JP5512940B2 - Electrodeposition coating pretreatment composition and electrodeposition coating method - Google Patents
Electrodeposition coating pretreatment composition and electrodeposition coating method Download PDFInfo
- Publication number
- JP5512940B2 JP5512940B2 JP2008213338A JP2008213338A JP5512940B2 JP 5512940 B2 JP5512940 B2 JP 5512940B2 JP 2008213338 A JP2008213338 A JP 2008213338A JP 2008213338 A JP2008213338 A JP 2008213338A JP 5512940 B2 JP5512940 B2 JP 5512940B2
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- Prior art keywords
- electrodeposition coating
- pretreatment
- composition
- metal
- electrodeposition
- Prior art date
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Images
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- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、電着塗装前処理用組成物および電着塗装方法に関する。 The present invention relates to an electrodeposition coating pretreatment composition and an electrodeposition coating method.
従来から、家電機器、音響機器、電子機器、通信機器、精密機器、光学機器、輸送機器、レジャー・スポーツ用品、装飾品、家具、建材などの広範な工業製品において、部品の保護、装飾などを目的として部品表面に金属めっきを施すことが一般的に行われる。また、金属めっきは、大気中の酸素、硫黄酸化物、雨水、海水などによって腐蝕する場合があるので、その耐食性を向上させて腐蝕を防止するために、金属表面に保護用塗膜が形成される。保護用塗膜の形成には、一般に、電着塗装法が利用される。電着塗装によれば、電荷を付与した塗膜形成成分を含む浴中に、保護用塗膜を形成しようとする金属めっきを施した被処理品を浸漬させ、浴内において通電し、該被処理品の金属めっき表面に塗膜成形成分を析出さ、焼付け処理を施して保護用塗膜を形成する。このとき、塗膜形成成分に顔料などの着色剤を含有させておけば、被処理品の多色化も容易である。また、金属めっきとともに金属めっき表面に電着塗装塗膜を形成することによって、被処理品の耐久性、表面平滑性、質感などが向上し、該被処理品の商品価値を大幅に増加させる。また、被処理品の形状に左右されず均一な膜厚に塗装でき、定量的に膜厚を管理でき、塗料損失が少なく、限外ろ過により塗料を容易に回収ができる。さらに火災の心配がなく衛生的である。したがって、現在において電着塗装は重要な塗装技術の１つに数えられる。 Conventionally, protection and decoration of parts in a wide range of industrial products such as home appliances, acoustic equipment, electronic equipment, communication equipment, precision equipment, optical equipment, transportation equipment, leisure and sports equipment, ornaments, furniture, building materials, etc. For the purpose, metal plating is generally performed on the part surface. Also, since metal plating may be corroded by atmospheric oxygen, sulfur oxides, rainwater, seawater, etc., a protective coating film is formed on the metal surface in order to improve its corrosion resistance and prevent corrosion. The In general, an electrodeposition coating method is used to form a protective coating film. According to electrodeposition coating, an object to be treated with metal plating intended to form a protective coating film is immersed in a bath containing a coating film-forming component imparted with electric charge, energized in the bath, A coating film forming component is deposited on the metal plating surface of the treated product and subjected to a baking treatment to form a protective coating film. At this time, if the coating film forming component contains a colorant such as a pigment, it is easy to increase the color of the article to be processed. Moreover, by forming an electrodeposition coating film on the surface of the metal plating together with the metal plating, the durability, surface smoothness, texture, etc. of the processed product are improved, and the commercial value of the processed product is greatly increased. Moreover, it can be applied to a uniform film thickness regardless of the shape of the product to be processed, the film thickness can be controlled quantitatively, there is little paint loss, and the paint can be easily recovered by ultrafiltration. Furthermore, there is no worry about fire and it is hygienic. Therefore, at present, electrodeposition coating is counted as one of important coating techniques.
