JP4549928B2 - Method for producing high adhesion high corrosion resistance steel material and method for improving adhesion of coating film - Google Patents
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- JP4549928B2 JP4549928B2 JP2005152419A JP2005152419A JP4549928B2 JP 4549928 B2 JP4549928 B2 JP 4549928B2 JP 2005152419 A JP2005152419 A JP 2005152419A JP 2005152419 A JP2005152419 A JP 2005152419A JP 4549928 B2 JP4549928 B2 JP 4549928B2
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- 239000011248 coating agent Substances 0.000 title claims description 51
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- 230000001464 adherent effect Effects 0.000 claims description 5
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- DWJXWSIJKSXJJA-UHFFFAOYSA-N 4-n-[4-(4-aminoanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC(C=C1)=CC=C1NC1=CC=C(N)C=C1 DWJXWSIJKSXJJA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
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- XNGVWYNAWQUVQV-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC2=C(C(=C(C)C=C3)C)C3=C21 Chemical compound N=C=O.N=C=O.C1=CC=CC2=C(C(=C(C)C=C3)C)C3=C21 XNGVWYNAWQUVQV-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
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- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、高密着高耐蝕性鉄鋼材の製造方法および塗膜の密着性向上方法に関する。 The present invention relates to a method for producing a highly adherent and highly corrosion-resistant steel material and a method for improving the adhesion of a coating film.
多くの構造材が鉄材や鋼材で作られているが、これらは空気中の酸素や、水分の影響で錆びるため、種々の防錆・防蝕手段が取られている。 Many structural materials are made of iron or steel, but since these rust due to the influence of oxygen and moisture in the air, various rust and corrosion prevention measures have been taken.
古くから、鉄や鋼で作られた鉄鋼材に塗料を塗布し、防錆・防蝕が行われているが、通常の塗料による防錆・防蝕効果は弱く、繰り返し塗布しなければ十分な効果が得られないという問題があった。 For a long time, paint has been applied to steel materials made of iron or steel to prevent rust and corrosion. However, the usual rust and corrosion protection effects of paints are weak, and it is sufficient if it is not applied repeatedly. There was a problem that it could not be obtained.
最近、電気伝導性を有する有機高分子化合物を用いて、鉄鋼材上に防錆皮膜を形成せしめ防蝕する技術が開発され、実用に供されている(非特許文献1)。この技術は、導電性ポリマー粒子を含有するプライマーを鉄鋼材上に塗布するもので、鉄鋼材表面を不動態化させ、その表面電位を貴金属と同じ程度にまで上げるものである。そして、このプライマー層上に塗料を塗布することにより、高い防錆・防蝕性能を得ることが可能となった(特許文献1)。 Recently, using an organic polymer compound having electrical conductivity, a technique for forming a rust preventive film on a steel material to prevent corrosion is developed and put into practical use (Non-Patent Document 1). In this technique, a primer containing conductive polymer particles is applied on a steel material, the surface of the steel material is passivated, and its surface potential is increased to the same level as that of a noble metal. And it became possible by applying a coating material on this primer layer to obtain high rust prevention and corrosion prevention performance (patent document 1).
しかしながら、上記のプライマーを使用する防蝕方法においても、十分な防錆・防蝕効果が得られる場合と、そうでない場合があり、この原因を解明し、常に安定した高い防錆・防蝕効果を得るための手段の開発が求められていた。 However, even in the anticorrosion method using the above primer, there are cases where sufficient rust prevention / corrosion effect can be obtained or not, in order to elucidate the cause and always obtain a stable and high rust prevention / corrosion effect. Development of the means was demanded.
従って本発明は、導電性ポリマー粒子を含有するプライマーを利用し、常に安定した高い防錆・防蝕効果を得るための技術の提供をその課題とするものである。 Accordingly, an object of the present invention is to provide a technique for obtaining a stable and high antirust / corrosion effect by using a primer containing conductive polymer particles.
