick film of marine settings | |
| US5760103A (en) | Copper marine cladding composition | |
| US4501832A (en) | Water-reducible epoxy coating compositions | |
| EP0433401A1 (en) | Copper marine cladding composition. | |
| JP2555164B2 (en) | Anticorrosion construction method | |
| JPS61110545A (en) | Rust-proof coated steel material | |
| CN105368250A (en) | Novel environment-friendly anticorrosive paint applied to deep sea environment and preparation method thereof |