JP5246977B1 - Water-based anticorrosion coating method and coated body - Google Patents
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Abstract
【課題】優れた耐候性及び防食性を付与することが可能な水性防食塗装方法を提供する。
【解決手段】被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成し、その後、該下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する水性防食塗装方法であって、前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が多液反応硬化型であり（要件ａ）、前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度が低く（要件ｂ）、前記上塗り塗膜は、紫外線透過率が０．２％以下である（要件ｃ）という３つの要件を満たすことを特徴とする水性防食塗装方法である。
【選択図】なしAn aqueous anticorrosion coating method capable of imparting excellent weather resistance and anticorrosion properties is provided.
A water-based anticorrosive coating method in which a water-based epoxy resin base coat is applied to a surface to be coated to form a base coat, and then a water-based top coat is applied to the base coat to form a top coat. And both the water-based epoxy resin base coating and the water-based top coating are multi-component reaction curable (requirement a), and the water-based top coating has a lower pigment volume concentration than the water-based epoxy resin base coating ( Requirement b), the top coat film is an aqueous anticorrosion coating method characterized by satisfying three requirements that the ultraviolet transmittance is 0.2% or less (requirement c).
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Description
本発明は、水性防食塗装方法及び塗装体に関し、特には、優れた耐候性及び防食性を付与することが可能な水性防食塗装方法に関するものである。 The present invention relates to a water-based anticorrosion coating method and a coated body, and particularly relates to a water-based anticorrosion coating method capable of imparting excellent weather resistance and corrosion resistance.
従来、橋梁、プラント及びタンク等の各種陸上鋼構造物や海洋鋼構造物には、防食目的としての塗装（以下、防食塗装ともいう）が施されている。 Conventionally, various onshore steel structures such as bridges, plants and tanks, and marine steel structures have been coated for corrosion protection (hereinafter also referred to as corrosion protection coating).
一般に、防食塗装では、被塗装物に防食・防錆機能を付与する目的として下塗り塗料が適用されると共に、被塗装物の美観保持を目的として耐候性に優れた上塗り塗料が適用されている。このような防食塗装システムでは、いずれの塗料にも有機溶剤系塗料を使用することが一般的であった。 In general, in the anticorrosion coating, an undercoat paint is applied for the purpose of imparting an anticorrosion / rust prevention function to the object to be coated, and a topcoat paint having excellent weather resistance is applied for the purpose of maintaining the aesthetic appearance of the object to be coated. In such an anticorrosion coating system, it is common to use an organic solvent-based paint for any paint.
しかしながら、近年、大気汚染防止や省資源等の観点から、有機溶剤系塗料から水性塗料への転換が強く要望されるようになってきており、使用する全ての塗料を水性塗料に転換した水性防食塗装システムが求められている。 However, in recent years, there has been a strong demand for switching from organic solvent-based paints to water-based paints from the viewpoint of preventing air pollution and saving resources. There is a need for a painting system.
特開２００９−２２１２５６号公報（特許文献１）には、エポキシ樹脂を含む防食塗装用の水性塗料組成物が提案されている。しかしながら、防食性を付与するために、特開２００９−２２１２５６号公報に記載の水性塗料組成物を下塗り塗料として適用した上で、上述のような防食塗装システムによって下塗り塗膜及び上塗り塗膜を備える複合塗膜を形成した場合、上塗り塗料の種類によっては複合塗膜に期待される耐候性や防食性等の耐久性が得られないという課題があった。 Japanese Unexamined Patent Application Publication No. 2009-212256 (Patent Document 1) proposes an aqueous coating composition for anticorrosion coating containing an epoxy resin. However, in order to impart anticorrosive properties, the aqueous coating composition described in JP-A-2009-212256 is applied as an undercoat, and the undercoat and overcoat are provided by the anticorrosion coating system as described above. When the composite coating film is formed, there is a problem that the durability such as weather resistance and corrosion resistance expected for the composite coating film cannot be obtained depending on the type of the top coating material.
また、特開２００８−２７２６６６号公報（特許文献２）には、使用される全ての塗料が水性塗料である水性防食塗装システムが提案されているものの、この場合、上塗り塗料の紫外線透過率によっては経年劣化によって、層間剥離、例えば下塗り塗膜と上塗り塗膜間での剥離が生じるという課題があった。 Japanese Patent Application Laid-Open No. 2008-272666 (Patent Document 2) proposes a water-based anticorrosion coating system in which all paints used are water-based paints. In this case, depending on the ultraviolet transmittance of the top-coat paint. Due to the deterioration over time, there was a problem that delamination occurred, for example, delamination between the undercoat film and the topcoat film.
そこで、本発明の目的は、上記従来技術の問題を解決し、優れた耐候性及び防食性を付与することが可能な水性防食塗装方法を提供することにある。また、本発明の目的は、かかる水性防食塗装方法によって得られる塗装体を提供することにある。 Then, the objective of this invention is providing the water-based anticorrosion coating method which can solve the problem of the said prior art and can provide the outstanding weather resistance and corrosion resistance. Moreover, the objective of this invention is providing the coating body obtained by this water-based anticorrosion coating method.
本発明者は、上記目的を達成するために鋭意検討した結果、使用される全ての塗料が水性塗料である水性防食塗装システムにおいて、下塗り塗料及び上塗り塗料の両方に多液反応硬化型の水性塗料を使用し、上塗り塗料の顔料容積濃度（Ｐｉｇｍｅｎｔ Ｖｏｌｕｍｅ Ｃｏｎｃｅｎｔｒａｔｉｏｎ；以下、ＰＶＣともいう）を下塗り塗料のＰＶＣより低くし、更に上塗り塗膜の紫外線透過率を特定の範囲内に制御することによって、有機溶剤系塗料が使用されていた防食塗装システム（即ち、有機溶剤系防食塗装システム）と同等の優れた耐候性を付与できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventor, as a result, in a water-based anticorrosion coating system in which all paints used are water-based paints, a multi-component reaction-curable water-based paint for both the undercoat paint and the topcoat paint. The pigment volume concentration (hereinafter also referred to as PVC) of the top coating is made lower than the PVC of the base coating, and the UV transmittance of the top coating is controlled within a specific range. The present inventors have found that excellent weather resistance equivalent to that of an anticorrosion coating system in which a solvent-based paint has been used (that is, an organic solvent-based anticorrosion coating system) can be imparted, and the present invention has been completed.
即ち、本発明の水性防食塗装方法は、被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成し、その後、該下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する水性防食塗装方法であって、下記ａ）〜ｃ）の要件を満たし、前記水性エポキシ樹脂下塗り塗料が、エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤とを含み、前記アミン樹脂エマルジョンが、アミノ基にエポキシ基が付加したエポキシアダクトタイプの変性ポリアミン樹脂が水性媒体中で分散してなる乳濁液であることを特徴とする。
ａ）前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が、多液反応硬化型である。
ｂ）前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度が低い。
ｃ）前記上塗り塗膜は、紫外線透過率が０．２％以下である。
That is, the water-based anticorrosive coating method of the present invention comprises forming an undercoat film by applying an aqueous epoxy resin undercoat on the surface to be coated, and then applying an aqueous overcoat onto the undercoat. an aqueous anticorrosive coating method for forming a meets the following requirements a) to c), the aqueous epoxy resin primer coating comprises a hardening agent comprising a main agent and an amine resin emulsion containing an epoxy resin emulsion, the The amine resin emulsion is characterized by being an emulsion in which an epoxy adduct type modified polyamine resin having an epoxy group added to an amino group is dispersed in an aqueous medium .
a) Both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable.
b) The water-based top coating has a lower pigment volume concentration than the water-based epoxy resin base coating.
c) The top coat film has an ultraviolet transmittance of 0.2% or less.