本発明者らは、上記課題を解決すべく、まず、導電性ポリマー粒子を含有するプライマーを利用しながら十分な防錆・防蝕効果が得られない原因の究明を行った。そしてその結果、例えば、ポリアニリンは、酸化還元反応により、エメラルジン塩(ES)、ロイコエメラルジン(LE)およびエメラルジン塩基(EB)となるが、このうち、絶縁性は高いが脆いEBがプライマー中に生成された場合、外力が加わることにより、剥離やクラックが起きやすく、塗膜全体の防錆・防蝕効果を低下させていることを知った。そして、更にこのEBの生成の原因を追及していたところ、プライマー層上に塗布する塗料の層と密接な関係があることを見出した。すなわち、塗料によって上記EB層が生成しやすいものと生成しにくいものがあり、EB層が生成しにくいものを選択することにより、高密着かつ高耐食性の被膜が形成しうることを見出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors first investigated the cause of the inability to obtain a sufficient rust prevention and corrosion prevention effect while using a primer containing conductive polymer particles. As a result, for example, polyaniline is converted into emeraldine salt (ES), leucoemeraldine (LE), and emeraldine base (EB) by oxidation-reduction reaction. When it was generated, it was found that peeling and cracking were likely to occur due to the application of external force, reducing the rust prevention and corrosion prevention effect of the entire coating film. Further, when the cause of the generation of EB was further investigated, it was found that there was a close relationship with the paint layer applied on the primer layer. That is, it has been found that a coating with high adhesion and high corrosion resistance can be formed by selecting a coating material that is likely to produce the EB layer and a coating material that are difficult to produce. Was completed.
従って本発明は、鉄鋼材上に、導電性ポリマー粒子を有効成分として含有するプライマーを塗布し、次いでその上に硬化剤としてイソシアネート系化合物を使用するエポキシ系、ウレタン系またはフッ素系樹脂塗料を塗布する高耐蝕性鉄鋼材の製造方法である。 Accordingly, in the present invention, a primer containing conductive polymer particles as an active ingredient is applied on a steel material, and then an epoxy, urethane, or fluororesin paint using an isocyanate compound as a curing agent is applied thereon. This is a method for producing a highly corrosion-resistant steel material.
また本発明は、被保護鉄鋼材上に、導電性ポリマー粒子を有効成分として含有するプライマーを塗布し、次いでその上に硬化剤としてイソシアネート系化合物を使用するエポキシ系、ウレタン系またはフッ素系樹脂塗料を塗布する塗膜の密着性向上方法である。 The present invention also provides an epoxy-based, urethane-based or fluorine-based resin paint in which a primer containing conductive polymer particles as an active ingredient is applied onto a protected steel material, and then an isocyanate compound is used as a curing agent on the primer. This is a method for improving the adhesion of a coating film to which is applied.
本発明の高密着高耐蝕性鉄鋼材の製造方法によれば、塗布プライマー層中にEBが生成しにくく、安定して高い防錆・防蝕効果を有し密着性の良い高密着高耐蝕性鉄鋼材が得られる。また、本発明の塗膜の密着性向上方法によれば、被保護鋼材上に、密着性の高い塗膜を形成させることができ、長期間安定した防錆・防蝕効果が期待できる。 According to the method for producing a high adhesion and high corrosion resistance steel material of the present invention, EB is hardly generated in the coated primer layer, and has a high adhesion and high corrosion resistance steel having a stable and high antirust / corrosion effect and good adhesion. A material is obtained. Further, according to the method for improving the adhesion of a coating film of the present invention, a coating film with high adhesion can be formed on the steel material to be protected, and a long-term stable rust prevention and corrosion prevention effect can be expected.
本明細書中において鉄鋼材とは、鉄や鋼で作られた構造材等の材料の他、鉄とそれ以外の金属の合金で作られた材料を意味する。 In this specification, a steel material means a material made of an alloy of iron and other metals in addition to a material such as iron or a structural material made of steel.
