JP2014169406A - Heavy-duty rust proofing primer - Google Patents
Heavy-duty rust proofing primer Download PDFInfo
- Publication number
- JP2014169406A JP2014169406A JP2013042386A JP2013042386A JP2014169406A JP 2014169406 A JP2014169406 A JP 2014169406A JP 2013042386 A JP2013042386 A JP 2013042386A JP 2013042386 A JP2013042386 A JP 2013042386A JP 2014169406 A JP2014169406 A JP 2014169406A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- resin
- primer
- epoxy resin
- heavy
- 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 25
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 37
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 6
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 4
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 239000003795 chemical substances by application Substances 0.000 claims description 13
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- 150000001412 amines Chemical class 0.000 claims description 10
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- 239000002253 acid Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
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- 125000002723 alicyclic group Chemical group 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 38
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- 238000004140 cleaning Methods 0.000 abstract 2
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- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Abstract
Description
本発明は、還元剤、樹脂及び亜鉛粉末を含有する水系又は溶剤系重防錆用プライマーに関する。 The present invention relates to a water-based or solvent-based heavy rust preventive primer containing a reducing agent, a resin and zinc powder.
ジンクリッチペイントの鉄に対する防食効果は古くから知られており、亜鉛を高濃度で含む防食塗料が使用されている。このジンクリッチペイントのビヒクルは、有機系と無機系に分けられている。有機系は、無機系に比べ防食性は劣るもののハンドリング、増膜性、密着性の面で有利である。
近年、戦後復興期に建てた橋、道路をはじめとする建築物は、老朽化の時期を迎え、そのメンテナンス方法及び費用は莫大であり検討が必要である。現工法では老朽化した鉄部の処理としてサンドブラスト、ショットブラスト等を行っているが騒音、環境、コスト面で問題となっている。
The anticorrosive effect of zinc rich paint on iron has been known for a long time, and anticorrosive paints containing zinc at a high concentration are used. The zinc rich paint vehicle is divided into an organic type and an inorganic type. The organic system is advantageous in terms of handling, film-thickness, and adhesion, although it is inferior in anticorrosion properties to the inorganic system.
In recent years, buildings such as bridges and roads built in the post-war reconstruction period have come to age, and their maintenance methods and costs are enormous and need to be studied. In the current construction method, sand blasting, shot blasting, etc. are carried out as a treatment of aging iron parts, but there are problems in terms of noise, environment and cost.
一般的な重防食塗料としては、ビスフェノールＡ型から構成されるエポキシ樹脂やウレタン樹脂が使用されているが、サンドブラストは必要である（例えば、特許文献１）。
そこでこれらの樹脂の中にタルク等の扁平顔料を用いて防食の向上を図っているがこの場合もサンドブラストは必要である。
また、水系又は溶剤系のジンクリッチペイントを用いた防錆塗料は数多くあるが、鉄部の処理はサンドブラストを必要であり抜本的な解決には至っていない（例えば、特許文献２又は特許文献３）。
一方、アクリル樹脂、ウレタン樹脂と有機キレート剤を混ぜることにより還元性を持たせた樹脂材料も提唱されているが、この方法も塩水噴霧試験７２時間程度の試験の結果が開示されている（例えば特許文献４）。
As a general heavy anticorrosion paint, epoxy resin or urethane resin composed of bisphenol A type is used, but sandblasting is necessary (for example, Patent Document 1).
Therefore, a flat pigment such as talc is used in these resins to improve anticorrosion. However, sandblasting is also necessary in this case.
There are many anti-corrosion paints using water-based or solvent-based zinc rich paints, but the treatment of the iron part requires sandblasting and has not led to a radical solution (for example, Patent Document 2 or Patent Document 3). .
On the other hand, a resin material having a reducing property by mixing an acrylic resin, a urethane resin and an organic chelating agent has been proposed, but this method also discloses a result of a test for about 72 hours in a salt spray test (for example, Patent Document 4).
しかしながら、サンドブラスト不要かつ塩水に対して長時間耐えうることができる重防錆用プライマーは提供できていなく、改良の余地がある。
本発明は上記事情に鑑みられたものであって、サンドブラストを行わず、３種ケレン程度で鉄部処理が簡略化でき、且つ、塩水に対して長時間耐えうることができる重防錆用プライマーを提供することを課題とする。
However, a heavy rust preventive primer that does not require sandblasting and can withstand salt water for a long time cannot be provided, and there is room for improvement.
The present invention has been made in view of the above circumstances, and does not perform sand blasting. The iron part treatment can be simplified with about 3 types of keren and can withstand a long period of time against salt water. It is an issue to provide.