本発明の水性防食塗装方法の好適例においては、前記水性上塗り塗料を塗布する前に、水性エポキシ樹脂塗料及び水性ウレタン樹脂塗料から選ばれる多液反応硬化型の水性中塗り塗料を前記下塗り塗膜上に塗布し、中塗り塗膜が形成されている。 In a preferred example of the water-based anticorrosive coating method of the present invention, before applying the water-based top coat, a multi-component reaction curing type water-based intermediate coating selected from a water-based epoxy resin paint and a water-based urethane resin paint is applied to the primer coating film. An intermediate coating film is formed on the top surface.
本発明の水性防食塗装方法の他の好適例において、前記被塗装面には、ジンクリッチペイント処理、亜鉛メッキ処理及び金属溶射から選ばれる処理が施され、防食下地が形成されている。 In another preferred embodiment of the water-based anticorrosion coating method of the present invention, the surface to be coated is subjected to a treatment selected from zinc rich paint treatment, galvanization treatment and metal spraying to form an anticorrosion base.
本発明の水性防食塗装方法の他の好適例においては、前記被塗装面の少なくとも一部が、旧塗膜の表面であることを特徴とする。なお、「旧塗膜」とは、本発明の水性防食塗装方法において、水性エポキシ樹脂下塗り塗料が塗布される前に予め形成されている塗膜を意味する。 In another preferred embodiment of the water-based anticorrosion coating method of the present invention, at least a part of the surface to be coated is the surface of an old coating film. The “old coating film” means a coating film that is formed in advance before the aqueous epoxy resin primer coating is applied in the aqueous anticorrosion coating method of the present invention.
また、本発明の塗装体は、上記の水性防食塗装方法によって被塗装面上に複合塗膜が形成されていることを特徴とする。なお、「複合塗膜」とは、少なくとも下塗り塗膜及び上塗り塗膜を備える塗膜を指し、下塗り塗膜と上塗り塗膜の間に中塗り塗膜を備える場合もある。 Further, the coated body of the present invention is characterized in that a composite coating film is formed on the surface to be coated by the above-mentioned water-based anticorrosion coating method. The “composite coating film” refers to a coating film provided with at least a base coating film and a top coating film, and may include an intermediate coating film between the base coating film and the top coating film.
本発明の水性防食塗装方法によれば、使用される全ての塗料が水性塗料である水性防食塗装システムにおいて、下塗り塗料及び上塗り塗料の両方に多液反応硬化型の水性塗料を使用し、上塗り塗料のＰＶＣを下塗り塗料のＰＶＣより低くし、更に上塗り塗膜の紫外線透過率を特定の範囲内に制御することによって、優れた耐候性及び防食性を付与することができる。また、かかる水性防食塗装方法によって、耐候性及び防食性に優れる塗装体を提供することができる。 According to the water-based anticorrosion coating method of the present invention, in a water-based anticorrosion coating system in which all paints used are water-based paints, a multi-component reaction curing type water-based paint is used for both the undercoat paint and the topcoat paint. It is possible to impart excellent weather resistance and corrosion resistance by lowering the PVC of PVC from that of the undercoating material and further controlling the ultraviolet transmittance of the top coating film within a specific range. Moreover, the coating body which is excellent in a weather resistance and corrosion resistance can be provided by this water-based anticorrosion coating method.
＜水性防食塗装方法＞
以下に、本発明の水性防食塗装方法を詳細に説明する。本発明の水性防食塗装方法は、被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成し、その後、該下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する水性防食塗装方法であって、前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が多液反応硬化型であり（要件ａ）、前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度（ＰＶＣ）が低く（要件ｂ）、前記上塗り塗膜は、紫外線透過率が０．２％以下である（要件ｃ）という３つの要件を満たすことを特徴とする。上記３つの要件ａ〜ｃを満たす水性防食塗装方法であれば、被塗装面に優れた耐候性及び防食性を付与することができる。なお、水性防食塗装方法とは、防食性の付与を目的とした塗装方法のうち、水性塗料を用いた塗装方法を指す。
<Waterproof anticorrosion coating method>
Below, the aqueous | water-based anticorrosion coating method of this invention is demonstrated in detail. In the water-based anticorrosive coating method of the present invention, a water-based epoxy resin base coat is formed on a surface to be coated to form a base coat, and then a water base top coat is applied on the base coat to form a top coat. A water-based anticorrosion coating method in which both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable (requirement a), and the water-based top coat is a pigment rather than the water-based epoxy resin base coat. The volume concentration (PVC) is low (requirement b), and the top coat film satisfies the three requirements that the ultraviolet transmittance is 0.2% or less (requirement c). If it is the water-based anticorrosion coating method satisfying the above three requirements a to c, excellent weather resistance and corrosion resistance can be imparted to the surface to be coated. The water-based anticorrosion coating method refers to a coating method using a water-based paint among the coating methods aimed at imparting anticorrosion properties.
本発明の水性防食塗装方法は、上記水性エポキシ樹脂下塗り塗料及び上記水性上塗り塗料の両方が多液反応硬化型であることを要する。これら２種の塗料が多液反応硬化型の塗料であれば、緻密な硬化塗膜が得られ、腐食因子を遮蔽する効果が高くなるとともに、上塗り塗料の場合には紫外線等からの劣化を遅らせることが出来る。なお、多液反応硬化型の塗料とは、塗膜の母材として使用される樹脂を含む主剤と、該樹脂に対する反応性を有する成分を含む硬化剤とを組み合わせたものを指す。 The water-based anticorrosion coating method of the present invention requires that both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable. If these two types of coatings are multi-component reaction curable coatings, a dense cured coating can be obtained, and the effect of shielding corrosion factors will be enhanced. In the case of top coatings, deterioration from ultraviolet rays and the like will be delayed. I can do it. The multi-component reaction curable paint refers to a combination of a main agent containing a resin used as a base material of a coating film and a curing agent containing a component having reactivity with the resin.
また、本発明の水性防食塗装方法において、上記水性上塗り塗料は、上記水性エポキシ樹脂下塗り塗料よりもＰＶＣが低いことを要する。水性上塗り塗料のＰＶＣが水性エポキシ樹脂下塗り塗料よりも低い場合、下塗り塗膜に対する上塗り塗膜の追従性が改善され、これにより、経時での層間の密着性が高くなる。そのため、複合塗膜の耐候性や防食性が向上する。一方、水性上塗り塗料のＰＶＣが水性エポキシ樹脂下塗り塗料よりも高い場合には、経年劣化により塗膜に割れやはがれが発生する場合がある。なお、本発明における顔料容積濃度とは、塗料固形分中に占める顔料の割合（体積％）を指す。 Moreover, in the water-based anticorrosion coating method of the present invention, the water-based top coating material needs to have a lower PVC than the water-based epoxy resin base coating material. When the PVC of the water-based top coat is lower than that of the water-based epoxy resin base coat, the followability of the top coat with respect to the base coat is improved, thereby increasing the adhesion between layers over time. Therefore, the weather resistance and corrosion resistance of the composite coating film are improved. On the other hand, when the PVC of the water-based top coating is higher than that of the water-based epoxy resin base coating, cracking or peeling may occur in the coating due to deterioration over time. In addition, the pigment volume concentration in this invention refers to the ratio (volume%) of the pigment which occupies for paint solid content.
