JP4150104B2 - Anticorrosion paint composition - Google Patents
Anticorrosion paint composition Download PDFInfo
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- JP4150104B2 JP4150104B2 JP14835398A JP14835398A JP4150104B2 JP 4150104 B2 JP4150104 B2 JP 4150104B2 JP 14835398 A JP14835398 A JP 14835398A JP 14835398 A JP14835398 A JP 14835398A JP 4150104 B2 JP4150104 B2 JP 4150104B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
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- Oil, Petroleum & Natural Gas (AREA)
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- Polymers & Plastics (AREA)
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- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、タール系エポキシ塗料の代替塗料であって、特に海水と接触する部位、例えば船舶のバラストタンク内の塗装に有用な防食塗料組成物に関するものである。
【0002】
【従来の技術】
従来、船舶、鋼構造物等の防食塗料としてタール系エポキシ塗料が使用されている。この塗料は防食性、耐水性、耐薬品性などに優れているが、タールを含有することから衛生上の問題が懸念されるのみならず、黒色であるために維持管理が困難であり、密閉した場所では暗くなるので作業に危険が伴うなどの問題があった。
【0003】
【従来技術の課題】
近年、タールの代わりに石油系の樹脂を用いたノンタール系のエポキシ塗料も開発されている。例えば特公昭第59―52656号公報や特開平9―263713号公報等に提案がなされている。すなわち特公昭第59―52656号公報に記載された樹脂は水酸基を含むものであり、実施例においてナフサのクラッキングから得られた不飽和成分を含む留分をフェノール共存下に重合し軟化点93℃の樹脂を得ている。また、特開平9―263713号公報には、実施例において1分子中の水酸基含有量が1〜1.1モルのジビニルトルエン−インデン共重合体(軟化点100℃)を用いたエポキシ樹脂系の防食塗料が開示されている。しかしながら、上記公報記載のエポキシ塗料については、エポキシ樹脂、硬化剤特にアミン硬化剤からなる硬化樹脂と石油系の樹脂との相溶性に問題があり、特に高度の防食性、耐水性などが要求される海水に直接接触する部位の塗装、例えば船舶のバラストタンク内に適用するには不十分である。
【0004】
【課題を解決するための手段】
本発明者は、上記の問題を解決すべく鋭意検討した結果、インデン類含有率を特定した芳香族留分を原料とする樹脂を用いるとともに、フェノール性水酸基の含有量を比較的低減した樹脂を用いることにより、エポキシ樹脂や硬化剤、特にアミン系硬化剤との相溶性に優れ、その結果、衛生上問題がなく、防食性、耐水性、付着性等に優れ、しかも明色の塗膜を形成し得る防食塗料組成物が得られることを見出して本発明に到達した。
【0005】
すなわち、本発明の第1は、エポキシ樹脂(A)、硬化剤、好ましくはアミン系硬化剤(B)、および石油類の熱分解により得られる分解油のうち主として 140〜220℃の沸点範囲にある成分を含む留分から蒸留により得られるインデン類含有率60〜90重量%の分解油留分を、フェノール類の共存下にフリーデル−クラフツ触媒により重合してなる、フェノール性水酸基を1分子当たり 0.1個以上、1.0個未満含有する芳香族性石油樹脂(C)からなり、芳香族性石油樹脂(C)をエポキシ樹脂100重量部に対して1〜500重量部含有することを特徴とする防食塗料組成物に関するものである。
本発明の第2は、本発明の第1において、分解油留分の共役ジエン含有率が5重量%以下である防食塗料組成物に関する。
【0006】
以下、本発明について詳細に説明する。
本発明で使用するエポキシ樹脂(A)は、1分子中に少なくとも2個以上のエポキシ基を有するものであり、エポキシ当量150〜600のものが適当であり、好ましくは180〜500である。このようなエポキシ樹脂としては、例えばビスフェノール型エポキシ樹脂、脂肪族エポキシ樹脂、グリシジルエステル系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾール型エポキシ樹脂、ダイマー酸変性エポキシ樹脂などの従来公知のものが挙げられ、これらは1種のみで、または2種以上混合して使用することができる。
【0007】
本発明で使用される硬化剤(B)は、エポキシ樹脂の硬化剤として従来公知のものが用いられる。例えば、各種脂肪族または芳香族アミン類、ポリアミド樹脂、酸無水物類、フェノール樹脂、ポリイソシアネート等が例示される。これらは1種のみで、または2種以上混合して使用することができる。