本発明の高密着高耐蝕性鉄鋼材を製造するには、まず、適当な清浄化処理を行った鉄鋼材に導電性ポリマー粒子を含有するプライマー(以下、「防蝕プライマー」という)を塗布する。この防蝕プライマーは、主に導電性ポリマー粒子と、塗膜形成成分、溶剤等から構成されるものである。これには、必要により有機顔料を加えても良い。 In order to produce the highly adherent and highly corrosion-resistant steel material of the present invention, first, a primer containing conductive polymer particles (hereinafter referred to as “corrosion resistant primer”) is applied to a steel material that has been subjected to an appropriate cleaning treatment. This anticorrosion primer is mainly composed of conductive polymer particles, a coating film forming component, a solvent and the like. If necessary, an organic pigment may be added thereto.
防蝕プライマー中の導電性ポリマー粒子の量は、0.1から45質量%(以下、「%」という)程度であり、1から20%であることがより好ましい。 The amount of the conductive polymer particles in the anticorrosion primer is about 0.1 to 45% by mass (hereinafter referred to as “%”), and more preferably 1 to 20%.
この導電性ポリマー粒子は、ポリ共役π電子系を有する有機ポリマーの粒子であり、ポリアニリン、ポリピロール、ポリチオフェン等が挙げられる。このうち、ポリアニリンがより好ましい。このポリアニリンとしては、例えば、特許文献2(PCT/EP 88/00798の実施例2により合成される)や、特許文献3(VERSICON アライドシグナル社製)などで開示されているものを使用することができる。 The conductive polymer particles are organic polymer particles having a polyconjugated π electron system, and examples thereof include polyaniline, polypyrrole, and polythiophene. Of these, polyaniline is more preferable. As this polyaniline, for example, those disclosed in Patent Document 2 (synthesized according to Example 2 of PCT / EP 88/00798) and Patent Document 3 (manufactured by VERSICON Allied Signal) may be used. it can.
また、この導電性ポリマー粒子の粒径は特に制約されるものではないが、平均粒子径が10nm〜500nm程度のものが好ましい。 The particle diameter of the conductive polymer particles is not particularly limited, but those having an average particle diameter of about 10 nm to 500 nm are preferable.
なお、市販のポリアニリンプライマーとして、「CORRPASSIV」(日本オルメコン社製)が使用されているので、これを防蝕プライマーとして使用することもできる。 In addition, since "CORRPASSIV" (manufactured by Nippon Olmecon) is used as a commercially available polyaniline primer, it can also be used as an anticorrosion primer.
上記した防蝕プライマーの塗布は、特に制限はなく、一般的な塗布方法、例えば、はけ塗り、吹きつけ塗装、浸漬塗装、静電スプレー塗装等で行うことができる。また塗布回数は、1回塗り、多層塗りのいずれであっても良いが、例えば、9ないし60μm程度の適度な厚さのプライマー層を均一に形成させるためには、多層塗りを行うことが好ましい。 Application of the above-described anticorrosion primer is not particularly limited, and can be performed by a general application method such as brush coating, spray coating, dip coating, electrostatic spray coating, or the like. The number of coatings may be either one-time coating or multi-layer coating. For example, in order to uniformly form a primer layer having an appropriate thickness of about 9 to 60 μm, it is preferable to perform multi-layer coating. .
以上のようにして、防蝕プライマー層が形成された鉄鋼材は、次に硬化剤としてイソシアネート系化合物を使用するエポキシ系、ウレタン系またはフッ素系樹脂塗料(以下、「上塗塗料」という)が塗布される。 The steel material on which the anticorrosive primer layer is formed as described above is then coated with an epoxy, urethane or fluorine resin paint (hereinafter referred to as “top coat paint”) using an isocyanate compound as a curing agent. The
この上塗塗料であるエポキシ系、ウレタン系またはフッ素系樹脂塗料は、その塗膜形成成分としては、従来公知のエポキシ樹脂、ポリウレタン樹脂およびフッ素樹脂が挙げられる。これらの樹脂は、必要とされる塗膜の強度、厚さに応じ適宜選択使用される。 The epoxy-based, urethane-based, or fluorine-based resin coatings that are the top coating materials include conventionally known epoxy resins, polyurethane resins, and fluorine resins as coating film forming components. These resins are appropriately selected and used according to the required strength and thickness of the coating film.