本発明は、還元剤、樹脂及び亜鉛粉末を含有することを特徴とする重防錆用プライマーである。
前記還元剤としては、クエン酸ナトリウム、コハク酸、Ｌ−リンゴ酸、酒石酸、クエン酸、グリコール酸、グルコン酸、りん酸、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトロ三酢酸（ＮＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ヒドロキシエチルイミノジ酢酸（ＨＩＤＡ）、ジヒドロキシエチルグリシン（ＤＨＥＧ）、１−ヒドロキシエタン−1，1−ジホスホン酸（ＨＥＤＰ）、ニトリロトリス（メチレンホスホン酸）（ＮＴＭＰ）、ビタミンＡ、ビタミンＥ、カテキン、縮合型タンニン、３，４，５−トリヒドロキシ安息香酸（没食子酸）、及びポリフェノール、並びにそれらの塩化合物からなる群より選ばれる少なくとも１種のキレート剤であることが好ましい。
前記還元剤の含有量は、０．１質量％〜３０質量％であることが好ましい。
前記樹脂がブチラール樹脂、エポキシ樹脂、フェノール樹脂、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂及びフッ素樹脂、並びにそれらの変性体からなる群より選ばれる少なくとも１種であることが好ましい。
前記エポキシ樹脂の平均分子量は、５０００以下であることが好ましい。
前記エポキシ樹脂は、一液性及び二液性エポキシ樹脂であり、主剤及び硬化剤からなる二液性エポキシ樹脂の場合、前記硬化剤が、脂肪族ポリアミン、芳香族ポリアミン、脂環族ポリアミン、ポリアミドアミン及びエポキシアダクトアミンからなる群より選ばれる少なくとも１種であることが好ましい。
前記亜鉛粉末の平均粒径は、５００μｍ以下あり、前記エポキシ樹脂との比率が、２０/１〜１/２０であることが好ましい。
This invention is a primer for heavy rust prevention characterized by containing a reducing agent, resin, and zinc powder.
Examples of the reducing agent include sodium citrate, succinic acid, L-malic acid, tartaric acid, citric acid, glycolic acid, gluconic acid, phosphoric acid, ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), diethylenetriaminepentaacetic acid ( DTPA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), nitrilotris (methylenephosphonic acid) (NTMP), vitamin A, vitamin E It is preferably at least one chelating agent selected from the group consisting of catechin, condensed tannin, 3,4,5-trihydroxybenzoic acid (gallic acid), polyphenol, and salt compounds thereof.
The content of the reducing agent is preferably 0.1% by mass to 30% by mass.
The resin is preferably at least one selected from the group consisting of a butyral resin, an epoxy resin, a phenol resin, a polyester resin, an acrylic resin, a urethane resin, a fluororesin, and a modified product thereof.
The average molecular weight of the epoxy resin is preferably 5000 or less.
The epoxy resin is a one-component or two-component epoxy resin. In the case of a two-component epoxy resin comprising a main agent and a curing agent, the curing agent is an aliphatic polyamine, an aromatic polyamine, an alicyclic polyamine, a polyamide. It is preferably at least one selected from the group consisting of amines and epoxy adduct amines.
It is preferable that the average particle diameter of the zinc powder is 500 μm or less, and the ratio to the epoxy resin is 20/1 to 1/20.
本発明によれば、サンドブラストを行わず、３種ケレン程度で鉄部処理が簡略化でき、且つ、塩水に対して長時間耐えうることができる重防錆用プライマーを提供することができる。 According to the present invention, it is possible to provide a heavy rust preventive primer that can simplify the iron part treatment with about 3 kinds of keren without sandblasting and can withstand salt water for a long time.
本発明の重防錆用プライマーは、還元剤、樹脂及び亜鉛粉末を含有することを特徴とする。 The primer for heavy rust prevention according to the present invention contains a reducing agent, a resin and zinc powder.