更に、本発明の水性防食塗装方法においては、上記上塗り塗膜は、紫外線透過率が０．２％以下であることを要する。上塗り塗膜の紫外線透過率が０．２％を超えると、上塗り塗膜を透過した紫外線によって、下塗り塗膜や中塗り塗膜等の塗膜表面の劣化が起こり、層間剥離が生じる。なお、本発明における塗膜の紫外線透過率とは、波長３８０ｎｍの光線を塗膜に当てたときの透過率（％）を指す。 Furthermore, in the water-based anticorrosive coating method of the present invention, the top coat film needs to have an ultraviolet transmittance of 0.2% or less. When the UV transmittance of the top coat film exceeds 0.2%, the UV light transmitted through the top coat film causes the surface of the coat film such as the undercoat film or the intermediate coat film to deteriorate, resulting in delamination. In addition, the ultraviolet-ray transmittance of the coating film in this invention refers to the transmittance | permeability (%) when a light beam with a wavelength of 380 nm is applied to a coating film.
本発明の水性防食塗装方法は、まず、被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成する工程が行われる。下塗り塗膜の母材にエポキシ樹脂を用いることで、優れた防食性が得られる。なお、水性エポキシ樹脂下塗り塗料とは、エポキシ樹脂及び水を含有する下塗り塗料を意味する。 In the water-based anticorrosive coating method of the present invention, first, a step of applying a water-based epoxy resin primer to the surface to be coated to form a primer coating film is performed. By using an epoxy resin as the base material of the undercoat coating film, excellent anticorrosion properties can be obtained. In addition, a water-based epoxy resin undercoat paint means an undercoat paint containing an epoxy resin and water.
上記被塗装面としては、防食性の付与が必要な表面であれば特に制限されるものではないが、橋梁やプラント等の構造物の表面、より具体的には、鉄道橋、道路橋、ガスタンク、石油タンク、鉄塔等の炭素鋼等の材料からなる基材表面が挙げられる。 The surface to be coated is not particularly limited as long as it is a surface that needs to be provided with anticorrosion properties, but more specifically, the surface of a structure such as a bridge or a plant, more specifically, a railway bridge, a road bridge, a gas tank. And base material surfaces made of carbon steel materials such as oil tanks and steel towers.
上記水性エポキシ樹脂下塗り塗料は、多液反応硬化型であり且つ上記水性上塗り塗料よりもＰＶＣが高いことを除き特に制限されるものではないが、エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤とを含むことが好ましい。この場合、上記水性エポキシ樹脂下塗り塗料は、主剤と硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、主剤と硬化剤を混合する時期は、塗装の直前が好ましい。 The water-based epoxy resin base coating is not particularly limited except that it is a multi-component reaction curable type and has a higher PVC than the water-based top coating, but is a curing containing an epoxy resin emulsion and an amine resin emulsion. It is preferable to contain an agent. In this case, the water-based epoxy resin primer can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating.
上記水性エポキシ樹脂下塗り塗料において、エポキシ樹脂エマルジョンは、エポキシ樹脂が水等の水性媒体中で分散してなる乳濁液であり、特に制限されるものではないが、通常の強制乳化方式（乳化剤及び高速攪拌機等を使用する方式）によって、水等の水性媒体中でエポキシ樹脂を乳化させることにより調製される。 In the above-mentioned water-based epoxy resin primer, the epoxy resin emulsion is an emulsion in which the epoxy resin is dispersed in an aqueous medium such as water, and is not particularly limited. It is prepared by emulsifying the epoxy resin in an aqueous medium such as water by a method using a high-speed stirrer or the like.
上記エポキシ樹脂エマルジョンを構成するエポキシ樹脂は、１分子中に少なくとも２個のエポキシ基を有する樹脂である限り、特に限定されないが、例えば、多価アルコール又は多価フェノールとハロヒドリンとを反応させて得られるものであり、具体例としては、ビスフェノールＡ型エポキシ樹脂、ハロゲン化ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリグリコール型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、エポキシ化油、１，６−ヘキサンジオールジグリシジルエーテル及びネオペンチルグリコールジグリシジルエーテル等が挙げられる。これらの中でも、塗膜の機械的耐久性や防食性、被塗装面（例えば基材表面）との付着性等の観点から、ビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂が好ましい。なお、これらエポキシ樹脂は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、エポキシ樹脂エマルジョンの市販品としては、例えば、エポルジョンＥＡ１、２、３、７、１２、２０、５５及びＨＤ２（日本ＮＳＣ社製、商品名）；アクアトート２０５、５１０、３５２０、３５４０、３５２０１、５００３、及び５５２０（東都レジン化工社製、商品名）；ユカレジンＫＥ−００２、ＫＥ−１１６、Ｅ−１０２２、ＫＥ−３０１Ｃ（吉村油化学社製、商品名）；及びＥＭ−１０１−５０（アデカ社製、商品名）が挙げられる。 The epoxy resin constituting the epoxy resin emulsion is not particularly limited as long as it is a resin having at least two epoxy groups in one molecule. For example, it is obtained by reacting a polyhydric alcohol or polyhydric phenol with a halohydrin. Specific examples include bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, novolac type epoxy resin, polyglycol type epoxy resin, bisphenol F type epoxy resin, epoxidized oil, 1,6-hexane Examples include diol diglycidyl ether and neopentyl glycol diglycidyl ether. Among these, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoints of mechanical durability and corrosion resistance of the coating film, adhesion to the surface to be coated (for example, the surface of the substrate), and the like. In addition, these epoxy resins may be used independently and may be used in combination of 2 or more type. Moreover, as a commercial item of an epoxy resin emulsion, for example, Epourgeon EA1, 2, 3, 7, 12, 20, 55 and HD2 (Nippon NSC company make, brand name); Aquatote 205, 510, 3520, 3540, 35201 , 5003, and 5520 (trade name, manufactured by Toto Resin Chemical Co., Ltd.); Yuka Resin KE-002, KE-116, E-1022, KE-301C (trade name, manufactured by Yoshimura Oil Chemical Co., Ltd.); and EM-101-50 ( Adeka's product name).
上記主剤は、上記エポキシ樹脂エマルジョンの他、塗膜の可撓性を向上させる目的として、反応性希釈剤や非反応性希釈剤等の一般的に使用される希釈剤を含有してもよい。反応性希釈剤としては、例えば、カージュラＥ１０（油化シェルエポキシ社製、商品名）、ネオトートＳ（東都化成社製、商品名）、及びアデカグリシロールＥＤ５０２（旭電化工業社製、商品名）等の１官能性エポキシ樹脂が挙げられる。一方、非反応性希釈剤としては、例えば、ニカノールＬＬＬ等の石油樹脂及びクマロン樹脂等が挙げられる。これら希釈剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In addition to the epoxy resin emulsion, the main agent may contain a commonly used diluent such as a reactive diluent or a non-reactive diluent for the purpose of improving the flexibility of the coating film. Examples of reactive diluents include Cardura E10 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Neotote S (trade name, manufactured by Toto Kasei Co., Ltd.), and Adeka Glycilol ED502 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.). Monofunctional epoxy resins such as On the other hand, examples of the non-reactive diluent include petroleum resins such as Nicanol LLL and coumarone resins. These diluents may be used alone or in combination of two or more.