この上塗塗料においては、硬化剤の選択が重要である。すなわち、使用される硬化剤としては、イソシアネート系化合物であることが必要である。このイソシアネート系化合物としては、ヘキサエチレンジイソシアネート、ヘキサメチレンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、ジメチルビフェニレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、ジイソシアネートジメチルベンゼン、ジイソシアネートジメチルシクロヘキサン等が挙げられる。なお、上記した上塗塗料の硬化剤としては、イソシアネート系化合物以外に、ポリアミドアミン、ポリアミン、ケチミン等が使用されるが、これらを使用した場合には、防蝕プライマー中にEB層が形成され、密着性や耐食性が低下することがある。 In this top coat, selection of a curing agent is important. That is, it is necessary that the curing agent used is an isocyanate compound. These isocyanate compounds include hexaethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, diisocyanate dimethylbenzene, diisocyanate dimethylcyclohexane. Etc. In addition to the isocyanate compound, polyamidoamine, polyamine, ketimine, and the like are used as the curing agent for the above-described top coating, but when these are used, an EB layer is formed in the anticorrosion primer, and adhesion And corrosion resistance may decrease.
本発明の上塗塗料中には、前記塗膜成分の他、各種の顔料を配合することができる。このうち、有色顔料として、各種の無機顔料、例えば、酸化鉄、カーボンブラック、酸化クロム、紺青、群青等や、有機顔料、例えば、タール系色素をレーキ化したもの等の配合が可能である。 In the top coating composition of the present invention, various pigments can be blended in addition to the coating film components. Of these, various inorganic pigments such as iron oxide, carbon black, chromium oxide, bitumen, ultramarine blue, and the like, and organic pigments such as those obtained by lacquering tar dyes can be used as colored pigments.
また、本発明の上塗塗料は、水系塗料であっても溶剤系塗料であっても良く、その溶剤成分としては、水や、炭化水素系溶剤、脂肪族系溶剤、芳香族系溶剤、アルコール系溶剤、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、塩素系溶剤等の有機系溶剤が使用される。これらの溶剤成分は、塗膜形成成分等の他の配合成分に応じ、適宜選択使用することができる。 The top coating composition of the present invention may be a water-based paint or a solvent-based paint, and the solvent component thereof is water, a hydrocarbon-based solvent, an aliphatic solvent, an aromatic solvent, an alcohol-based paint. Organic solvents such as solvents, ester solvents, ketone solvents, ether solvents, and chlorine solvents are used. These solvent components can be appropriately selected and used according to other compounding components such as a coating film forming component.
更にまた、本発明の上塗塗料は、上記した成分の他、一般に塗料組成物において用いられる各種添加剤を適宜使用することができる。このような添加剤としては、例えば、可塑剤、顔料分散剤、乳化剤、増粘剤、飛散防止剤などが挙げられる。 Furthermore, in the top coating composition of the present invention, various additives generally used in coating compositions can be appropriately used in addition to the above-described components. Examples of such additives include plasticizers, pigment dispersants, emulsifiers, thickeners, antiscattering agents, and the like.
上記の上塗塗料の塗布は、通常の塗料の塗布方法により実施することができる。すなわち、はけ塗り、吹きつけ塗装、浸漬塗装、静電スプレー塗装、静電粉体塗装、電着塗装等の種々の塗装方法を用いて、前記防蝕プライマー層が形成された鉄鋼材上に塗布することが可能である。またその塗布も、1回塗り、多層塗りのいずれであっても良い。 The above-mentioned top coating can be applied by a normal coating method. That is, it is applied on the steel material on which the anticorrosive primer layer is formed using various coating methods such as brush coating, spray coating, dip coating, electrostatic spray coating, electrostatic powder coating, and electrodeposition coating. Is possible. Also, the coating may be either one-time coating or multilayer coating.