前記還元剤としては、クエン酸、コハク酸、Ｌ−リンゴ酸、酒石酸、クエン酸、グリコール酸、グルコン酸、りん酸、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトロ三酢酸（ＮＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ヒドロキシエチルイミノジ酢酸（ＨＩＤＡ）、ジヒドロキシエチルグリシン（ＤＨＥＧ）、１−ヒドロキシエタン−１，１−ジホスホン酸（ＨＥＤＰ）、ニトリロトリス（メチレンホスホン酸）（ＮＴＭＰ）、ビタミンＡ、ビタミンＥ、カテキン、縮合型タンニン、３，４，５−トリヒドロキシ安息香酸（没食子酸）、ピロガロ−ル及びポリフェノール、並びにそれらの塩化合物からなる群より選ばれる少なくとも１種のキレート剤であることが好ましい。これらの中でも、クエン酸、ＥＤＴＡ、３，４，５−トリヒドロキシ安息香酸（没食子酸）及びピロガロ−ル又はこれらの塩化合物がより好ましく、３，４，５−トリヒドロキシ安息香酸（没食子酸）及びピロガロ−ルが特に好ましい。
前記還元剤の含有量は、０．１質量％〜３０質量％であることが好ましい。
Examples of the reducing agent include citric acid, succinic acid, L-malic acid, tartaric acid, citric acid, glycolic acid, gluconic acid, phosphoric acid, ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA). ), Hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), nitrilotris (methylenephosphonic acid) (NTMP), vitamin A, vitamin E, Preferable is at least one chelating agent selected from the group consisting of catechin, condensed tannin, 3,4,5-trihydroxybenzoic acid (gallic acid), pyrogallol and polyphenol, and their salt compounds. Among these, citric acid, EDTA, 3,4,5-trihydroxybenzoic acid (gallic acid) and pyrogallol or their salt compounds are more preferable, and 3,4,5-trihydroxybenzoic acid (gallic acid). And pyrogallol are particularly preferred.
The content of the reducing agent is preferably 0.1% by mass to 30% by mass.
本発明の重防錆用プライマーにおいて、前記還元剤は、０．１質量％〜３０質量％含有することが好ましく、０．２質量％〜２０．０質量％含有することがより好ましく、０．５質量％〜１０．０質量％含有することが特に好ましい。
還元剤の含有量を前記範囲の下限値より多くすることにより防錆効果を高めることができ、上限値より少なくすることにより膜の密着性及び耐水性の劣化を防ぐことができる。
In the primer for heavy rust prevention of the present invention, the reducing agent is preferably contained in an amount of 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20.0% by mass. It is particularly preferable to contain 5% by mass to 10.0% by mass.
By increasing the content of the reducing agent from the lower limit of the above range, the rust prevention effect can be enhanced, and by reducing the content of the reducing agent below the upper limit, deterioration of film adhesion and water resistance can be prevented.
前記樹脂はブチラール樹脂、エポキシ樹脂、フェノール樹脂、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂、フッ素樹脂及びその変性体からなる群より選ばれる少なくとも１種であることが好ましい。 The resin is preferably at least one selected from the group consisting of a butyral resin, an epoxy resin, a phenol resin, a polyester resin, an acrylic resin, a urethane resin, a fluororesin, and a modified product thereof.
ブチラール樹脂の具体例としてはポリビニルブチラール樹脂等が挙げられる。 Specific examples of the butyral resin include polyvinyl butyral resin.
エポキシ樹脂の具体例としては、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、ビス（４−ヒドロキシフェニル）エーテル等のビスフェノール類とエピクロロヒドリンの共重合体等が挙げられる。これらビスフェノール類は１種類を単独で使用してもよいし、２種類以上併用してもよい。 Specific examples of the epoxy resin include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 1,1-bis (4-hydroxyphenyl) cyclohexane. And a copolymer of bisphenols such as 1,1-bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) ether and epichlorohydrin. These bisphenols may be used alone or in combination of two or more.
フェノール樹脂の具体例としては、熱可塑性ノボラック樹脂、熱硬化性レゾール樹脂等が挙げられる。 Specific examples of the phenol resin include a thermoplastic novolac resin and a thermosetting resol resin.
ポリエステル樹脂の具体例としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等が挙げられる。 Specific examples of the polyester resin include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
アクリル樹脂の具体例としては、メタクリル酸、アクリル酸、メタクリル酸メチル、アクリル酸メチル、メタクリル酸エチル、アクリル酸エチル、メタクリル酸プロピル、アクリル酸プロピル、メタクリル酸イソプロピル、アクリル酸イソプロピル、メタクリル酸ｎ−ブチル、アクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、アクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、アクリル酸ｔ−ブチル、メタクリル酸ｎ−ヘキシル、アクリル酸ｎ−ヘキシル等や、これらの共重合体等が挙げられる。 Specific examples of the acrylic resin include methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, isopropyl methacrylate, isopropyl acrylate, methacrylic acid n- Butyl, n-butyl acrylate, i-butyl methacrylate, i-butyl acrylate, t-butyl methacrylate, t-butyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, etc. Examples include coalescence.
ウレタン樹脂の具体例としては、一液湿気硬化性ウレタン樹脂等が挙げられる。 Specific examples of the urethane resin include one-part moisture curable urethane resin.
フッ素樹脂の具体例としては、ルミフロン（旭硝子（株）製）、Ｄｕｆｌｏｎ（日本ペイント（株）製）、ボンフロン（ＡＧＣコーテック（株）製）等が挙げられる。 Specific examples of the fluororesin include Lumiflon (manufactured by Asahi Glass Co., Ltd.), Duflon (manufactured by Nippon Paint Co., Ltd.), Bonflon (manufactured by AGC Co-Tech Co., Ltd.) and the like.