なお、上記主剤は、上記エポキシ樹脂エマルジョンと、必要に応じて適宜選択される各種成分とを混合することにより調製できる。 In addition, the said main ingredient can be prepared by mixing the said epoxy resin emulsion and the various components suitably selected as needed.
上記硬化剤を構成するアミン樹脂エマルジョンとは、アミン樹脂が水等の水性媒体中で分散してなる乳濁液であり、ここで、アミン樹脂とは、１分子中に２個以上のアミノ基を含有するポリアミン樹脂である。上記ポリアミン樹脂としては、例えば、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、トリアミノプロパン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、イソホロンジアミン、及び１，３−ビスアミノメチルシクロヘキサン等の脂肪族ポリアミン；フェニレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、及びジアミノジフエニルメタン等の芳香族ポリアミン；ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、トリエチレングリコールジアミン、及びトリプロピレングリコールジアミン等の他のポリアミン化合物と、これらポリアミン樹脂のアミノ基を変性してなる変性ポリアミン樹脂とが挙げられる。なお、上記ポリアミン樹脂の変性には、既知の方法が利用でき、変性反応の例としては、アミノ基のアミド化、アミノ基とカルボニル化合物のマンニッヒ反応、アミノ基とエポキシ基の付加反応等が挙げられる。ここで、アミノ基にエポキシ基等が付加したタイプの変性ポリアミン樹脂をアダクトタイプの変性ポリアミン樹脂といい、防食性の観点から、アミノ基にエポキシ基が付加したエポキシアダクトタイプの変性ポリアミン樹脂が好ましい。 The amine resin emulsion constituting the curing agent is an emulsion in which an amine resin is dispersed in an aqueous medium such as water. Here, the amine resin means two or more amino groups in one molecule. Is a polyamine resin containing Examples of the polyamine resin include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, and 1,3-bisaminomethylcyclohexane. Aliphatic polyamines; aromatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane; such as polyoxyethylenediamine, polyoxypropylenediamine, triethyleneglycoldiamine, and tripropyleneglycoldiamine Examples include other polyamine compounds and modified polyamine resins obtained by modifying the amino groups of these polyamine resins. For modification of the polyamine resin, known methods can be used. Examples of the modification reaction include amidation of an amino group, Mannich reaction of an amino group and a carbonyl compound, addition reaction of an amino group and an epoxy group, and the like. It is done. Here, a modified polyamine resin in which an epoxy group or the like is added to an amino group is referred to as an adduct type modified polyamine resin, and an epoxy adduct type modified polyamine resin in which an epoxy group is added to an amino group is preferable from the viewpoint of corrosion resistance. .
なお、上記硬化剤は、上記アミン樹脂エマルジョンと、必要に応じて適宜選択される各種成分とを混合することにより調製できる。 In addition, the said hardening | curing agent can be prepared by mixing the said amine resin emulsion and the various components suitably selected as needed.
また、上記主剤及び／又は硬化剤は、その他塗料に一般的に使用される着色顔料、防錆顔料及び体質顔料等を特に制限無く含有することができる。着色顔料、防錆顔料及び体質顔料の具体例としては、酸化チタン、ベンガラ、黄色酸化鉄、カーボンブラック、トリポリリン酸アルミニウム、リン酸亜鉛、メタホウ酸バリウム、炭酸カルシウム、硫酸バリウム、タルク、クレー、マイカ、アルミナ、ミョウバン、白土、水酸化マグネシウム、及び酸化マグネシウム等の無機顔料や、フタロシアニンブルー、フタロシアニングリーン、ナフトールレッド、キナクリドンレッド、ベンズイミダゾロンイエロー、ハンザイエロー、ベンズイミダゾロンオレンジ、及びジオキサジンバイオレット等の有機顔料が挙げられる。これら顔料は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The main agent and / or curing agent may contain other color pigments, rust preventive pigments, extender pigments and the like that are generally used in other paints. Specific examples of color pigments, rust preventive pigments and extender pigments include titanium oxide, bengara, yellow iron oxide, carbon black, aluminum tripolyphosphate, zinc phosphate, barium metaborate, calcium carbonate, barium sulfate, talc, clay, mica , Inorganic pigments such as alumina, alum, clay, magnesium hydroxide, and magnesium oxide, phthalocyanine blue, phthalocyanine green, naphthol red, quinacridone red, benzimidazolone yellow, hansa yellow, benzimidazolone orange, and dioxazine violet And organic pigments. These pigments may be used alone or in combination of two or more.
更に、上記主剤及び／又は硬化剤には、水性エポキシ樹脂下塗り塗料に各種機能を付与するため、増粘剤、分散剤、消泡剤、沈降防止剤、防カビ剤、防腐剤、紫外線吸収剤、又は光安定剤等が適宜添加されてもよい。また、エポキシ樹脂エマルジョンを構成するエポキシ樹脂とアミン樹脂エマルジョンを構成するポリアミン樹脂との融着を促進するため、上記主剤及び／又は硬化剤には、有機溶剤を配合することも可能である。有機溶剤としては、例えば、エチレングリコールモノｎ−ブチルエーテル、エチレングリコールモノｉ−ブチルエーテル、エチレングリコールモノｎ−プロピルエーテル、エチレングリコールモノｉ−プロピルエーテル、ジエチレングリコールモノｎ−ブチルエーテル、ジエチレングリコールモノｉ−ブチルエーテル、ジエチレングリコールモノｎ−プロピルエーテル、ジエチレングリコールモノｉ−プロピルエーテル、ジプロピレングリコールモノｎ−ブチルエーテル、ジプロピレングリコールモノｉ−ブチルエーテル、ジプロピレングリコールモノｎ−プロピルエーテル、ジプロピレングリコールモノｉ−プロピルエーテル、ジエチレングリコールジエチルエーテル、及びジエチレングリコールジブチルエーテル等のグリコールエーテル類、２，２，４−トリメチルペンタンジオールモノイソブチレート、及び２，２，４−トリメチルペンタンジオールジイソブチレート等が挙げられる。これら有機溶剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Further, the main agent and / or curing agent has a thickener, a dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, and an ultraviolet absorber for imparting various functions to the water-based epoxy resin primer. Or a light stabilizer etc. may be added suitably. Moreover, in order to accelerate | stimulate melt | fusion of the epoxy resin which comprises an epoxy resin emulsion, and the polyamine resin which comprises an amine resin emulsion, it is also possible to mix | blend an organic solvent with the said main ingredient and / or a hardening | curing agent. Examples of the organic solvent include ethylene glycol mono n-butyl ether, ethylene glycol mono i-butyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono i-butyl ether, diethylene glycol. Mono n-propyl ether, diethylene glycol mono i-propyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono i-butyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono i-propyl ether, diethylene glycol diethyl ether And glycol ethers such as diethylene glycol dibutyl ether , 2,2,4-trimethyl pentanediol mono-isobutyrate, and 2,2,4-trimethyl pentanediol diisobutyrate and the like. These organic solvents may be used alone or in combination of two or more.