特に好ましくは、アミン系硬化剤であり、例えばメタキシレンジアミン、イソホロンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルメタンなどの脂肪族ポリアミン類、脂環族ポリアミン類、芳香族ポリアミン類、これらポリアミン類のエポキシ樹脂アダクト物、ポリアミドアミン類、ポリアミド樹脂などが挙げられる。これらは1種のみで、または2種以上混合して使用することができる。
【0008】
上記エポキシ樹脂(A)および硬化剤(B)の混合割合は、両成分の種類により適宜選択することができる。一般的には、エポキシ樹脂100重量部当たり硬化剤1〜200重量部の範囲から選択される。硬化剤(B)として好ましいアミン系硬化剤を用いる場合には、通常、(B)中の活性水素当量/(A)中のエポキシ当量の当量比が0.5〜1.0の範囲になるように選択することが適当である。
【0009】
本発明において使用する芳香族性石油樹脂(C)としては、フェノール性水酸基を含有する常温で固形状の石油樹脂であって、軟化点が50〜150℃、好ましくは80〜110℃のものを使用する。
【0010】
上記石油樹脂としては、エチレン、プロピレン等を製造するためにナフサ、ブタン等の炭化水素を熱分解する際に副生する分解油のうち、主として沸点範囲が140〜220℃の範囲にある成分を含む留分を原料とする。このような留分には、スチレン、α−またはβ―メチルスチレン、ビニルトルエン、インデン、メチルインデンの他、ジシクロペンタジエン、ジメチルシクロペンタジエン等の不飽和成分、およびエチルベンゼン、トリメチルベンゼン、インダン、メチルインダン、ナフタレン等の飽和成分が含まれる。さらに、蒸留操作の際にジシクロペンタジエン、ジメチルシクロペンタジエン等が熱分解することにより生成したシクロペンタジエン、メチルシクロペンタジエン等の共役ジエンも含まれている。
【0011】
本発明においては、前記分解油の蒸留により得られる留分であって、インデン類含有率が60〜90重量%の留分を原料とする。この範囲を外れる留分を用いると、結果として防食塗料組成物としての性能が低下するので好ましくない。ここで、インデン類含有率(重量%)は、(インデンおよびメチルインデン等のアルキルインデンの合計量)/(分解油留分中の全不飽和成分含有量)×100で定義される。
好ましくは、シクロペンタジエン、メチルシクロペンタジエン等の共役ジエン類含有率が5重量%以下の留分を用いる。共役ジエン類の含有率を5重量%以下にすることにより、防食塗料としての性能をさらに向上させることができる。ここで、共役ジエン類含有率(重量%)は、(共役ジエンの合計量)/(分解油留分中の全不飽和成分含有量)×100で定義される。
なお上記各成分の分析は公知のガスクロマトグラフ法により容易に行うことができる。
また上記組成の分解油留分は、熱分解で副生する分解油に対して適宜に公知の蒸留方法を組み合わせて処理することにより容易に得ることができる。
【0012】
本発明の原料樹脂は、上記分解油留分の100重量部に、フェノール類1.0〜10.0重量部を共存させ、分解油留分に対して0.01〜3重量%のフリーデル−クラフツ触媒を用いて10〜100℃の範囲で重合させることにより製造することができる。
フェノール類としては、フェノールのほかに、クレゾール、キシレノール、 tert−ブチルフェノール、ノニルフェノール等のアルキル基置換のフェノールを例示することができる。これらは混合して使用することもできる。好ましくはフェノールである。フェノール類は、後記のフリーデル−クラフツ触媒の1成分として反応系に存在させることも可能であるが、通常は触媒とは別個に所定量のフェノールを反応系に供給することが多い。
【0013】
フリーデル−クラフツ触媒としては、ハロゲン化金属、好ましくは三弗化ホウ素、またはそのフェノール、エチルエーテル、ブチルエーテル、ブチルアルコール、メチルアルコール等の含酸素化合物との錯体が用いられる。
重合時間は、バッチ式の場合に0.5〜10時間の範囲から選択することができる。
上記分解油留分、フェノール類、フリーデル−クラフツ触媒等を所定量仕込み、公知の方法により重合することにより所定の軟化点の樹脂が得られる。重合後は、アルカリなどを用いて適宜に触媒を失活した後、未反応油や低重合物を適宜に蒸留等で分離除去すれば目的とする樹脂が得られる。
【0014】
本発明の塗料組成物に用いる石油樹脂(C)は、石油樹脂1分子中に0.1個以上、1.0個未満のフェノール性水酸基を含有するものである。好ましくは0.5〜0.9個である。なお重合に際しては、各原料の張込み量、重合条件等を適宜に調整することにより、フェノール性水酸基の量が上記範囲にある樹脂を得ることができる。
本発明で用いる上記石油樹脂(C)の1分子中にフェノール性水酸基が1.0個以上存在すると、防食塗料用の樹脂としては好ましくない。また0.1個未満では、エポキシ樹脂との相溶性が低下し同様に好ましくない。なお、得られた樹脂中に存在するフェノール性水酸基の量は、例えば、I. E. C. Anal. Ed. 17 (1945) p. 394 に記載された方法により測定することができる。
【0015】
また上記樹脂(C)の軟化点は、前記のように50〜150℃、好ましくは 80〜110℃の範囲である。軟化点がが50℃未満では防食塗膜の耐水性が低く、塗膜表面に樹脂成分がブリードして粘着性が残存する場合があり、一方 150℃を越えると塗料粘度が高くなり作業性が低下したり、塗膜物性が低下するので望ましくない。なお、本発明に用いる樹脂(C)の分子量は、数平均分子量として500〜3000の範囲である。