前記樹脂としては、水系樹脂又は溶剤系樹脂であることが好ましい。
水系樹脂とは、上記に例示した樹脂のうち、水を溶媒として用いたものをいう。
溶剤系樹脂とは、上記に例示した樹脂を、有機溶剤に溶解したものをいう。有機溶媒としては、メタノール、エタノール、イソプロピルアルコール、プロピルアルコール、ブタノール、ペンタノール等のアルコール類；アセトン、メチルエチルケトン、エチルイソブチルケトン、メチルイソブチルケトン等のケトン類；エチレングリコール、エチレングリコールメチルエーテル、エチレングリコールモノ−ｎ−プロピルエーテル等のエチレングリコール類等が挙げられる。
The resin is preferably a water-based resin or a solvent-based resin.
The aqueous resin refers to a resin using water as a solvent among the resins exemplified above.
The solvent-based resin refers to a resin obtained by dissolving the resin exemplified above in an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, and pentanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, ethylene glycol methyl ether, and ethylene glycol And ethylene glycols such as mono-n-propyl ether.
前記樹脂ｐＨは、特に限定されないが、ｐＨ３〜１０が好ましく、ｐＨ４．０〜ｐＨ１０が更に好ましく、ｐＨ７〜ｐＨ９．５が特に好ましい。
前記樹脂のｐＨが３以上であることにより、塩水に対する長時間耐久性があり、ｐＨが７以上であれば特に塩水噴霧試験１０００時間以上という高い耐久性が得られる。
The pH of the resin is not particularly limited, but is preferably pH 3 to 10, more preferably pH 4.0 to pH 10, and particularly preferably pH 7 to pH 9.5.
When the pH of the resin is 3 or more, the resin has long-term durability against salt water. When the pH is 7 or more, particularly high durability of 1000 hours or more for the salt spray test can be obtained.
前記樹脂としては、濡れ性及び鉄部と密着する樹脂であれば使用可能であるが、例えばエポキシ樹脂、ウレタン樹脂、アルキド樹脂が好ましく、エポキシ樹脂が特に好ましい。
前記樹脂がエポキシ樹脂である場合、該エポキシ樹脂の分子量は５０００以下であることが好ましく、２００〜３０００であることがより好ましく、３００〜２０００であることが特に好ましい。
エポキシ樹脂の分子量が前記範囲内であることにより、分子量が大きすぎると膜が硬くなりすぎ、割れが発生したり、密着性が劣る。
As the resin, any resin can be used as long as it is a resin that adheres to the wettability and the iron part. For example, an epoxy resin, a urethane resin, and an alkyd resin are preferable, and an epoxy resin is particularly preferable.
When the resin is an epoxy resin, the molecular weight of the epoxy resin is preferably 5000 or less, more preferably 200 to 3000, and particularly preferably 300 to 2000.
When the molecular weight of the epoxy resin is within the above range, if the molecular weight is too large, the film becomes too hard, cracking occurs, and adhesion is inferior.
本発明においては、前記エポキシ樹脂は、一液性及び二液性エポキシ樹脂であり、主剤及びアミン硬化剤からなる二液性エポキシ樹脂を用いる場合、硬化剤として、脂肪族ポリアミン、芳香族ポリアミン、脂環族ポリアミン、ポリアミドアミン及びエポキシアダクトアミンからなる群より選ばれる少なくとも１種を用いることが好ましく、脂肪族ポリアミンがより好ましい。 In the present invention, the epoxy resin is a one-part or two-part epoxy resin, and when a two-part epoxy resin comprising a main agent and an amine curing agent is used, an aliphatic polyamine, an aromatic polyamine, It is preferable to use at least one selected from the group consisting of alicyclic polyamines, polyamide amines and epoxy adduct amines, and aliphatic polyamines are more preferable.
前記亜鉛粉末としては、従来公知のものを使用できるが、亜鉛粉末の粒度は、５００μｍ以下あり、前記エポキシ樹脂との比率が、２０/１〜１/２０であることが好ましい。
亜鉛粉末の粒度は、より好ましくは３μｍ〜１００μｍであり、特に好ましくは３μｍ〜５０μｍである。
前記亜鉛粉末と前記エポキシ樹脂との比率は１／１０〜１０／１であることがより好ましく、１／１〜１０／１であることが特に好ましい。
A conventionally well-known thing can be used as said zinc powder, However, It is preferable that the particle size of zinc powder is 500 micrometers or less, and a ratio with the said epoxy resin is 20/1-1/20.
The particle size of the zinc powder is more preferably 3 μm to 100 μm, and particularly preferably 3 μm to 50 μm.