電着塗装の塗膜形成成分には、表面硬度、機械的強度などを考慮して熱硬化性樹脂が用いられるけれども、熱硬化性樹脂は１００℃以上の非常に高い温度で硬化させるのが一般的である。このような高温での硬化は、工程管理を複雑化し、作業者の安全性の面からも対策を講じる必要がある。このため、電荷を付与した紫外線硬化性塗膜形成成分を用い、加熱ではなくて紫外線照射によって塗膜を硬化させるＵＶ電着塗装法が開発されている。ＵＶ電着塗装法においても、種々の改良が要求され、特に、ＵＶ電着塗装法によって形成される塗膜は充分な耐磨耗性を有しないという点が重要な解決課題になる。たとえば、塗膜形成成分に官能基数の多い多官能（メタ）アクリレートを含有させれば、形成される電着塗装塗膜の硬度、耐磨耗性などは向上するものの、金属めっきと電着塗装塗膜との密着性が低下し、該塗膜の脆性破壊が起こり易くなるという欠点がある。 Although a thermosetting resin is used as a coating film forming component of electrodeposition coating in consideration of surface hardness, mechanical strength, etc., the thermosetting resin is generally cured at a very high temperature of 100 ° C. or higher. Is. Such high-temperature curing complicates process management and requires measures from the viewpoint of worker safety. For this reason, a UV electrodeposition coating method has been developed in which an ultraviolet curable coating film-forming component imparted with an electric charge is used and the coating film is cured by ultraviolet irradiation instead of heating. Various improvements are also required in the UV electrodeposition coating method, and in particular, the point that the coating film formed by the UV electrodeposition coating method does not have sufficient wear resistance is an important solution. For example, if polyfunctional (meth) acrylates with a large number of functional groups are included in the coating film forming component, the hardness and abrasion resistance of the formed electrodeposition coating film will be improved, but metal plating and electrodeposition coating will occur. Adhesiveness with a coating film falls and there exists a fault that the brittle fracture of this coating film occurs easily.
従来のＵＶ電着塗装法としては、たとえば、１分子中に３個以上のアクリロイル基を有する多官能（メタ）アクリレートの１０重量部以上、７０重量部未満と、３級アミノ基を含有し、平均分子量２０００〜３００００のカチオン電着性樹脂の３０重量部以上、９０重量部未満とからなる塗膜形成成分を含む紫外線硬化性カチオン電着塗料を用いる方法が提案されている（たとえば、特許文献１参照）。そして、カチオン電着性樹脂としては、３級アミノ基含有ビニルモノマーと、α，β−エチレン性不飽和モノカルボン酸ヒドロキシエステル、α，β−エチレン性不飽和モノカルボン酸アルキルエステルおよびα，β−エチレン性不飽和化合物から選ばれる１種または２種以上のモノマーとの共重合体が用いられる。この電着塗料によって形成される塗膜は、耐磨耗性に優れ、高い表面硬度を有するだけでなく、金属めっきに対して良好な密着性を示し、脆性破壊も起こり難い。しかしながら、各種製品に対するさらなる高性能化が要求される現状にあっては、ＵＶ電着塗装法によって形成される塗膜にも一層の性能向上が求められる。 As a conventional UV electrodeposition coating method, for example, 10 parts by weight or more and less than 70 parts by weight of a polyfunctional (meth) acrylate having 3 or more acryloyl groups in one molecule, and a tertiary amino group, There has been proposed a method using an ultraviolet curable cationic electrodeposition coating material containing a coating film forming component composed of 30 parts by weight or more and less than 90 parts by weight of a cationic electrodeposition resin having an average molecular weight of 2000 to 30000 (for example, Patent Documents). 1). As the cationic electrodeposition resin, tertiary amino group-containing vinyl monomer, α, β-ethylenically unsaturated monocarboxylic acid hydroxy ester, α, β-ethylenically unsaturated monocarboxylic acid alkyl ester and α, β -A copolymer with one or more monomers selected from ethylenically unsaturated compounds is used. The coating film formed by this electrodeposition coating is not only excellent in abrasion resistance and high surface hardness, but also exhibits good adhesion to metal plating and is less susceptible to brittle fracture. However, in the current situation where higher performance is required for various products, further improvement in performance is required for coating films formed by the UV electrodeposition coating method.