【0016】
本発明組成物を得るには、エポキシ樹脂(A)100重量部に対して、上記フェノール性水酸基を含有する石油樹脂(C)を1〜500重量部、好ましくは 10〜300重量部配合する。上記配合量が1重量部未満では得られた組成物に十分な耐水性が得られず、一方500重量部を越えると塗膜が脆くなり良好な物性が得られなくなるので、いずれも好ましくない。
【0017】
本発明の防食塗料組成物には、さらに可撓性を付与するために、その他の液状の改質剤、例えばキシレン樹脂、トルエン樹脂;ブチルグリシジルエーテル等のエポキシ化合物などの反応性希釈剤等を、硬化樹脂固形分100重量部に対して50重量部以下の範囲で添加してもよい。これらのうちでは、耐水性維持の面から芳香族系のものが好適に使用される。
【0018】
本発明の組成物には、さらに必要に応じて、体質顔料、防錆顔料、着色顔料等の顔料類;反応性希釈剤;有機溶剤、沈降防止剤、タレ止め剤、湿潤剤、反応促進剤、付着性付与剤、脱水剤等の通常の塗料用添加剤などを適宜配合してもよい。
【0019】
また本発明の組成物は、エポキシ樹脂を含む主剤と硬化剤、好ましくはアミン系硬化剤からなる二液型塗料であり、通常、ジンクプライマーなどの一次防錆塗膜上に塗装される。すなわち、まず鋼板にショットブラストをかけてミルスケールを除き、エチルシリケート系などの無機ジンクショッププライマーを塗布し、その後本発明の塗料組成物の塗布を行う。プライマーはジンクシリケートなどに限らず各種のプライマーを使用することができる。またプライマーなしの鋼板等であっても塗装が可能であり、十分な防食効果が得られる。
塗装方法としては、エアスプレー、エアレススプレー、刷毛塗り、ローラーなど従来公知の方法を採用することができ、上記塗料組成物を乾燥膜厚で150〜500μmになるように塗布することができる。
【0020】
【発明の実施の形態】
以下、実施例を挙げて本発明をさらに詳細に説明する。尚、「部」及び「%」はそれぞれ「重量部」および「重量%」を示す。
【実施例】
<製造例>
ナフサの熱分解により得られる分解油から、沸点範囲が140〜220℃の留分を分留することにより、全不飽和成分量51%、インデン類含有率70%、共役ジエン類含有率0.5%に調整された分解油留分を得た。
次に、上記分解油留分100gにフェノール5gを添加し、三弗化ホウ素−フェノール錯体を0.5g加えて、30℃で3時間重合した後、苛性ソーダ水溶液で触媒を除去し、次いで水洗した後、蒸留により未反応油および低重合物を除去して石油樹脂(A)56gを得た。
得られた樹脂の軟化点は103℃であり、分析の結果フェノール性水酸基を分子1個当たり0.8個有することを確認した。
【0021】
<比較製造例>
上記製造例と同様にして、インデン類含有率20%、共役ジエン含有率6%の分解油留分を得た。
これを同様にして重合させることにより、軟化点85℃、フェノール性水酸基を分子1個当たり0.8個有する石油樹脂(B)を得た。
【0022】
<実施例1>
容器に、エポキシ樹脂100部、チタン白30部、タルク100部、製造例で得た石油樹脂(A)100部、炭化水素系可塑剤20部、タレ止め剤5部ならびにキシレン、MIBKおよびシクロヘキサンの等量混合溶剤150部を添加し撹拌機で混合撹拌して分散させることにより主剤とした。これに硬化剤としてポリアミド樹脂80部(固形分換算)を添加し、混合撹拌して防食塗料組成物を得た。組成および結果を表1に示す。
【0023】
<実施例2、比較例>
表1に示す配合で同様に組成物を製造した。比較例では、比較製造例の石油樹脂(B)を用いた。結果を表1に示す。
【0024】
【表1】
【0025】
なお、防食塗料組成物の性能試験の方法は以下の通りである。
(1)耐衝撃性試験(デュポン式)
各試料を、脱脂した磨き軟鋼板(200×100×0.6mm)にアプリケーターににより約250μmの乾燥膜厚になるように塗装し、20℃×65%RHの雰囲気下で7日間乾燥して各試験塗板を作成した。
上記塗板について、20℃の雰囲気中でJIS K5400―1990に規定するデュポン式衝撃試験を行った。
(2)耐冷熱繰返し性試験
脱脂した磨き軟鋼板に、シリケートジンクプライマーを約25μmの乾燥膜厚になるように塗装し、1日乾燥した。この上に、各試料をそれぞれアプリケーターにより約250μmの乾燥膜厚になるように塗装し、20℃×65%RHの雰囲気下で7日間乾燥して各試験片を得た。
これらの試験片について、JIS K5400―1990に従い耐冷熱繰返し性試験を行った。
(3)耐海水性試験
上記(2)耐冷熱繰返し性試験において作成したと同様の試験片を、50℃の海水中に6ヶ月浸漬し、その後の塗面状態を目視で評価した。評価の基準は以下の通りである。
○:異常なし
△:フクレがわずかに発生
×:フクレが著しく発生
【0026】
【発明の効果】
本発明の防食塗料組成物は、インデン類含有率を特定したフェノール性水酸基含有石油樹脂を用いているので、エポキシ樹脂や硬化剤特にアミン系硬化剤と石油樹脂との相溶性が良好であり、衛生上問題がなく、防食性、耐水性、付着性などに優れ、しかも明色の塗膜を形成することができ、船舶や構造物の防食塗料として非常に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an anticorrosive coating composition that is an alternative coating for a tar-based epoxy coating, and is particularly useful for coating in a portion that comes into contact with seawater, for example, a ship's ballast tank.