上記水性エポキシ樹脂下塗り塗料において、アミン樹脂エマルジョンを含む硬化剤の配合割合は、塗膜の硬化性及び防食性等の観点から、主剤中に含まれるエポキシ樹脂エマルジョンを構成するエポキシ樹脂のエポキシ基１当量に対して、アミン樹脂エマルジョンを構成するアミン樹脂の活性水素が、通常０．５〜２．０当量の範囲内であるのが好ましい。 In the water-based epoxy resin undercoat paint, the blending ratio of the curing agent containing the amine resin emulsion is the epoxy group 1 of the epoxy resin constituting the epoxy resin emulsion contained in the main agent from the viewpoint of the curability of the coating film and the corrosion resistance. It is preferable that the active hydrogen of the amine resin constituting the amine resin emulsion is usually in the range of 0.5 to 2.0 equivalents with respect to the equivalent.
本発明の水性防食塗装方法において、上記水性エポキシ樹脂下塗り塗料を塗布した後に形成される下塗り塗膜の膜厚（乾燥膜厚）は、通常２０〜２５０μｍの範囲内であり、３０〜１５０μｍの範囲内であるのが好ましい。また、上記水性エポキシ樹脂下塗り塗料の塗装方法としては、特に制限されず、既知の塗装手段、例えば、エアスプレー塗装、エアレススプレー塗装、刷毛塗り、又はローラー塗り等が利用できる。なお、これら塗装手段を複数回利用し、水性エポキシ樹脂下塗り塗料を塗り重ねることも可能である。また、塗装環境は、特に制限されるものではないが、０℃以下のような極端な低温環境や被塗装表面の温度が８０℃以上のような高温環境は避けることが望ましい。水性エポキシ樹脂下塗り塗料の乾燥時間は、気温や湿度等の養生環境条件によって異なる。例えば、気温２３℃、相対湿度５０％の条件であれば７日間程度の乾燥時間が望ましいが、積層塗膜を形成するために次工程の塗料を塗り重ねる場合には、支障なく塗り重ねることができる。なお、形成された積層塗膜が、本来の性能を発揮できるのであれば、これに限定されない。 In the water-based anticorrosion coating method of the present invention, the film thickness (dry film thickness) of the undercoat film formed after applying the water-based epoxy resin undercoat is usually in the range of 20 to 250 μm and in the range of 30 to 150 μm. Is preferably within. The method for applying the water-based epoxy resin primer is not particularly limited, and known coating means such as air spray coating, airless spray coating, brush coating, or roller coating can be used. In addition, it is also possible to use these coating means a plurality of times and repeatedly apply the water-based epoxy resin primer. The coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C. or less or a high temperature environment where the temperature of the surface to be coated is 80 ° C. or more. The drying time of the water-based epoxy resin undercoat varies depending on the curing environment conditions such as temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the next coating material is applied repeatedly to form a laminated coating film, it can be applied without any trouble. it can. In addition, if the formed laminated coating film can exhibit original performance, it will not be limited to this.
本発明の水性防食塗装方法は、次いで、下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する工程が行われる。 In the water-based anticorrosive coating method of the present invention, a step of forming a topcoat film by applying an aqueous topcoat onto the undercoat film is then performed.
上記水性上塗り塗料は、多液反応硬化型であり、水性エポキシ樹脂下塗り塗料よりもＰＶＣが低く、且つ形成される上塗り塗膜の紫外線透過率が０．２％以下である限り特に制限されるものではないが、水性ウレタン樹脂塗料、水性フッ素樹脂塗料等が好ましい。 The above-mentioned water-based top coating is a multi-component reaction curable type, and is particularly limited as long as the PVC is lower than the water-based epoxy resin base coating and the UV transmittance of the formed top coating is 0.2% or less. However, water-based urethane resin paints, water-based fluororesin paints and the like are preferable.
上記水性ウレタン樹脂塗料は、例えば、１分子中に複数の水酸基を有するアクリル樹脂が水等の水性媒体中で分散してなる分散液又は乳濁液を含む主剤と、１分子中に１つのイソシアネート基を有するイソシアネート樹脂又は１分子中に複数のイソシアネート基を有するポリイソシアネート樹脂を含む硬化剤とからなる。この場合、上記水性ウレタン樹脂塗料は、主剤と硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、主剤と硬化剤を混合する時期は、塗装の直前が好ましく、塗装後に硬化反応を開始し、塗膜が形成される。 The aqueous urethane resin paint includes, for example, a main agent containing a dispersion or emulsion in which an acrylic resin having a plurality of hydroxyl groups per molecule is dispersed in an aqueous medium such as water, and one isocyanate per molecule. And a curing agent containing an isocyanate resin having a group or a polyisocyanate resin having a plurality of isocyanate groups in one molecule. In this case, the water-based urethane resin coating can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating, and after the coating, a curing reaction is started and a coating film is formed.
上記水性フッ素樹脂塗料は、例えば、１分子中に複数の水酸基を有するフッ素樹脂が水等の水性媒体中で分散してなる分散液又は乳濁液を含む主剤と、１分子中に１つのイソシアネート基を有するイソシアネート樹脂又は１分子中に複数のイソシアネート基を有するポリイソシアネート樹脂を含む硬化剤とからなる。この場合、上記水性フッ素樹脂塗料は、主剤と硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、主剤と硬化剤を混合する時期は、塗装の直前が好ましく、塗装後に硬化反応を開始し、塗膜が形成される。 The water-based fluororesin coating material includes, for example, a main agent containing a dispersion or emulsion in which a fluororesin having a plurality of hydroxyl groups per molecule is dispersed in an aqueous medium such as water, and one isocyanate per molecule. And a curing agent containing an isocyanate resin having a group or a polyisocyanate resin having a plurality of isocyanate groups in one molecule. In this case, the aqueous fluororesin coating material can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating, and after the coating, a curing reaction is started and a coating film is formed.
なお、上記アクリル樹脂が分散してなる分散液又は乳濁液としては、バーノックＷＥ−３０１、ＷＥ−３０４、ＷＥ−３０６、ＷＥ−３１０、ＷＤ−５５１（ＤＩＣ社製、商品名）等が挙げられ、上記フッ素樹脂が分散してなる分散液又は乳濁液としては、ルミフロンＦＥ−４２００、ＦＥ−４３００、ＦＥ−４４００、ＦＥ−４５００（旭硝子社製、商品名）等が挙げられ、イソシアネート樹脂又はポリイソシアネート樹脂としては、バーノックＤＮＷ−５５００、ＤＮＷ−６０００（ＤＩＣ社製、商品名）、デュラネートＷＢ４０−１００、ＷＴ２０−１００、ＷＴ３０−１００、ＷＥ５０−１００（旭化成ケミカルズ社製、商品名）等が挙げられる。これら配合剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Examples of the dispersion or emulsion obtained by dispersing the acrylic resin include Barnock WE-301, WE-304, WE-306, WE-310, WD-551 (manufactured by DIC, trade name). Examples of the dispersion or emulsion obtained by dispersing the fluororesin include Lumiflon FE-4200, FE-4300, FE-4400, FE-4500 (trade name, manufactured by Asahi Glass Co., Ltd.), and the like. Or as polyisocyanate resin, Bernock DNW-5500, DNW-6000 (made by DIC, trade name), Duranate WB40-100, WT20-100, WT30-100, WE50-100 (made by Asahi Kasei Chemicals, trade name), etc. Is mentioned. These compounding agents may be used alone or in combination of two or more.