また、上記上塗塗料による塗布は、これを中塗り塗装とし、その上に更に仕上塗装を行っても、また、これを最終塗装としても良い。 In addition, the above-described coating with the top coating may be an intermediate coating, and a finish coating may be further performed thereon, or this may be a final coating.
本発明方法により、安定した防錆・防蝕効果が得られる理由は、まだ明確でない部分もあるが、一応次のように考えられている。すなわち、塗料中に強アルカリ性の成分が含まれている場合、この塗料層と接するプライマー層中のポリアニリンは、EBに変化し、EB層が形成される。そしてこのEB層は、弾力のないものであるため、外力により簡単に破壊され、この結果腐食が進行する。これに対し、塗料中に強アルカリ性の成分を含まない場合は、EB層の形成を防ぎ、高い密着強度を得ることができるため、十分な耐蝕性を有するのである。 The reason why a stable rust prevention and corrosion prevention effect can be obtained by the method of the present invention is still unclear, but is considered as follows. That is, when a strongly alkaline component is contained in the paint, the polyaniline in the primer layer in contact with the paint layer changes to EB, and an EB layer is formed. And since this EB layer is a thing without elasticity, it is easily destroyed by external force, and corrosion progresses as a result. On the other hand, when a strong alkaline component is not included in the coating material, the formation of the EB layer can be prevented and high adhesion strength can be obtained, so that the coating material has sufficient corrosion resistance.
次に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれら実施例に何ら制約されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.
参 考 例 1
プライマー組成物の製造:
以下に示した成分を、常法により混合し、プライマー組成物を製造した。
Reference example 1
Production of primer composition:
The components shown below were mixed by a conventional method to produce a primer composition.
( 組 成 )
成 分 質量%
1. 変成アルコール 55
2. ブチラール樹脂 10
3. ポリアニリン 8
4. ブラウン顔料 4
5. ブタノール 残部
(Composition)
Component Mass%
1. Denatured alcohol 55
2. Butyral resin 10
3. Polyaniline 8
4). Brown pigment 4
5). Butanol remaining
実 施 例 1
密着性試験:
(1)参考例1のプライマー組成物を、その平均厚さが約15μmとなるよう酸洗い鋼板(1.6×70×150mm)にバーコーターにより塗布した(下塗)。このプライマー層を常温で乾燥させた後、表1に示す各種の塗料を、エアスプレーを使用する吹き付け塗装によりその平均厚さが約30μmとなるよう塗布し(中塗)、更に室温で乾燥させ、試験試料を得た。
Example 1
Adhesion test:
(1) The primer composition of Reference Example 1 was applied to a pickled steel plate (1.6 × 70 × 150 mm) by a bar coater (undercoating) so that the average thickness thereof was about 15 μm. After drying this primer layer at room temperature, the various paints shown in Table 1 were applied by spray coating using air spray so that the average thickness was about 30 μm (intermediate coating), and further dried at room temperature, A test sample was obtained.
(2)得られた各試料について、引張試験機(引張付着試験器ADO−90;(株)サンコウ電子研究所製)を用い下記の方法で引張試験を行った。すなわち、試験試料と引張試験用ジグの両方の表面を#240程度のサンドペーパーで荒らし、2液型のエポキシ樹脂接着剤で接着した。次いで、この接着部分をクランプで締め付けて固定し、少なくとも3日間以上硬化乾燥させた。引張試験用ジグの周辺の塗膜を専用工具で削り取り、付着抵抗する面積を試験試料と引張試験用ジグの接着面とした。更に、引張試験用治具を接着した試験試料を引張試験機にセットし、引張試験機上部のハンドルを一定速度となるように回して行き、塗膜が破断した時の引張強度の数値を引張試験機から読み取り、これを破壊強度とした。また、この破断部分について、どこで破断が生じたか観察を行った。この結果も表1に併せて示す。 (2) About each obtained sample, the tension test was done with the following method using the tension tester (Tensile adhesion tester ADO-90; Co., Ltd. product made from Sanko Electronics Laboratory). That is, the surfaces of both the test sample and the tensile test jig were roughened with sandpaper of about # 240 and adhered with a two-pack type epoxy resin adhesive. Next, the bonded portion was clamped and fixed, and cured and dried for at least 3 days. The coating film around the tensile test jig was scraped off with a dedicated tool, and the adhesion resistance area was defined as the adhesion surface between the test sample and the tensile test jig. In addition, set the test sample with the tensile test jig attached to the tensile tester, turn the handle at the top of the tensile tester to a constant speed, and pull the tensile strength value when the paint film breaks. This was read from the testing machine and this was taken as the breaking strength. In addition, it was observed where the fracture occurred on this fractured portion. The results are also shown in Table 1.