[0002]
[Prior art]
Conventionally, tar-based epoxy paints are used as anticorrosive paints for ships, steel structures and the like. This paint is excellent in corrosion resistance, water resistance, chemical resistance, etc., but since it contains tar, not only is it concerned about hygiene problems, but it is black and difficult to maintain and seals. There was a problem that the work was dangerous because it was dark in the place.
[0003]
[Prior art issues]
In recent years, non-tar epoxy paints using petroleum-based resins instead of tar have also been developed. For example, Japanese Patent Publication No. 59-52656 and Japanese Patent Laid-Open No. 9-263713 have been proposed. That is, the resin described in JP-B-59-52656 contains a hydroxyl group, and in the examples, a fraction containing an unsaturated component obtained from cracking of naphtha is polymerized in the presence of phenol to have a softening point of 93 ° C. Has obtained a resin. JP-A-9-263713 discloses an epoxy resin system using a divinyltoluene-indene copolymer (softening point 100 ° C.) having a hydroxyl group content of 1 to 1.1 mol in one molecule in Examples. An anticorrosion paint is disclosed. However, the epoxy paint described in the above publication has a problem in compatibility between the epoxy resin, a curing agent, particularly a cured resin composed of an amine curing agent, and a petroleum-based resin, and particularly requires high corrosion resistance and water resistance. It is not sufficient to apply the coating directly in contact with seawater, for example, in a ship's ballast tank.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor used a resin made from an aromatic fraction with a specified indenes content, and a resin with a relatively reduced content of phenolic hydroxyl groups. By using it, it has excellent compatibility with epoxy resins and curing agents, especially amine-based curing agents, and as a result, there are no sanitary problems, excellent corrosion resistance, water resistance, adhesion, etc., and a light-colored coating film It has been found that an anticorrosive coating composition that can be formed is obtained, and the present invention has been achieved.