また、上記水性上塗り塗料（具体的には水性ウレタン樹脂塗料及び水性フッ素樹脂塗料）には、上記水性エポキシ樹脂下塗り塗料にも配合できる配合剤、例えば着色顔料、体質顔料、有機顔料、増粘剤、分散剤、消泡剤、沈降防止剤、防カビ剤、防腐剤、紫外線吸収剤、光安定剤、有機溶剤等を必要に応じて配合してもよい。 In addition, the water-based top coat (specifically, water-based urethane resin paint and water-based fluororesin paint) can be blended with the water-based epoxy resin base coat, for example, coloring pigment, extender pigment, organic pigment, thickener. A dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, an ultraviolet absorber, a light stabilizer, an organic solvent and the like may be blended as necessary.
本発明の水性防食塗装方法において、上記水性上塗り塗料を塗布した後に形成される上塗り塗膜の膜厚（乾燥膜厚）は、通常１０〜２００μｍの範囲内であり、２０〜１００μｍの範囲内であるのが好ましい。また、上記水性上塗り塗料の塗装方法としては、特に制限されず、既知の塗装手段、例えば、エアスプレー塗装、エアレススプレー塗装、刷毛塗り、又はローラー塗り等が利用できる。なお、塗装は、１回に限定されず、合計膜厚が１０〜２００μｍの範囲内にあれば、複数回に分けて塗装を行ってもよい。また、上記水性上塗り塗料の塗装環境や乾燥時間については、水性エポキシ樹脂下塗り塗料について記載したものと同じ条件が適用できる。 In the water-based anticorrosive coating method of the present invention, the film thickness (dry film thickness) of the top coat film formed after applying the water-based top coat is usually in the range of 10 to 200 μm and in the range of 20 to 100 μm. Preferably there is. The method for applying the water-based top coating is not particularly limited, and known coating means such as air spray coating, airless spray coating, brush coating, or roller coating can be used. The coating is not limited to one time, and the coating may be performed in a plurality of times as long as the total film thickness is in the range of 10 to 200 μm. The same conditions as those described for the water-based epoxy resin undercoating can be applied to the coating environment and drying time of the water-based top coating.
本発明の水性防食塗装方法において、上記被塗装面には、ジンクリッチペイント処理、亜鉛メッキ処理及び金属溶射から選ばれる処理が施され、防食下地が形成されていることが好ましい。上記水性エポキシ樹脂下塗り塗料を塗布する前に、かかる処理を施すことによって、防食性を更に向上させることができる。なお、ジンクリッチペイントとは、高濃度の亜鉛を含有する塗料を意味し、水を溶媒とする水性ジンクリッチペイントが好適である。なお、被塗装面に防食下地が形成されているため、水性エポキシ樹脂下塗り塗料は、該防食下地の上に塗布されることになる。 In the water-based anticorrosion coating method of the present invention, the surface to be coated is preferably subjected to a treatment selected from zinc rich paint treatment, galvanization treatment and metal spraying to form an anticorrosion base. By applying such treatment before applying the water-based epoxy resin primer, the anticorrosion can be further improved. In addition, a zinc rich paint means the coating material containing high concentration zinc, and the water-based zinc rich paint which uses water as a solvent is suitable. In addition, since the anti-corrosion base is formed in the to-be-coated surface, the water-based epoxy resin undercoat paint is applied on the anti-corrosion base.
また、本発明の水性防食塗装方法においては、上記被塗装面の少なくとも一部が、旧塗膜の表面であってもよい。例えば、基材面上に予め形成した塗膜が経年しても、その状態が健全であれば、該塗膜の表面上に、上記水性エポキシ樹脂下塗り塗料を直接塗布することができる。 Moreover, in the water-based anticorrosive coating method of the present invention, at least a part of the surface to be coated may be the surface of an old coating film. For example, even if the coating film previously formed on the substrate surface is aged, if the state is healthy, the water-based epoxy resin primer can be directly applied on the surface of the coating film.
更に、本発明の水性防食塗装方法においては、上記水性上塗り塗料を塗布する前に、多液反応硬化型の水性中塗り塗料を上記下塗り塗膜上に塗布し、中塗り塗膜が形成されていることが好ましい。このように下塗り塗膜と上塗り塗膜の間に中塗り塗膜が組み込まれた複合塗膜は、中塗り塗膜に各種機能を期待でき、例えば、上塗り塗膜の仕上がり外観を向上させることも可能である。なお、下塗り塗膜上に中塗り塗膜が形成されているため、水性上塗り塗料は、該中塗り塗膜上に塗布されることになる。上記水性中塗り塗料は、多液反応硬化型である限り特に制限されるものではないが、水性エポキシ樹脂塗料及び水性ウレタン樹脂塗料等が好ましい。なお、上記水性エポキシ樹脂塗料には、上述の水性エポキシ樹脂下塗り塗料が使用でき、また、上記水性ウレタン樹脂塗料には、水性上塗り塗料として使用できる上述の水性ウレタン樹脂塗料が使用できる。 Furthermore, in the water-based anticorrosive coating method of the present invention, before applying the water-based top coating, a multi-component reaction curing type water-based intermediate coating is applied onto the base coating to form an intermediate coating. Preferably it is. Thus, the composite coating film in which the intermediate coating film is incorporated between the undercoating film and the top coating film can be expected to have various functions in the intermediate coating film, for example, to improve the finished appearance of the top coating film. Is possible. In addition, since the intermediate coating film is formed on the undercoat coating film, the water-based top coating composition is applied onto the intermediate coating film. The aqueous intermediate coating is not particularly limited as long as it is a multi-component reaction curable type, but an aqueous epoxy resin coating and an aqueous urethane resin coating are preferable. In addition, the above-mentioned water-based epoxy resin undercoat can be used for the water-based epoxy resin paint, and the above-mentioned water-based urethane resin paint that can be used as a water-based top coat can be used for the water-based urethane resin paint.
＜塗装体＞
次に、本発明の塗装体を詳細に説明する。本発明の塗装体は、上述の水性防食塗装方法によって被塗装面上に複合塗膜が形成されていることを特徴とする。複合塗膜を備えた物体、例えば橋梁やプラント等の構造物は、耐候性及び防食性に優れる。
<Painted body>
Next, the coated body of the present invention will be described in detail. The coated body of the present invention is characterized in that a composite coating film is formed on a surface to be coated by the above-described aqueous anticorrosion coating method. An object provided with a composite coating film, such as a structure such as a bridge or a plant, is excellent in weather resistance and corrosion resistance.
以下、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。なお、下記例中、「部」及び「％」は、それぞれ「質量部」及び「質量％」を意味する。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited only to these Examples. In the following examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.
＜製造例１＞
混合機に、イオン交換水を１１部投入し、これに分散剤１部、消泡剤０．３部、酸化チタン１０部、トリポリリン酸アルミニウム５部、沈降性硫酸バリウム２０部、及びカオリンクレー８部を撹拌環境下で除々に投入し、投入完了後、粒度が５０μｍ以下になるまで混合した。次いで、混合機に、エポキシ樹脂エマルジョン４５部、及びエチレングリコールモノｎ−ブチルエーテル４部を撹拌環境下で徐々に投入し、１０分間撹拌を行い、下塗り塗料１の主剤を調製した。この主剤に硬化剤としてアミン樹脂エマルジョン１２部を塗装直前に混合し、下塗り塗料１を調製した。
<Production Example 1>
11 parts of ion-exchanged water is added to a mixer, and 1 part of a dispersant, 0.3 part of an antifoaming agent, 10 parts of titanium oxide, 5 parts of aluminum tripolyphosphate, 20 parts of precipitated barium sulfate, and kaolin clay 8 Portions were gradually added under a stirring environment, and after completion of the addition, mixing was performed until the particle size became 50 μm or less. Next, 45 parts of the epoxy resin emulsion and 4 parts of ethylene glycol mono-n-butyl ether were gradually added to the mixer in a stirring environment, and the mixture was stirred for 10 minutes to prepare the main component of the undercoat paint 1. Undercoat paint 1 was prepared by mixing 12 parts of an amine resin emulsion as a curing agent with this main agent immediately before coating.