The ratio of the zinc powder to the epoxy resin is more preferably 1/10 to 10/1, and particularly preferably 1/1 to 10/1.
前記樹脂には、ｐＨを調整するために添加剤を添加してもよい。添加剤としては、クエン酸等の有機酸やケイ酸塩、メタノール、水、等が挙げられる。 An additive may be added to the resin in order to adjust the pH. Examples of the additive include organic acids such as citric acid, silicates, methanol, water, and the like.
本発明によれば、サンドブラストを行わず、３種ケレン程度で鉄部処理が簡略化でき、且つ、塩水噴霧試験１０００時間以上耐えうることができる重防錆用プライマーを提供することができる。
その理由は定かではないが、以下のように推測される。
鉄部を還元させるとさびの発生が抑えられることは鉄のｐＨ−電位のプールベ図で説明される。一般的な鉄の電位は、−０．４２ｍＶ〜−０．４４ｍＶであり、この図を引用するとこの電位が−０．６ｍＶ以下になるとｐＨ＝９．０以下で鉄は、安定領域（錆びない領域）になる。つまり、鉄部に還元が強くかかるとこの領域になる。これは、鉄を還元焼成すると錆びにくくなることと似ていると考えられる。本発明における還元剤は、３種ケレンを行っても未だ赤錆（ＦｅＯ（ＯＨ））が存在していることを想定している。赤錆はＦｅ３＋であることから還元剤に使用する材料も骨格中に３つの不対電子、水酸基及びカルボキシル基が存在すると直接的及び間接的に結合し鉄の価数が小さくなると思われる。このような構造を持つ材料としては、有機キレート剤ではタンニン酸よりも五倍子酸に起因する没食子酸が挙げられる。無機キレート剤でもリン酸及びそれの化合物は、３つの不対電子を有しているためこの考えに当てはまるが還元力を考慮すると有機キレート剤を使用することが有利である。その結果、価数が小さくなると黒錆（Ｆｅ３Ｏ４）に変化する。非可逆である黒錆の粒子は、非常に小さいため防食効果も期待できると考えられる。
他方、鉄表面に他の化合物を形成することにより防食を持たせる方法があり一般的には酸性領域でリン酸、リン酸亜鉛等のリン酸化合物がある。
According to the present invention, it is possible to provide a heavy rust preventive primer that can simplify the iron treatment with about 3 kinds of keren without sandblasting and can withstand a salt spray test for 1000 hours or more.
The reason is not clear, but is presumed as follows.
The fact that the occurrence of rust is suppressed when the iron part is reduced is explained by the pH-potential pool diagram of iron. The general potential of iron is -0.42 mV to -0.44 mV. When this figure is quoted, if this potential is -0.6 mV or less, the pH is 9.0 or less and the iron is in a stable region (not rusting). Area). In other words, this region is obtained when the iron part is strongly reduced. This is thought to be similar to the fact that when iron is reduced and fired, it becomes difficult to rust. The reducing agent in the present invention assumes that red rust (FeO (OH)) is still present even when three kinds of keren are applied. Since red rust is Fe 3+ , the material used for the reducing agent is considered to be directly and indirectly bonded and have a reduced valence of iron when three unpaired electrons, a hydroxyl group and a carboxyl group are present in the skeleton. As a material having such a structure, an organic chelating agent includes gallic acid caused by pentaploid acid rather than tannic acid. Even in the case of inorganic chelating agents, phosphoric acid and its compounds have three unpaired electrons, so this idea is applicable, but considering the reducing power, it is advantageous to use organic chelating agents. As a result, when the valence becomes small, it changes to black rust (Fe 3 O 4 ). Since the irreversible black rust particles are very small, the anticorrosive effect is expected.
On the other hand, there is a method of providing corrosion protection by forming another compound on the iron surface, and generally there are phosphate compounds such as phosphoric acid and zinc phosphate in the acidic region.