[0005]
That is, the first of the present invention is mainly in the boiling range of 140 to 220 ° C. among the epoxy resin (A), the curing agent, preferably the amine-based curing agent (B), and the cracked oil obtained by pyrolysis of petroleum. A phenolic hydroxyl group obtained by polymerizing a cracked oil fraction obtained by distillation from a fraction containing a certain component with a Friedel-Crafts catalyst in the presence of phenols in the presence of phenols. It consists of aromatic petroleum resin (C) containing 0.1 or more and less than 1.0, and containing 1 to 500 parts by weight of aromatic petroleum resin (C) with respect to 100 parts by weight of epoxy resin. The present invention relates to a characteristic anticorrosion coating composition.
2nd of this invention is related with the anticorrosion coating composition whose conjugated diene content rate of a cracked oil fraction is 5 weight% or less in 1st of this invention.
[0006]
Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the present invention has at least two epoxy groups in one molecule, and those having an epoxy equivalent of 150 to 600 are suitable, preferably 180 to 500. Examples of such epoxy resins include conventional bisphenol type epoxy resins, aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, cresol type epoxy resins, dimer acid modified epoxy resins, and the like. A well-known thing is mentioned, These can be used only by 1 type or in mixture of 2 or more types.
[0007]
A conventionally well-known thing is used for the hardening | curing agent (B) used by this invention as a hardening | curing agent of an epoxy resin. Examples include various aliphatic or aromatic amines, polyamide resins, acid anhydrides, phenol resins, polyisocyanates and the like. These may be used alone or in combination of two or more.
Particularly preferred are amine-based curing agents, such as aliphatic polyamines such as metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, alicyclic polyamines, aromatic polyamines, and epoxies of these polyamines. Examples thereof include resin adducts, polyamidoamines, and polyamide resins. These may be used alone or in combination of two or more.
[0008]
The mixing ratio of the epoxy resin (A) and the curing agent (B) can be appropriately selected depending on the types of both components. Generally, it is selected from the range of 1 to 200 parts by weight of the curing agent per 100 parts by weight of the epoxy resin. When a preferred amine curing agent is used as the curing agent (B), the equivalent ratio of active hydrogen equivalent in (B) / epoxy equivalent in (A) is usually in the range of 0.5 to 1.0. It is appropriate to select as follows.
[0009]
The aromatic petroleum resin (C) used in the present invention is a petroleum resin solid at room temperature containing a phenolic hydroxyl group and having a softening point of 50 to 150 ° C, preferably 80 to 110 ° C. use.
[0010]
As the above-mentioned petroleum resin, among the cracked oil by-produced when pyrolyzing hydrocarbons such as naphtha and butane in order to produce ethylene, propylene and the like, components having a boiling range of 140 to 220 ° C are mainly used. The fraction containing is used as a raw material. Such fractions include styrene, α- or β-methylstyrene, vinyltoluene, indene, methylindene, unsaturated components such as dicyclopentadiene, dimethylcyclopentadiene, and ethylbenzene, trimethylbenzene, indane, methyl. Contains saturated components such as indane and naphthalene. Furthermore, conjugated dienes such as cyclopentadiene and methylcyclopentadiene produced by thermal decomposition of dicyclopentadiene, dimethylcyclopentadiene and the like during distillation operation are also included.
[0011]
In the present invention, a fraction obtained by distillation of the cracked oil and having an indene content of 60 to 90% by weight is used as a raw material. If a fraction outside this range is used, the performance as an anticorrosion coating composition is lowered as a result, which is not preferable. Here, the indens content (% by weight) is defined by (total amount of alkylindene such as indene and methylindene) / (total unsaturated component content in cracked oil fraction) × 100.
Preferably, a fraction having a conjugated diene content such as cyclopentadiene or methylcyclopentadiene of 5% by weight or less is used. By setting the content of conjugated dienes to 5% by weight or less, the performance as an anticorrosion paint can be further improved. Here, the conjugated diene content (% by weight) is defined as (total amount of conjugated diene) / (total unsaturated component content in cracked oil fraction) × 100.
The above components can be easily analyzed by a known gas chromatographic method.
The cracked oil fraction having the above composition can be easily obtained by appropriately treating the cracked oil by-produced by thermal cracking with a combination of known distillation methods.
[0012]
In the raw material resin of the present invention, 1.0 to 10.0 parts by weight of phenols coexist in 100 parts by weight of the cracked oil fraction, and 0.01 to 3% by weight of Friedel based on the cracked oil fraction. -It can manufacture by polymerizing in the range of 10-100 degreeC using a crafts catalyst.
Examples of phenols include, in addition to phenol, alkyl group-substituted phenols such as cresol, xylenol, tert-butylphenol, and nonylphenol. These can also be used as a mixture. Preferably it is phenol. Phenols can be present in the reaction system as a component of the Friedel-Crafts catalyst described later, but usually a predetermined amount of phenol is often supplied to the reaction system separately from the catalyst.