一方、鋼板表面に、エポキシ樹脂、ポリウレタンなどのマトリックス樹脂とともにシランカップリング剤を含む樹脂被膜を形成し、電着塗装性の良好な樹脂塗装鋼板が提案されている（たとえば、特許文献２参照）。すなわちこの特許文献には、鋼板に電着塗装を施すに先立ち、前記マトリックス樹脂とシランカップリング剤とを含む組成物によって鋼板表面を前処理する技術が記載されると言い換えることができる。そして、この樹脂塗装鋼板に電着塗装を行えば、優れた外観を有する電着塗膜が得られ、樹脂被膜を介して鋼板と電着塗膜との密着性が向上することが、たとえば特許文献２の段落［００１１］および［００１２］に記載される。しかしながら、この特許文献には、金属表面をシランカップリング剤のみを用いて前処理した後に電着塗装を行うこと、およびシランカップリング剤による前処理を施すことによって、耐磨耗性に優れる電着塗膜が得られることについては記載がない。さらに、この特許文献には、樹脂塗装鋼板に電着塗装を行う際に、電着塗膜を紫外線によって硬化させるとの記載はない。また、自動車車体に電着塗装を施す前に、ノニオン性界面活性剤を含む水によって自動車車体を処理することが提案されている（たとえば、特許文献３）。特許文献３に記載の技術は、塗膜焼付け後に硬化塗膜表面にすじむらが発生するのを防止するものである。しかしながら、特許文献３には、シランカップリング剤とノニオン性界面活性剤とを併用すること、およびその併用によって得られる効果について一切記載がない。 On the other hand, a resin-coated steel sheet having a good electrodeposition coating property by forming a resin film containing a silane coupling agent together with a matrix resin such as epoxy resin and polyurethane on the steel sheet surface has been proposed (see, for example, Patent Document 2). . That is, it can be said that this patent document describes a technique for pretreating the steel sheet surface with a composition containing the matrix resin and the silane coupling agent prior to electrodeposition coating on the steel sheet. And if electrodeposition coating is applied to this resin-coated steel sheet, an electrodeposition coating film having an excellent appearance can be obtained, and the adhesion between the steel sheet and the electrodeposition coating film can be improved through the resin coating. Document 2 paragraphs [0011] and [0012]. However, in this patent document, an electrodeposition coating is performed after pretreating a metal surface using only a silane coupling agent, and by applying a pretreatment with a silane coupling agent, an electrode having excellent wear resistance is disclosed. There is no description about obtaining a coating film. Furthermore, this patent document does not describe that the electrodeposition coating film is cured by ultraviolet rays when electrodeposition coating is performed on a resin-coated steel sheet. Further, it has been proposed to treat an automobile body with water containing a nonionic surfactant before applying electrodeposition coating to the automobile body (for example, Patent Document 3). The technique described in Patent Document 3 prevents streaks from occurring on the surface of a cured coating film after baking of the coating film. However, Patent Document 3 has no description of the combined use of a silane coupling agent and a nonionic surfactant and the effects obtained by the combined use.
本発明の目的は、紫外線による塗膜硬化を利用する電着塗装において、金属表面との密着性が実用上問題ない程度であり、優れた耐磨耗性を示し、多彩な色を呈する電着塗膜を形成するための電着塗装前処理用組成物および該組成物を用いる電着塗装方法を提供することである。 The object of the present invention is to provide an electrodeposition coating that uses UV-cured film coating, and has a practically no problem with adhesion to a metal surface, exhibits excellent wear resistance, and exhibits various colors. An electrodeposition coating pretreatment composition for forming a coating film and an electrodeposition coating method using the composition are provided.
本発明は、シランカップリング剤と、
界面活性剤とを含む電着塗装前処理用組成物であって、
前記シランカップリング剤１〜２０重量％と、前記界面活性剤０．１〜２．０重量％とを含み、残部が水であり、
前記シランカップリング剤が、グリシジル基含有アルコキシシラン化合物であり、
前記界面活性剤が、ノニオン系界面活性剤であることを特徴とする電着塗装前処理用組成物である。
The present invention includes a silane coupling agent ,
A composition for electrodeposition coating pretreatment comprising a surfactant,
Containing 1 to 20% by weight of the silane coupling agent and 0.1 to 2.0% by weight of the surfactant, the balance being water,
The silane coupling agent is a glycidyl group-containing alkoxysilane compound,
The composition for electrodeposition coating pretreatment , wherein the surfactant is a nonionic surfactant .