しかしながら本発明においては、亜鉛粉末との併用系であるため、鉄表面に防食性化合物を形成させることとは抜本的に思想が異なる。本発明は、電気的考察が必要であり亜鉛粉末との通電性が必要条件となる。酸化物で鉄部を覆ってしまうと通電性が小さく又はなくなり、ジンクリッチとしての効果がなくなるため、通電性を持たせる範囲での還元であることが必要となると思われる。
加熱硬化型及び常温硬化型のエポキシ樹脂系であり水系及び溶剤系でも可能である。このシステムは、一液性や、二液性の場合はアミンを硬化剤としており亜鉛粉末及び還元剤が配合されている。水系の場合、ジンクリッチペイントは非常に不安定になることが知られているが溶剤を水溶性溶媒（アルコール系）にすることにより解消した。又、ジンクリッチの分散を考えるとその粒度は、小さい方が好ましいと考えられる。
ジンクリッチペイントの犠牲防食は、一般的に知られているがこれは金属のイオン化傾向で説明されている。外部（上部）からの腐食は、このジンクリッチイントで止まり、鉄部まで到達できないが、これだけでは内部からの腐食は防止できない。つまり、ジンクリッチペイントのみでは、長時間（塩水噴霧１０００時間以上）は実現できないと考えられる。
従って、本発明では還元剤及びジンクリッチペイントの組み合わせにより内部及び外部からの腐食を遮断し、さらには鉄部処理としてサンドブラストを行う必要がなく３種ケレン程度で済み長時間（塩水噴霧１０００時間以上）が実現可能となったと推測される。
本発明の重防錆プライマーを用いることにより老朽化した橋、船舶、プラント、建物等さらには鉄を使用しているあらゆる部分に対し３種ケレン程度で重防食性を発揮し環境面、コスト面で非常に有利である。従って、本発明は、産業上極めて有用である。
However, in the present invention, since it is a combined system with zinc powder, the idea is fundamentally different from forming an anticorrosive compound on the iron surface. In the present invention, electrical considerations are necessary, and electrical conductivity with zinc powder is a necessary condition. If the iron part is covered with an oxide, the electrical conductivity is reduced or lost, and the effect as zinc rich is lost. Therefore, it is considered necessary to perform reduction within a range in which electrical conductivity is imparted.
Heat curing type and room temperature curing type epoxy resin systems, which can be water based or solvent based. In this system, in the case of one-pack or two-pack, amine is used as a curing agent, and zinc powder and a reducing agent are blended. In the case of water system, zinc rich paint is known to be very unstable, but it was solved by making the solvent a water-soluble solvent (alcohol system). Further, considering the zinc rich dispersion, it is considered preferable that the particle size is smaller.
The sacrificial protection of zinc rich paint is generally known, but this is explained by the tendency to ionize the metal. Corrosion from the outside (upper part) stops at this zinc rich int and cannot reach the iron part, but this alone cannot prevent corrosion from the inside. That is, it is considered that a long time (1000 hours or more of salt water spray) cannot be realized with only zinc rich paint.
Therefore, in the present invention, the combination of the reducing agent and the zinc rich paint is used to block corrosion from the inside and the outside, and further, it is not necessary to perform sand blasting as an iron part treatment, and only about 3 types of kelen can be used (salt water spraying time of 1000 hours or more). ) Is assumed to be feasible.
By using the heavy rust preventive primer of the present invention, it is possible to demonstrate heavy anticorrosion with about 3 types of keren for any part using iron, such as bridges, ships, plants, buildings, etc. Is very advantageous. Therefore, the present invention is extremely useful industrially.
以下、実施例により本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.
銅板を約３カ月間放置し錆を発生させ、３種ケレン処理を行った基板を以下用いた。 A copper plate was allowed to stand for about 3 months to generate rust, and a substrate subjected to three types of kelen treatment was used below.
（参考例）
還元剤と水性樹脂の種類及びその樹脂のｐＨの安定性に関する試験である。以下に使用樹脂、還元剤及びその他の添加剤とその配合量を記載する。また、表１における配合量は質量％とする。
(Reference example)
It is a test regarding the type of reducing agent and aqueous resin and the stability of the pH of the resin. The resin used, the reducing agent and other additives and their blending amounts are described below. Moreover, the compounding quantity in Table 1 shall be the mass%.
還元剤；関東化学（株）製試薬 没食子酸（３，４，５−トリヒドロキシ安息香酸）
クエン酸；昭和化学（株）製
ＥＤＴＡ；キレスト（株）製
メタノール；日本ケミカルズ（株）製
Reducing agent: Reagent manufactured by Kanto Chemical Co., Inc. Gallic acid (3,4,5-trihydroxybenzoic acid)
Citric acid; Showa Chemical Co., Ltd. EDTA; Kirest Co., Ltd. Methanol; Nippon Chemicals Co., Ltd.
表１に示すエポキシ樹脂、アクリル樹脂及びウレタン樹脂を表１中の配合比で室温中約２０分混合し、所定の塗料を得た。各種塗料を鉄鋼部に全塗膜厚約１００μｍの厚みで塗布し３日室温放置後特性を評価した。表１中の二液性エポキシ樹脂は、主剤及びアミン硬化剤を混合しているものである。また、エポキシ樹脂の種類は、使用ｐＨに応じて変えている。
表１の結果から、還元剤を添加した系において密着性及び耐水性は、大きく異なり、試験４の配合が良好であることが判る。この結果は、鉄部に対する樹脂の構造からのぬれ性が起因していると考えられる。
The epoxy resin, acrylic resin, and urethane resin shown in Table 1 were mixed at room temperature for about 20 minutes at the blending ratio in Table 1 to obtain a predetermined paint. Various paints were applied to the steel part with a total coating thickness of about 100 μm, and the properties were evaluated after standing at room temperature for 3 days. The two-component epoxy resin in Table 1 is a mixture of a main agent and an amine curing agent. Moreover, the kind of epoxy resin is changed according to use pH.