[0013]
As the Friedel-Crafts catalyst, a metal halide, preferably boron trifluoride, or a complex thereof with an oxygen-containing compound such as phenol, ethyl ether, butyl ether, butyl alcohol, or methyl alcohol is used.
The polymerization time can be selected from the range of 0.5 to 10 hours in the case of a batch system.
A resin having a predetermined softening point is obtained by charging a predetermined amount of the cracked oil fraction, phenols, Friedel-Crafts catalyst and the like and polymerizing by a known method. After polymerization, the catalyst is appropriately deactivated using alkali or the like, and then the unreacted oil or low polymer is appropriately separated and removed by distillation or the like to obtain the desired resin.
[0014]
The petroleum resin (C) used in the coating composition of the present invention contains 0.1 or more and less than 1.0 phenolic hydroxyl groups in one molecule of petroleum resin. The number is preferably 0.5 to 0.9. In the polymerization, a resin in which the amount of phenolic hydroxyl group is within the above range can be obtained by appropriately adjusting the amount of each raw material and the polymerization conditions.
When 1.0 or more phenolic hydroxyl groups are present in one molecule of the petroleum resin (C) used in the present invention, it is not preferable as a resin for anticorrosion coating. On the other hand, if it is less than 0.1, the compatibility with the epoxy resin is lowered, which is also not preferable. The amount of phenolic hydroxyl group present in the obtained resin can be measured, for example, by the method described in IEC Anal. Ed. 17 (1945) p. 394.
[0015]
The softening point of the resin (C) is in the range of 50 to 150 ° C., preferably 80 to 110 ° C. as described above. If the softening point is less than 50 ° C, the water resistance of the anticorrosion coating is low, and the resin component may bleed on the surface of the coating and stickiness may remain. On the other hand, if it exceeds 150 ° C, the viscosity of the coating will increase and workability will be increased. It is not desirable because it lowers and physical properties of the coating film deteriorate. In addition, the molecular weight of resin (C) used for this invention is the range of 500-3000 as a number average molecular weight.
[0016]
In order to obtain the composition of the present invention, 1 to 500 parts by weight, preferably 10 to 300 parts by weight of the petroleum resin (C) containing the phenolic hydroxyl group is blended with 100 parts by weight of the epoxy resin (A). If the blending amount is less than 1 part by weight, sufficient water resistance cannot be obtained for the obtained composition. On the other hand, if it exceeds 500 parts by weight, the coating film becomes brittle and good physical properties cannot be obtained.
[0017]
In order to impart further flexibility to the anticorrosive coating composition of the present invention, other liquid modifiers such as xylene resin, toluene resin; reactive diluents such as epoxy compounds such as butyl glycidyl ether, and the like. Further, it may be added in a range of 50 parts by weight or less with respect to 100 parts by weight of the cured resin solid content. Of these, aromatics are preferably used from the viewpoint of maintaining water resistance.
[0018]
If necessary, the composition of the present invention may further include pigments such as extender pigments, rust preventive pigments, and colored pigments; reactive diluents; organic solvents, anti-settling agents, anti-sagging agents, wetting agents, and reaction accelerators. Ordinary paint additives such as an adhesion-imparting agent and a dehydrating agent may be appropriately blended.
[0019]
The composition of the present invention is a two-component paint comprising an epoxy resin-containing main agent and a curing agent, preferably an amine curing agent, and is usually applied onto a primary anticorrosive coating such as a zinc primer. That is, first, shot blasting is applied to the steel plate to remove the mill scale, and an inorganic zinc shop primer such as ethyl silicate is applied, and then the coating composition of the present invention is applied. The primer is not limited to zinc silicate, and various primers can be used. Further, even a steel plate without a primer can be coated, and a sufficient anticorrosion effect can be obtained.
As a coating method, conventionally known methods such as air spray, airless spray, brush coating, and roller can be adopted, and the coating composition can be applied so as to have a dry film thickness of 150 to 500 μm.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” indicate “parts by weight” and “% by weight”, respectively.
【Example】
<Production example>
By fractionating a fraction having a boiling range of 140 to 220 ° C. from cracked oil obtained by thermal decomposition of naphtha, the total unsaturated component amount is 51%, the indene content is 70%, and the conjugated diene content is 0. A cracked oil fraction adjusted to 5% was obtained.