また本発明は、少なくとも表面の一部または全面が金属からなる被処理品の金属表面に電着塗装によって塗膜を形成し、この塗膜に紫外線を照射して硬化させる電着塗装方法において、該被処理品の金属表面を前述のいずれか１つの電着塗装前処理用組成物によって前処理した後に、電着塗装によって金属表面に塗膜を形成することを特徴とする電着塗装方法である。 Further, the present invention provides an electrodeposition coating method in which a coating film is formed by electrodeposition coating on a metal surface of an article to be treated, at least a part of or the entire surface of which is made of metal, and the coating film is cured by irradiation with ultraviolet rays. An electrodeposition coating method characterized in that after the metal surface of the article to be treated is pretreated with any one of the above-described compositions for electrodeposition coating pretreatment, a coating film is formed on the metal surface by electrodeposition coating. is there.
さらに本発明の電着塗装方法は、少なくとも表面の一部または全面が金属からなる被処理品を電着塗装前処理用組成物中に浸漬することによって、金属表面に前処理を施すことを特徴とする。 Furthermore, the electrodeposition coating method of the present invention is characterized in that a metal surface is pretreated by immersing an article to be treated comprising at least a part or the entire surface of a metal in a composition for pretreatment of electrodeposition coating. And
さらに本発明の電着塗装方法は、少なくとも表面の一部または全面が金属からなる被処理品を、液温２５〜６０℃の電着塗装前処理用組成物に１０〜１８０秒間浸漬することを特徴とする。 Furthermore, the electrodeposition coating method of the present invention is to immerse an article to be treated which is at least partly or entirely made of metal for 10 to 180 seconds in an electrodeposition coating pretreatment composition having a liquid temperature of 25 to 60 ° C. Features.
本発明によれば、電着塗装方法において金属表面に電着塗膜を形成するに先立ち、シランカップリング剤としてグリシジル基含有アルコキシシラン化合物を１〜２０重量％、界面活性剤としてノニオン系界面活性剤を０．１〜２．０重量％とを含む電着塗装前処理用組成物にて金属表面を処理することによって、電着塗膜と金属表面との密着性の低下を実用上問題ない程度に抑制しつつ、電着塗膜の耐磨耗性を向上させることができる。したがって、本発明の電着塗装前処理用組成物を用いて前処理を行えば、電着塗膜と金属表面との密着性および電着塗膜の耐磨耗性という、従来は相反すると考えられてきた２つの特性を高水準で併せ持つ電着塗装体が得られる。さらに、本発明の電着塗装処理用組成物は安全性が高いので、作業者にとって好適である。 According to the present invention, electrodeposition in coating process prior to forming the electrodeposited coating on the metal surface, 1 to 20% by weight of the glycidyl group-containing alkoxysilane compound as the silane coupling agent, a nonionic surface as a surface active agent By treating the metal surface with an electrodeposition coating pretreatment composition containing 0.1 to 2.0% by weight of an activator, there is a practical problem in reducing the adhesion between the electrodeposition coating film and the metal surface. It is possible to improve the wear resistance of the electrodeposition coating film while suppressing it to the extent possible. Therefore, if the pretreatment is performed using the composition for pretreatment of electrodeposition coating of the present invention, it is considered that the adhesion between the electrodeposition coating and the metal surface and the wear resistance of the electrodeposition coating are contradictory in the past. An electrodeposited body having both of the above two characteristics at a high level can be obtained. Furthermore, since the composition for electrodeposition coating treatment of the present invention has high safety, it is suitable for workers.
本発明によれば、前記電着塗装前処理用組成物を用いることによって、シランカップリング剤による処理効果が金属表面全域にわたって均一に発揮されるとともに、前処理後の電着塗装によって形成される電着塗膜の耐磨耗性が一層向上する。 According to the present invention, by using the electrodeposition coating pretreatment composition, together with the processing effect of the silane coupling agent is uniformly exerted over the metal surfaces throughout, it is formed by electrodeposition coating after the pretreatment The wear resistance of the electrodeposition coating is further improved.