＜下塗り塗料１〜２及び中塗り塗料＞
以下の表１には、下塗り塗料１〜２及び中塗り塗料の配合処方を示す。なお、下塗り塗料２及び中塗り塗料は、表１に示す処方に従って配合剤を配合した以外は、製造例１と同様にして、調製された。
<Undercoat paint 1-2 and intermediate paint>
Table 1 below shows the formulation of the undercoat paints 1-2 and the intermediate paint. The undercoat paint 2 and the intermediate coat paint were prepared in the same manner as in Production Example 1 except that the compounding agents were blended according to the formulation shown in Table 1.
＜製造例２＞
混合機に、イオン交換水８部を投入し、これに分散剤１部、及び酸化チタン２５部を撹拌環境下で除々に投入し、投入完了後、粒度が１０μｍ以下になるまで混合した。次いで、混合機に、アクリルポリオール樹脂エマルジョン６０部、ジエチレングリコールジｎ−ブチルエーテル４部、紫外線吸収剤０．５部、増粘剤１部、及び消泡剤０．５部を撹拌環境下で徐々に投入し、１０分間撹拌を行い、上塗り塗料１の主剤を調製した。この主剤にイソシアネート樹脂１０部を塗装直前に混合し、上塗り塗料１を調製した。
<Production Example 2>
8 parts of ion-exchanged water was added to the mixer, and 1 part of the dispersant and 25 parts of titanium oxide were gradually added in a stirring environment. After completion of the addition, mixing was performed until the particle size became 10 μm or less. Subsequently, 60 parts of an acrylic polyol resin emulsion, 4 parts of diethylene glycol di-n-butyl ether, 0.5 part of an ultraviolet absorber, 1 part of a thickener, and 0.5 part of an antifoaming agent are gradually added to a mixer in a stirring environment. Then, the mixture was stirred for 10 minutes to prepare the main agent of the top coat 1. Top coating composition 1 was prepared by mixing 10 parts of an isocyanate resin with this base material immediately before coating.
＜上塗り塗料１〜２＞
以下の表２には、上塗り塗料１〜２の配合処方を示す。なお、上塗り塗料２は、表２に示す処方に従って配合剤を配合した以外は、製造例２と同様にして、調製された。
<Topcoat paint 1-2>
Table 2 below shows the formulation of top coat paints 1-2. The top coat 2 was prepared in the same manner as in Production Example 2, except that the compounding agent was blended according to the formulation shown in Table 2.
なお、表１及び表２は、更に顔料容積濃度の設計値及び紫外線透過率を示しているが、これらの値は、以下の方法で算出される。 Tables 1 and 2 further show the design value and ultraviolet transmittance of the pigment volume concentration, and these values are calculated by the following method.
＜顔料容積濃度＞
塗料の顔料容積濃度（体積％）は、以下の式によって算出された。
顔料容積濃度 ＝ （顔料の体積）／ （塗料固形分の体積） × １００
塗料固形分の体積 ＝ 樹脂の体積 ＋ 顔料の体積
<Pigment volume concentration>
The pigment volume concentration (volume%) of the paint was calculated by the following formula.
Pigment volume concentration = (Pigment volume) / (Paint solids volume) × 100
Volume of paint solids = Resin volume + Pigment volume
＜紫外線透過率＞
ポリプロピレン板上に、乾燥膜厚が２５〜３５μｍになるようエアスプレーを用いて、上塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて７日間乾燥させ、その後、ポリプロピレン板から乾燥塗膜を剥がし、上塗り塗料の単離膜を作製した。次に、得られた単離膜の波長３８０ｎｍにおける紫外線透過率を島津製作所社製の紫外可視近赤外分析光度計ＵＶ３１００ＰＣを用いて測定した。
<Ultraviolet transmittance>
On the polypropylene plate, apply the top coat using air spray so that the dry film thickness is 25 to 35 μm, and dry it for 7 days under the conditions of 23 ° C. and 50% relative humidity. The film was peeled off to produce an isolated film for the top coat. Next, the ultraviolet transmittance at a wavelength of 380 nm of the obtained isolated membrane was measured using an ultraviolet-visible near-infrared analytical photometer UV3100PC manufactured by Shimadzu Corporation.
（注１）Ｄｉｓｐｅｒｂｙｋ−１９０（ビックケミー・ジャパン社製）
（注２）ＢＹＫ−０９３（ビックケミー・ジャパン社製）
（注３）エポルジョンＥＡ５５（日本ＮＳＣ社製；樹脂固形分５５％、エポキシ当量４９５ｇ／ｅｑ）
（注４）フジキュアーＦＸＳ−９１８−ＦＡ（Ｔ＆Ｋ ＴＯＫＡ社製；エポキシアダクトタイプの変性ポリアミン樹脂、樹脂固形分５６％）
（注５）バーノックＷＥ−３０１（ＤＩＣ社製；樹脂固形分４５％）
（注６）ＴＩＮＵＶＩＮ１１３０（ＢＡＳＦジャパン社製）
（注７）プライマルＲＭ−８Ｗ（ローム＆ハース社製）
（注８）バーノックＤＮＷ−６０００（ＤＩＣ社製；樹脂固形分１００％）
(Note 1) Disperbyk-190 (by Big Chemie Japan)
(Note 2) BYK-093 (by Big Chemie Japan)
(Note 3) Epourgeon EA55 (NSC Japan, resin solid content 55%, epoxy equivalent 495 g / eq)
(Note 4) Fuji Cure FXS-918-FA (manufactured by T & K TOKA; epoxy adduct type modified polyamine resin, resin solid content 56%)
(Note 5) Vernock WE-301 (manufactured by DIC; resin solid content 45%)
(Note 6) TINUVIN 1130 (manufactured by BASF Japan)
(Note 7) Primal RM-8W (Rohm & Haas)
(Note 8) Vernock DNW-6000 (manufactured by DIC; resin solid content 100%)
（実施例１〜３及び比較例１〜２）
以下の表３には、使用した材料を示す（使用した材料には「○」が付けられている）。なお、試験板としては、素地調整程度がＩＳＯ ８５０１−１ Ｓａ２．５のグリッドブラスト処理鋼板（１５０×７０×３．２ｍｍ）又はＪＩＳ Ｇ ３３０２に規定する亜鉛めっき鋼鈑ＳＧＨ４００ ＺＣ Ｚ２７（１５０×７０×２．３ｍｍ）のいずれかを用いた。
(Examples 1-3 and Comparative Examples 1-2)
Table 3 below shows the materials used (the materials used are marked with “◯”). In addition, as a test plate, the base grading degree is ISO 8501-1 Sa2.5 grid blasted steel plate (150 × 70 × 3.2 mm) or galvanized steel plate SGH400 ZC Z27 (150 × 70) specified in JIS G 3302 × 2.3 mm) was used.