Next, 5 g of phenol was added to 100 g of the cracked oil fraction, 0.5 g of boron trifluoride-phenol complex was added, polymerized at 30 ° C. for 3 hours, the catalyst was removed with an aqueous caustic soda solution, and then washed with water. Thereafter, unreacted oil and low polymer were removed by distillation to obtain 56 g of petroleum resin (A).
The resulting resin had a softening point of 103 ° C., and as a result of analysis, it was confirmed that the resin had 0.8 phenolic hydroxyl groups per molecule.
[0021]
<Comparative production example>
In the same manner as in the above production example, a cracked oil fraction having an indene content of 20% and a conjugated diene content of 6% was obtained.
This was polymerized in the same manner to obtain a petroleum resin (B) having a softening point of 85 ° C. and 0.8 phenolic hydroxyl groups per molecule.
[0022]
<Example 1>
In a container, 100 parts of epoxy resin, 30 parts of titanium white, 100 parts of talc, 100 parts of petroleum resin (A) obtained in the production example, 20 parts of hydrocarbon plasticizer, 5 parts of sagging agent and xylene, MIBK and cyclohexane An equivalent amount of 150 parts of a mixed solvent was added, mixed and stirred with a stirrer, and dispersed to obtain a main agent. To this was added 80 parts of polyamide resin (in terms of solid content) as a curing agent, mixed and stirred to obtain an anticorrosive coating composition. The composition and results are shown in Table 1.
[0023]
<Example 2, comparative example>
Compositions were similarly produced with the formulations shown in Table 1. In the comparative example, the petroleum resin (B) of the comparative production example was used. The results are shown in Table 1.
[0024]
[Table 1]
[0025]
In addition, the method of the performance test of anticorrosion coating composition is as follows.
(1) Impact resistance test (DuPont type)
Each sample was coated on a degreased polished mild steel plate (200 × 100 × 0.6 mm) with an applicator to a dry film thickness of about 250 μm and dried for 7 days in an atmosphere of 20 ° C. × 65% RH. Each test coating was prepared.
The coated plate was subjected to a DuPont impact test as defined in JIS K5400-1990 in an atmosphere of 20 ° C.
(2) Cold-heat repeatability test A silicate zinc primer was applied to a degreased polished mild steel sheet so as to have a dry film thickness of about 25 μm and dried for one day. On top of this, each sample was coated with an applicator so as to have a dry film thickness of about 250 μm, and dried for 7 days in an atmosphere of 20 ° C. × 65% RH to obtain each test piece.
These test pieces were subjected to a cold-heat repeatability test according to JIS K5400-1990.
(3) Seawater resistance test A test piece similar to that prepared in the above (2) cold-heat repeatability test was immersed in seawater at 50 ° C for 6 months, and the subsequent coating surface state was visually evaluated. The criteria for evaluation are as follows.
○: No abnormality △: Slight swelling occurs ×: Severe swelling occurs [0026]
【The invention's effect】
Since the anticorrosion coating composition of the present invention uses a phenolic hydroxyl group-containing petroleum resin that specifies the indenes content, the compatibility between the epoxy resin and the curing agent, in particular, the amine curing agent and the petroleum resin is good, There is no problem in terms of hygiene, excellent corrosion resistance, water resistance, adhesion, etc., and can form a light-colored coating film, which is very useful as an anticorrosion paint for ships and structures.