本発明によれば、前記組成物を用いれば、電着塗膜と金属表面との密着性の低下防止および電着塗膜の耐磨耗性の向上という効果が得られる。また、このような組成の電着塗装前処理用組成物を用いれば、少なくとも表面が金属からなる被処理品を該電着塗装前処理用組成物に浸漬するだけで前処理できるので、金属表面の前処理を円滑にかつ効率良く実施できる。また、該電着塗装前処理用組成物中におけるシランカップリング剤の分散性が非常に良好であり、長期保存してもシランカップリング剤の良好な分散性が安定的に保持され、成分の沈降、変質などを生じない。 According to this invention, if the said composition is used, the effect of the fall prevention of the adhesiveness of an electrodeposition coating film and a metal surface and the improvement of the abrasion resistance of an electrodeposition coating film will be acquired. In addition, if the composition for electrodeposition coating pretreatment having such a composition is used, it is possible to perform pretreatment simply by immersing the article to be treated, at least the surface of which is made of metal, in the composition for electrodeposition coating pretreatment. This pre-treatment can be carried out smoothly and efficiently. Further, the dispersibility of the silane coupling agent in the electrodeposition coating pretreatment composition is very good, and the good dispersibility of the silane coupling agent is stably maintained even after long-term storage. Does not cause sedimentation or alteration.
本発明によれば、シランカップリング剤としては、グリシジル基含有アルコキシシラン化合物が特に好ましい。このようなアルコキシシラン化合物を用いることによって、密着性の低下防止および耐磨耗性の向上という２つの効果が一層顕著になる。 According to the present invention, the silane coupling agent, grayed Rishijiru group-containing alkoxysilane compound is particularly preferable. By using such an alkoxysilane compound, the two effects of preventing the deterioration of adhesion and improving the abrasion resistance become more remarkable.
本発明によれば、界面活性剤としてノニオン系界面活性剤を用いることによって、本発明の電着塗装前処理用組成物による耐磨耗性向上効果が特に顕著になるとともに、シランカップリング剤の分散安定性がさらに向上する。 According to the present invention, by using a nonionic surfactant as the surfactant, the effect of improving the abrasion resistance by the electrodeposition coating pretreatment composition of the present invention becomes particularly significant, and the silane coupling agent Dispersion stability is further improved.
本発明によれば、少なくとも表面の一部または全面が金属からなる被処理品を本発明の電着塗装前処理用組成物によって前処理した後に、電着塗装によって金属表面に塗膜を形成し、この塗膜に紫外線を照射して硬化させることによって、金属表面に対して実用上問題ない程度の密着性を有し、耐磨耗性に優れる電着塗膜が形成される。 According to the present invention, after pretreatment of an article to be treated, at least partly or entirely of which is made of metal, with the electrodeposition coating pretreatment composition of the present invention, a coating film is formed on the metal surface by electrodeposition coating. By irradiating the coating film with ultraviolet rays and curing it, an electrodeposition coating film having an adhesive property with no practical problem on the metal surface and excellent in abrasion resistance is formed.
本発明によれば、少なくとも表面の一部または全面が金属からなる被処理品を電着塗装前処理用組成物中に浸漬するという簡易な操作によって金属表面に前処理を施すことが可能である。このため、余分な作業負荷を掛けることなく前処理を施せるので、一般的な電着塗装工程とほとんど変わらない作業効率で本発明の電着塗装方法を実施できる。 According to the present invention, it is possible to pre-treat a metal surface by a simple operation of immersing an article to be treated having at least a part or the entire surface of a metal in a composition for electrodeposition coating pretreatment. . For this reason, since pre-processing can be performed without applying an extra work load, the electrodeposition coating method of the present invention can be carried out with work efficiency almost the same as a general electrodeposition coating process.
本発明によれば、少なくとも表面の一部または全面が金属からなる被処理品を液温２５〜６０℃の電着塗装前処理用組成物に１０〜１８０秒間浸漬することによって、電着塗装前処理用組成物による効果が一層効率良く発揮されるとともに、短時間の浸漬で済むので、作業効率を向上させることができる。 According to the present invention, before the electrodeposition coating, by immersing the article to be processed, at least part of or the entire surface of which is made of metal, in the composition for electrodeposition coating pretreatment at a liquid temperature of 25 to 60 ° C. for 10 to 180 seconds. The effect of the treatment composition can be exhibited more efficiently, and the work efficiency can be improved because it can be dipped in a short time.