この結果から明らかなように、被膜型性樹脂がエポキシ系樹脂で、硬化剤がアミン系の塗料(番号1〜12、16)の塗膜の破断は、凝集破壊B(下塗塗膜内部破壊)もしくは界面破壊A/B(素地と下塗塗膜の層間破壊)が多い傾向であった。また、破断面の色調は青もしくは青に近い緑であり、破壊強度の数値の最高は1.6であった。この原因は下塗塗膜の全部または一部(上層部)がES体からEB体に変化したためと判断された。なお、これらのうち数種の塗膜の破断傾向は凝集破壊C(中塗塗膜内部破壊)であったが、その破壊強度の数字も最高が1.3であり、いずれも中塗塗膜の強度が弱かったためと考えられる。 As is apparent from this result, the film breakage of the paint film (numbers 1 to 12 and 16) in which the film-type resin is an epoxy resin and the curing agent is an amine resin is cohesive failure B (inner coating film internal destruction). Or, there was a tendency for interfacial fracture A / B (interlaminar fracture between the substrate and the undercoat film). The color of the fracture surface was blue or green close to blue, and the highest numerical value of fracture strength was 1.6. The cause was judged to be because all or part of the undercoat film (upper layer part) was changed from the ES body to the EB body. Of these, the breaking tendency of several types of coatings was cohesive failure C (intermediate coating internal fracture), but the maximum number of fracture strengths was 1.3, both of which were strong. This is probably because of the weakness.
これに対し、エポキシ、ウレタン系、フッ素の各樹脂を塗膜成分とし、硬化剤がイソシアネート系化合物である塗料(番号17〜24)の塗膜の破断傾向は、凝集破壊C(中塗塗膜内部破壊)もしくは凝集破壊B(下塗塗膜内部破壊)であり、界面破壊はなかった。そして、凝集破壊B(下塗塗膜内部破壊)の破断面の色調は緑でES体の状態であり、破壊強度の数値も最低値で2.0であった。また、凝集破壊C(中塗塗膜内部破壊)のもの数値には2.0以下のものがあったがこれは中塗塗膜の強度に問題があったと思われ、下塗塗膜はES体の状態であると判断された。 On the other hand, the rupture tendency of the paint film (numbers 17 to 24) in which epoxy, urethane, and fluorine resins are used as coating film components and the curing agent is an isocyanate compound is indicated by cohesive failure C (inner coating film inside) Failure) or cohesive failure B (primary coating internal destruction), and there was no interfacial failure. And the color tone of the fracture surface of cohesive failure B (undercoating paint internal fracture) was green and in the state of ES body, and the numerical value of the fracture strength was 2.0 at the lowest value. In addition, the value of cohesive failure C (intermediate coating film internal fracture) was 2.0 or less, which seems to have been a problem with the strength of the intermediate coating film. It was determined that
その他、酸化重合系各種塗料(番号13〜15、25〜27)の塗膜は、界面破壊B/Cもしくは凝集破壊Cであった。界面破壊B/Cのものは、破壊強度の数値自体が0.5〜1.2と低く、下塗塗膜との親和性に劣ると考えられた。また、凝集破壊Cのものも破壊強度の数値が0.7〜1.1と低く、中塗塗膜の強度が弱いものであった。 In addition, the coating films of the various oxidation polymerization-type paints (Nos. 13 to 15 and 25 to 27) were interface fracture B / C or cohesive fracture C. Interfacial fracture B / C was considered to be inferior in affinity with the undercoat film because the numerical value of the fracture strength itself was as low as 0.5 to 1.2. The cohesive fracture C also had a low fracture strength value of 0.7 to 1.1, and the intermediate coating film had a weak strength.