From the results shown in Table 1, it can be seen that the adhesion and water resistance are greatly different in the system to which the reducing agent is added, and the formulation of Test 4 is good. This result is considered to be due to the wettability of the resin structure with respect to the iron part.
（実施例）
還元剤を配合した水性塗料と亜鉛粉末の比率に対する安定性の試験である。以下に使用樹脂、還元剤及びその他の添加剤とその配合量を記載する。また、表２における配合量は質量部とする。
(Example)
It is a test of the stability with respect to the ratio of the water-based paint and zinc powder which mix | blended the reducing agent. The resin used, the reducing agent and other additives and their blending amounts are described below. Moreover, let the compounding quantity in Table 2 be a mass part.
還元剤；関東化学（株）製；没食子酸（３，４，５−トリヒドロキシ安息香酸）
メタノール；日本ケミカルズ（株）製
ジンクリッチ；（日本ペイント（株）製、商品名：ジンキ−Ｌ−４、粒度；４μｍ〜５μｍ）
Reducing agent; manufactured by Kanto Chemical Co., Inc .; gallic acid (3,4,5-trihydroxybenzoic acid)
Methanol: Zinc Rich manufactured by Nippon Chemicals Co., Ltd. (made by Nippon Paint Co., Ltd., trade name: Zinki-L-4, particle size: 4 μm to 5 μm)
表２に試験６の配合を基本としてジンクリッチの比率に対する樹脂及び還元剤の安定性を測定した。試験４の配合の樹脂部分とジンクリッチを上記表２中の配合比で室温中約２０分混合し、所定の塗料を得た。各種塗料を鉄部に約１００μｍの厚みで塗布し３日室温放置後特性を評価した。ジンクリッチの含有量が８０質量部までは、塗膜物性は良好であることが判った。 Table 2 shows the stability of the resin and the reducing agent with respect to the zinc rich ratio based on the formulation of test 6. The resin part and zinc rich of the blend of test 4 were mixed at the blending ratio shown in Table 2 for about 20 minutes at room temperature to obtain a predetermined paint. Various paints were applied to the iron part to a thickness of about 100 μm, and the properties were evaluated after standing at room temperature for 3 days. It was found that the physical properties of the coating film were good up to a zinc rich content of up to 80 parts by mass.
（実施例、比較例）
上記表２中の実施例３（試験９）において、ＪＩＳ Ｚ ２３７１に準じた中性塩水噴霧試験を行った。結果を以下表３に示す。また、表３における配合量は質量部とする。なお、比較例としてジンクリッチの有無、還元剤の有無を行った。
実施例４（試験１１）の還元剤有り、ジンクリッチ有りでは中性塩水噴霧試験１０００時間を達成することができた。
(Examples and comparative examples)
In Example 3 (Test 9) in Table 2 above, a neutral salt spray test according to JIS Z 2371 was performed. The results are shown in Table 3 below. Moreover, let the compounding quantity in Table 3 be a mass part. In addition, the presence or absence of zinc rich and the presence or absence of a reducing agent were performed as a comparative example.
With the reducing agent of Example 4 (Test 11) and with zinc rich, a neutral salt spray test of 1000 hours could be achieved.
（参考例）
還元剤と溶剤系樹脂の種類及びその樹脂のｐＨの安定性に関する試験である。以下に使用樹脂、還元剤及びその他の添加剤とその配合量を記載する。
(Reference example)
This is a test relating to the type of reducing agent and solvent-based resin and the pH stability of the resin. The resin used, the reducing agent and other additives and their blending amounts are described below.