本発明によれば、シランカップリング剤としては、グリシジル基含有アルコキシシラン化合物が特に好ましい。このようなアルコキシシラン化合物を用いることによって、密着性の低下防止および耐磨耗性の向上という２つの効果が一層顕著になる。 According to the present invention, the silane coupling agent, grayed Rishijiru group-containing alkoxysilane compound is particularly preferable. By using such an alkoxysilane compound, the two effects of preventing the deterioration of adhesion and improving the abrasion resistance become more remarkable.
〔式中、Ｒはアルキル基を示す。Ａはアルキレン基を示す。ｍは０、１または２を示す。ｎは０または１を示す。〕 [Wherein, R represents an alkyl group. A represents an alkylene group. m represents 0, 1 or 2; n represents 0 or 1. ]
で表されるグリシジル基含有アルコキシシランが挙げられる。一般式（１）において、符号Ｒで示されるアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基などの炭素数１〜４の直鎖状または分岐鎖状アルキル基が挙げられる。これらの中でも、炭素数１〜４の直鎖状アルキル基が好ましく、炭素数１〜２の直鎖状アルキル基がさらに好ましい。符号Ａで示されるアルキレン基としては、たとえば、メチレン、エチレン、トリメチレン、テトラメチレンなどの炭素数１〜４の直鎖状アルキレン基が挙げられる。これらの中でも、トリメチレンが好ましい。グリシジル基含有アルコキシシランの具体例としては、たとえば、グリシジルオキシメチルトリメトキシシラン、２−グリシジルオキシエチルトリメトキシシラン、３−グリシジルオキシプロピルトリメトキシシラン、３−グリシジルオキシプロピルトリエトキシシラン、３−グリシジルオキシプロピルメチルジメトキシシラン、３−グリシジルオキシプロピルメチルジエトキシシラン、４−グリシジルオキシブチルトリメトキシシラン、グリシジルメチルトリメトキシシラン、２−グリシジルエチルトリメトキシシラン、３−グリシジルトリメトキシシラン、４−グリシジルブチルトリメトキシシランなどが挙げられる。これらの中でも、３−グリシジルオキシプロピルトリメトキシシラン、３−グリシジルオキシプロピルトリエトキシシラン、３−グリシジルオキシプロピルメチルジメトキシシラン、３−グリシジルオキシプロピルメチルジエトキシシランなどが好ましく、電着塗膜と金属表面との密着性の低下抑制および電着塗膜の耐磨耗性向上という観点から、３−グリシジルオキシプロピルトリメトキシシラン、３−グリシジルオキシプロピルトリエトキシシラン、３−グリシジルオキシプロピルメチルジメトキシシランなどが好ましい。シランカップリング剤は市販品をも使用でき、たとえば、サイラエース５１０（商品名、チッソ（株）製）などが挙げられる。 The glycidyl group containing alkoxysilane represented by these is mentioned. In the general formula (1), examples of the alkyl group represented by the symbol R include a straight chain having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. A linear or branched alkyl group may be mentioned. Among these, a linear alkyl group having 1 to 4 carbon atoms is preferable, and a linear alkyl group having 1 to 2 carbon atoms is more preferable. Examples of the alkylene group represented by the symbol A include linear alkylene groups having 1 to 4 carbon atoms such as methylene, ethylene, trimethylene, and tetramethylene. Among these, trimethylene is preferable. Specific examples of the glycidyl group-containing alkoxysilane include, for example, glycidyloxymethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyl. Oxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 4-glycidyloxybutyltrimethoxysilane, glycidylmethyltrimethoxysilane, 2-glycidylethyltrimethoxysilane, 3-glycidyltrimethoxysilane, 4-glycidylbutyl Examples include trimethoxysilane. Among these, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and the like are preferable, and the electrodeposition coating film and metal 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, etc. from the viewpoint of suppressing the decrease in adhesion to the surface and improving the abrasion resistance of the electrodeposition coating film Is preferred . Silane-coupling agent can also be used commercially available products, for example, Sairae scan 5 10 (trade name, manufactured by Chisso Co., Ltd.), and the like.