このようなことから、ポリアニリン等の導電性ポリマーを含有する防蝕プライマーに組み合わせる中塗塗料としては、エポキシ系、ウレタン系、フッ素系樹脂である塗膜成分に、硬化剤としてイソシアネート系化合物を用いたものが良いことが明らかとなった。 For this reason, as an intermediate coating to be combined with an anticorrosive primer containing a conductive polymer such as polyaniline, an epoxy compound, a urethane component, a coating component that is a fluorine resin, and an isocyanate compound as a curing agent are used. It became clear that it was good.
以上説明した本発明の高耐蝕性鉄鋼材の製造方法および鉄鋼材の防蝕方法によれば、鉄鋼材中に塗布した防蝕プライマー層中にエメラルジン塩基(EB)層ができにくいため、防蝕プライマー層が本来有する防蝕効果を十分に発揮することができる。 According to the manufacturing method of the high corrosion resistance steel material and the corrosion prevention method of the steel material described above according to the present invention, since the emeraldine base (EB) layer is difficult to be formed in the corrosion protection primer layer applied to the steel material, The inherent anticorrosion effect can be sufficiently exhibited.
従って、本発明方法は、高耐蝕性鉄鋼材の製造方法として、あるいは既に設置された鉄鋼材の防蝕方法として有用なものである。
以 上
Accordingly, the method of the present invention is useful as a method for producing a highly corrosion-resistant steel material or as a method for preventing corrosion of already installed steel materials.
more than
Claims (6)
The method for improving the adhesion of a coating film according to claim 4 or 5, wherein the content of the polyaniline particles in the primer is 0.1 to 45 mass%.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05200362A (en) * | 1991-09-06 | 1993-08-10 | Mitsui Toatsu Chem Inc | Protecting and corrosion preventing method for steel product and steel pipe |
JPH10109063A (en) * | 1996-10-04 | 1998-04-28 | Nkk Corp | Precoated steel sheet having excellent formability and corrosion resistance |
JPH11245331A (en) * | 1998-03-05 | 1999-09-14 | Kawasaki Steel Corp | Polyurethane-covered steel material and polyurethane resin composition for covering steel material |
JPH11246819A (en) * | 1998-03-05 | 1999-09-14 | Kansai Paint Co Ltd | Coating material composition and coated steel sheet |
JP2002327151A (en) * | 2001-05-07 | 2002-11-15 | Tech Taiyo Kogyo Co Ltd | Coating composition and method for preventing corrosion of weather resistance steel by using the same |
JP2004223303A (en) * | 2002-11-27 | 2004-08-12 | Kansai Paint Co Ltd | Method for obtaining metal coating excellent in corrosion resistance |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05200362A (en) * | 1991-09-06 | 1993-08-10 | Mitsui Toatsu Chem Inc | Protecting and corrosion preventing method for steel product and steel pipe |
JPH10109063A (en) * | 1996-10-04 | 1998-04-28 | Nkk Corp | Precoated steel sheet having excellent formability and corrosion resistance |
JPH11245331A (en) * | 1998-03-05 | 1999-09-14 | Kawasaki Steel Corp | Polyurethane-covered steel material and polyurethane resin composition for covering steel material |
JPH11246819A (en) * | 1998-03-05 | 1999-09-14 | Kansai Paint Co Ltd | Coating material composition and coated steel sheet |
JP2002327151A (en) * | 2001-05-07 | 2002-11-15 | Tech Taiyo Kogyo Co Ltd | Coating composition and method for preventing corrosion of weather resistance steel by using the same |
JP2004223303A (en) * | 2002-11-27 | 2004-08-12 | Kansai Paint Co Ltd | Method for obtaining metal coating excellent in corrosion resistance |
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