アクリル樹脂；ＤＩＣ（株）製；アクリディック ５２−２０４
ウレタン樹脂；ＤＩＣ（株）製；バーノック
還元剤；関東化学（株）製 没食子酸（３，４，５−トリヒドロキシ安息香酸）
メタノール；日光ケミカルズ（株）製
アセトン；デルタ（株）製
Acrylic resin; manufactured by DIC Corporation; Acridic 52-204
Urethane resin; manufactured by DIC Corporation; burnock reducing agent; manufactured by Kanto Chemical Co., Inc. gallic acid (3,4,5-trihydroxybenzoic acid)
Methanol; Nikko Chemicals Acetone; Delta Corporation
上記表４にエポキシ樹脂、アクリル樹脂及びウレタン樹脂を上記表１中の配合比で室温中約２０分混合し、所定の塗料を得た。各種塗料を鉄部に約１００μｍの厚みで塗布し３日室温放置後特性を評価した。表４中の二液性エポキシ樹脂は、主剤及びアミン硬化剤を混合して用いている。試験１３が良好であることが判る。この結果は、鉄部に対する樹脂の構造からのぬれ性が起因していると考えられる。 In Table 4 above, an epoxy resin, an acrylic resin and a urethane resin were mixed at the blending ratio in Table 1 above for about 20 minutes at room temperature to obtain a predetermined paint. Various paints were applied to the iron part to a thickness of about 100 μm, and the properties were evaluated after standing at room temperature for 3 days. The two-part epoxy resin in Table 4 is used by mixing a main agent and an amine curing agent. It can be seen that Test 13 is good. This result is considered to be due to the wettability of the resin structure with respect to the iron part.
（実施例）
還元剤を配合した溶剤塗料とジンクリッチの比率に対する安定性の試験である。以下に使用樹脂、還元剤及びその他の添加剤とその配合量を記載する。
エポキシ樹脂；（株）アデカ製；アデカレジンＥＰ−５１００−７５Ｘ
アクリル樹脂；例えばＤＩＣ（株）製；アクリディック ５２−２０４
ウレタン樹脂；例えばＤＩＣ（株）製；バーノック ＤＮＷ−５５００
還元剤；関東化学（株）製試薬 没食子酸（３，４，５−トリヒドロキシ安息香酸）
メタノール；日本ケミカルズ（株）製
アセトン；デルタ（株）製
ジンクリッチ；（日本ペイント（株）製、商品名：ジンキ−Ｌ−４、粒度；４μｍ〜５μｍ）
(Example)
This is a test of the stability with respect to the ratio of solvent paint and zinc rich containing a reducing agent. The resin used, the reducing agent and other additives and their blending amounts are described below.
Epoxy resin; Adeka Co., Ltd .; Adeka Resin EP-5100-75X
Acrylic resin; for example, manufactured by DIC Corporation; Acridic 52-204
Urethane resin; for example, manufactured by DIC Corporation; Burnock DNW-5500
Reducing agent: Reagent manufactured by Kanto Chemical Co., Inc. Gallic acid (3,4,5-trihydroxybenzoic acid)
Methanol; Nippon Chemicals Co., Ltd. Acetone; Delta Co., Ltd. Zinc Rich; (Nihon Paint Co., Ltd., trade name: Zinki-L-4, particle size: 4 μm to 5 μm)
上記表５に試験１９の配合を基本としてジンクリッチの比率に対する安定性を評価した結果を示す。試験１９の配合の樹脂部分とジンクリッチを表５中の配合比で室温中約２０分混合し、所定の塗料を得た。各種塗料を鉄部に全塗膜厚約１００μｍの厚みで塗布し３日室温放置後特性を評価した。 Table 5 shows the results of evaluating the stability with respect to the zinc rich ratio based on the formulation of Test 19. The resin part of the blend of Test 19 and zinc rich were mixed at room temperature in Table 5 for about 20 minutes at room temperature to obtain a predetermined paint. Various paints were applied to the iron part with a total coating thickness of about 100 μm, and the properties were evaluated after standing at room temperature for 3 days.
（実施例、比較例）
表５中試験１９をＪＩＳ Ｚ ２３７１に準じた中性塩水噴霧試験を行った。結果を表６に示す。尚、比較としてジンクリッチ有りで、還元剤の有無を行った。
(Examples and comparative examples)
Test 19 in Table 5 was subjected to a neutral salt spray test according to JIS Z 2371. The results are shown in Table 6. For comparison, the presence or absence of a reducing agent was performed with zinc rich.
試験２０の還元剤有り、ジンクリッチ有りでは中性塩水噴霧試験１０００時間を達成することができた。 In the test 20 with a reducing agent and with zinc rich, a neutral salt spray test of 1000 hours could be achieved.
Claims (7)
The average particle diameter of the said zinc powder is 500 micrometers or less, and the ratio with the said epoxy resin is 20/1-1/20, The weight as described in any one of Claims 4-6 characterized by the above-mentioned. Antirust primer.
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| JP6055133B1 (en) * | 2016-03-11 | 2016-12-27 | 日本ペイント防食コーティングス株式会社 | Organic-inorganic composite zinc-rich coating composition |
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| CN110982387A (en) * | 2019-12-27 | 2020-04-10 | 常州市华菱新材料有限公司 | Water-based epoxy coating with good adhesive force and corrosion resistance on surface of metal substrate and preparation method thereof |
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