まず、試験板の両面に、乾燥膜厚が５５〜６５μｍになるようエアスプレーを用いて、下塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて１日間乾燥させ、下塗り塗膜を形成させた。実施例２においては、次に、試験板の両面に形成された２枚の下塗り塗膜上に、乾燥膜厚が２５〜３５μｍになるようエアスプレーを用いて、中塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて１日間乾燥させ、中塗り塗膜を形成させた。最後に、実施例１及び３並びに比較例１〜２においては、試験板の両面に形成された２枚の下塗り塗膜上に、実施例２においては、２枚の下塗り塗膜それぞれの上に形成された２枚の中塗り塗膜上に、乾燥膜厚が２５〜３５μｍになるようエアスプレーを用いて、上塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて７日間乾燥させ、複合塗膜を備えた試験片を作製した。これら試験片の防食性及び耐候性を以下の方法に従い評価した。結果を表３に示す。 First, on both surfaces of the test plate, an undercoat paint was applied using an air spray so that the dry film thickness was 55 to 65 μm, and dried for one day under conditions of 23 ° C. and 50% relative humidity. Formed. In Example 2, next, an intermediate coating was applied onto the two undercoat films formed on both sides of the test plate using an air spray so that the dry film thickness was 25 to 35 μm. It was dried for 1 day under the conditions of 50 ° C. and 50% relative humidity to form an intermediate coating film. Finally, in Examples 1 and 3 and Comparative Examples 1-2, on the two undercoat films formed on both sides of the test plate, in Example 2, on each of the two undercoat films. On the two intermediate coatings that were formed, the top coating was applied using air spray so that the dry film thickness was 25 to 35 μm, and dried for 7 days at 23 ° C. and 50% relative humidity. A test piece provided with a composite coating film was prepared. The corrosion resistance and weather resistance of these test pieces were evaluated according to the following methods. The results are shown in Table 3.
＜防食性＞
ＪＩＳ Ｋ５６００−７−１の耐中性塩水噴霧性に準じて、試験片を塩水噴霧に５００時間さらし、その後、該試験片に生じたサビ、フクレ等の発生程度を下記の基準に従って評価した。
◎：カット部から１ｍｍ以上離れた試験片表面にサビ、フクレ等の異常が無い。
○：カット部から３ｍｍ以上離れた試験片表面にサビ、フクレ等の異常が無い。
×：カット部から３ｍｍ以上離れた試験片表面にサビ、フクレが発生。
<Anti-corrosion>
In accordance with JIS K5600-7-1, the test piece was subjected to salt spray for 500 hours according to the medium-resistant salt spray property, and then the degree of occurrence of rust, swelling, etc. generated on the test piece was evaluated according to the following criteria.
A: There is no abnormality such as rust or swelling on the surface of the test piece 1 mm or more away from the cut part.
○: There is no abnormality such as rust and swelling on the surface of the test piece 3 mm or more away from the cut part.
X: Rust and swelling occur on the surface of the test piece 3 mm or more away from the cut part.
＜耐候性＞
ＪＩＳ Ｋ５６００−７−７の促進耐候性及び促進耐光性（キセノンランプ法）のサイクルＡに準じて、１０００時間照射した後の試験片の光沢保持率を算出し、また、該試験片に生じた割れ、はがれ、フクレ等の発生を下記の基準に従って評価した。なお、光沢保持率は、ＢＹＫガードナー社製の光沢計ＢＹＫガードナー・マイクロ−グロスによって照射前後の光沢値を測定し、以下の式によって算出された。
光沢保持率（％）＝ 照射後の光沢値／照射前の光沢値×１００
○：光沢保持率が７０％以上で、且つ割れ、はがれ、フクレ等の異常がない。
×：光沢保持率が７０％未満、若しくは割れ、はがれ、フクレが発生。
<Weather resistance>
In accordance with cycle A of accelerated weather resistance and accelerated light resistance (xenon lamp method) of JIS K5600-7-7, the gloss retention of the test piece after 1000 hours of irradiation was calculated, and occurred in the test piece. The occurrence of cracking, peeling, swelling, etc. was evaluated according to the following criteria. The gloss retention rate was calculated by the following equation after measuring the gloss value before and after irradiation with a gloss meter BYK Gardner Micro-Gloss manufactured by BYK Gardner.
Gloss retention (%) = Gloss value after irradiation / Gloss value before irradiation × 100
○: Gloss retention is 70% or more, and there is no abnormality such as cracking, peeling or swelling.
X: The gloss retention is less than 70%, or cracking, peeling, and swelling are generated.
Claims (5)
ａ）前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が、多液反応硬化型である。
ｂ）前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度が低い。
ｃ）前記上塗り塗膜は、紫外線透過率が０．２％以下である。 A water-based anticorrosion coating method in which a water-based epoxy resin base coat is applied on a surface to be coated to form a base coat, and then a water base coat is applied on the base coat to form a top coat. meets the following requirements a) to c), the aqueous epoxy resin primer coating comprises a hardening agent comprising a main agent and an amine resin emulsion containing an epoxy resin emulsion, the amine resin emulsion, an epoxy group to an amino group A water-based anticorrosive coating method, which is an emulsion in which an added epoxy adduct type modified polyamine resin is dispersed in an aqueous medium .
a) Both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable.
b) The water-based top coating has a lower pigment volume concentration than the water-based epoxy resin base coating.
c) The top coat film has an ultraviolet transmittance of 0.2% or less.
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| CN201380011848.8A CN104136559A (en) | 2012-03-23 | 2013-02-25 | Water-based epoxy resin paint composition, anticorrosive painting method, and painted body |
| CN201610515546.XA CN106118363B (en) | 2012-03-23 | 2013-02-25 | Aqueous epoxide resin paint composition, corrosion-proof coating method and coated-body |
| MYPI2014002151A MY166189A (en) | 2012-03-23 | 2013-02-25 | Aqueous anticorrosive coating method and painted body |
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| MYPI2017000285A MY179883A (en) | 2012-03-23 | 2013-02-25 | Water-soluble anticorrosive paint composition and corrosion protection method |
| PH12014501710A PH12014501710A1 (en) | 2012-03-23 | 2014-07-28 | Aqueous epoxy resin coating composition, anticorrosive coating method and coated body |
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| CN115651482A (en) * | 2022-11-04 | 2023-01-31 | 中远关西涂料（上海）有限公司 | High-gloss water-based epoxy coating for engineering machinery and preparation method thereof |
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| JPH0880471A (en) * | 1994-09-13 | 1996-03-26 | Toho Kengiyou Kk | Method for coating waterproof reactive polymer emulsion multi-layer coatings and its finish coating composition |
| JPH1121514A (en) * | 1997-06-30 | 1999-01-26 | Kansai Paint Co Ltd | Water-based flat coating material and process for finish coating therewith |
| JP4937629B2 (en) * | 2006-03-31 | 2012-05-23 | エスケー化研株式会社 | Coating method |
| JP5016887B2 (en) * | 2006-10-02 | 2012-09-05 | 関西ペイント株式会社 | How to paint concrete surface |
| JP2009046564A (en) * | 2007-08-17 | 2009-03-05 | Toshiba Corp | Extraheavy corrosion-resistant coating material, coating method thereof and coated material |
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| CN111636088A (en) * | 2020-04-26 | 2020-09-08 | 四川宁江山川机械有限责任公司 | Surface treatment process for rear damping workpiece of vehicle shock absorber |
| CN115651482A (en) * | 2022-11-04 | 2023-01-31 | 中远关西涂料（上海）有限公司 | High-gloss water-based epoxy coating for engineering machinery and preparation method thereof |
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