Claims (1)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14835398A JP4150104B2 (en) | 1998-05-13 | 1998-05-13 | Anticorrosion paint composition |
PCT/JP1999/002489 WO1999058618A1 (en) | 1998-05-13 | 1999-05-13 | Coating composition for corrosion proofing |
KR1019997012470A KR100577920B1 (en) | 1998-05-13 | 1999-05-13 | Coating Composition for Corrosion Proofing |
CNB998007374A CN1162486C (en) | 1998-05-13 | 1999-05-13 | Coating composition for corrosion proofing |
FI20000039A FI121995B (en) | 1998-05-13 | 2000-01-10 | Coating composition intended for corrosion protection |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14835398A JP4150104B2 (en) | 1998-05-13 | 1998-05-13 | Anticorrosion paint composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11323247A JPH11323247A (en) | 1999-11-26 |
JP4150104B2 true JP4150104B2 (en) | 2008-09-17 |
Family
ID=15450871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14835398A Expired - Lifetime JP4150104B2 (en) | 1998-05-13 | 1998-05-13 | Anticorrosion paint composition |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP4150104B2 (en) |
KR (1) | KR100577920B1 (en) |
CN (1) | CN1162486C (en) |
FI (1) | FI121995B (en) |
WO (1) | WO1999058618A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101194454B1 (en) * | 2005-03-24 | 2012-10-24 | 도호 가가꾸 고오교 가부시키가이샤 | Epoxy coating composition |
CN101379108B (en) | 2006-02-03 | 2011-11-30 | 旭化成电子材料株式会社 | Microcapsule based harderner for epoxy resin, masterbatch-based hardenercomposition for epoxy resin, one-part epoxy resin composition, and processed good |
JP5255192B2 (en) * | 2006-08-21 | 2013-08-07 | 中国塗料株式会社 | Epoxy resin composition capable of forming coating film having high elongation rate, anticorrosion coating composition, coating film thereof, base material coated with the coating film, and anticorrosion method for base material |
CN101522739B (en) * | 2006-10-04 | 2012-09-05 | 新日铁化学株式会社 | Epoxy resin, phenol resin, their production methods, epoxy resin composition and cured product |
CN101134867B (en) * | 2007-09-28 | 2012-05-23 | 中山大桥化工有限公司 | Shipping ballast cabin coating composition |
CN101880505B (en) * | 2010-07-06 | 2012-07-18 | 庞贝捷(涂料)昆山有限公司 | Thick film type antirust coating and preparation method thereof |
JP5860151B2 (en) | 2012-07-31 | 2016-02-16 | 旭化成イーマテリアルズ株式会社 | Epoxy resin composition, epoxy resin, and cured product |
KR101775613B1 (en) * | 2014-09-16 | 2017-09-07 | 주식회사 메디바이오랩 | Composition for preventing, alleviating or treating periodontal diseases comprising extract of Garcinia Mangostana or Alpha, Gamma-mangostins |
JP6712402B2 (en) | 2015-11-13 | 2020-06-24 | 味の素株式会社 | Coated particles |
CN106349871A (en) * | 2016-08-26 | 2017-01-25 | 江苏华夏制漆科技有限公司 | Waterborne epoxy quick-drying anti-corrosion coating and preparation method thereof |
TWI723252B (en) | 2017-03-17 | 2021-04-01 | 日商旭化成股份有限公司 | Thermosetting resin composition |
CN111788247B (en) | 2018-01-12 | 2023-07-18 | 味之素株式会社 | Coated particles |
CN111117418A (en) * | 2018-11-01 | 2020-05-08 | 庞贝捷涂料(昆山)有限公司 | Anticorrosive coating composition |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5952656B2 (en) * | 1977-04-11 | 1984-12-20 | 日石三菱株式会社 | epoxy resin composition |
JPS54131660A (en) * | 1978-04-03 | 1979-10-12 | Mitsui Petrochem Ind Ltd | Epoxy resin composition |
JPH0286644A (en) * | 1988-09-22 | 1990-03-27 | Nippon Steel Chem Co Ltd | Coumarone/indene resin emulsion composition and adhesive |
JP3044567B2 (en) * | 1990-11-06 | 2000-05-22 | 東ソー株式会社 | Hot melt adhesive |
JPH05105858A (en) * | 1991-10-17 | 1993-04-27 | Nippon Steel Chem Co Ltd | Hot-melt self-adhesive composition |
JP3339893B2 (en) * | 1992-12-01 | 2002-10-28 | 新日本石油化学株式会社 | Epoxy resin composition |
JPH09263713A (en) * | 1996-03-28 | 1997-10-07 | Kansai Paint Co Ltd | Anticorrosive coating composition |
JP3783167B2 (en) * | 1996-05-28 | 2006-06-07 | 新日本石油化学株式会社 | Hot melt composition and modified aromatic petroleum resin used therefor |
-
1998
- 1998-05-13 JP JP14835398A patent/JP4150104B2/en not_active Expired - Lifetime
-
1999
- 1999-05-13 CN CNB998007374A patent/CN1162486C/en not_active Expired - Lifetime
- 1999-05-13 KR KR1019997012470A patent/KR100577920B1/en not_active IP Right Cessation
- 1999-05-13 WO PCT/JP1999/002489 patent/WO1999058618A1/en active IP Right Grant
-
2000
- 2000-01-10 FI FI20000039A patent/FI121995B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JPH11323247A (en) | 1999-11-26 |
CN1162486C (en) | 2004-08-18 |
FI20000039A (en) | 2000-01-10 |
FI121995B (en) | 2011-07-15 |
WO1999058618A1 (en) | 1999-11-18 |
KR100577920B1 (en) | 2006-05-09 |
CN1272125A (en) | 2000-11-01 |
KR20010014326A (en) | 2001-02-26 |
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