シランカップリング剤は１種を単独で使用できまたは２種以上を併用できる。本発明の電着塗装前処理用組成物におけるシランカップリング剤の含有量は特に制限されないけれども、好ましくは電着塗装前処理用組成物全量の１〜２０重量％、さらに好ましくは３〜８重量％である。シランカップリング剤の含有量が１重量％未満では、シランカップリング剤の添加効果が不充分になり、電着塗装によって形成される硬化後の塗膜の耐磨耗性が不充分になるおそれがある。２０重量％を超えると、電着塗装によって形成される硬化後の塗膜の密着性が低下するおそれがある。また、塗膜を塗装できないおそれがある。 A silane coupling agent can be used individually by 1 type, or can use 2 or more types together. The content of the silane coupling agent in the composition for electrodeposition coating pretreatment of the present invention is not particularly limited, but is preferably 1 to 20% by weight, more preferably 3 to 8% by weight based on the total amount of the composition for electrodeposition coating pretreatment. %. If the content of the silane coupling agent is less than 1% by weight, the effect of adding the silane coupling agent is insufficient, and the abrasion resistance of the cured film formed by electrodeposition coating may be insufficient. There is. If it exceeds 20% by weight, the adhesion of the cured coating film formed by electrodeposition coating may be reduced. Moreover, there exists a possibility that a coating film cannot be painted.
さらに本発明の電着塗装用前処理液における界面活性剤としては、電着塗装によって形成される硬化後の塗膜が均一に付着することなどを考慮すると、ノニオン性界面活性剤が好ましい。ノニオン性界面活性剤としては、たとえば、ポリオキシエチレンラウリン酸エステル、ポリオキシエチレンステアリン酸エステル、ポリオキシエチレングリコールステアリン酸エステル、ポリオキシエチレンミリスチン酸エステル、ポリオキシエチレンパルミチン酸エステル、ポリオキシエチレンオレイン酸エステル、ポリオキシエチレングリコールオレイン酸エステル、ポリオキシエチレンヒドロキシステアリン酸エステル、ポリオキシエチレン９，１０−ジヒドロキシステアリン酸エステル、ポリオキシエチレンフェニルステアリン酸エステル、ポリオキシエチレン−ｏ−キシリルステアリン酸エステルなどのポリオキシエチレン脂肪酸エステル、ポリオキシエチレンラウリルアミン、ポリオキシエチレンステアリルアミンなどのポリオキシエチレンアルキルアミン、ポリオキシエチレンラウリルアマイドなどのポリオキシエチレンアルキルアマイド、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリオレエートなどのポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンラウリルアルコール、ポリオキシエチレンオレイルアルコールなどのポリオキシエチレン高級アルコール、ポリオキシエチレンオクチルフェノール、ポリオキシエチレンノニルフェノールなどのポリオキシエチレンアルキルフェノール、ポリオキシエチレンオクチルクレゾール、ポリオキシエチレンベンジルクレゾール、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェノールエーテル、ポリオキシエチレンオクタデカノールエーテル、ポリオキシエチレン−ポリオキシプロピレン−ポリオキシエチレングリコール、ポリオキシエチレン９，１０−オクタデカンジオール、ポリオキシエチレン９，１０−ジヒドロオキシステアロニトリルなどのポリオキシエチレン系ノニオン界面活性剤、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタントリステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタンセスキオレエート、グリセロールソルビタンラウレート、グリセロールマンニタンラウレートなどのソルビタン脂肪酸エステル、ポリエチレングリコールラウレート、ポリエチレングリコールステアレート、ポリエチレングリコールオレエート、ポリエチレングリコールトール油誘導体、ポリエチレングリコールソルビタンラウレート、ポリエチレングリコールソルビタンステアレート、ポリエチレングリコールソルビタンオレエート、ポリエチレングリコールラウリルエーテル、ポリエチレングリコールオレイルエーテル、ポリエチレングリコールノニルフェニルエーテル、ポリエチレングリコールウラリルアミン、ポリエチレングリコールステアリルアミンなどのポリエチレングリコールアルキルアミン、ポリエチレングリコールと酸化エチレンの付加物、ノニルフェノール、オクチルフェノール、モノグリセライド、ジグリセライド、グリセリンモノラウレート、グリセリンエステル、グリコールエステル、ラノリンおよびラノリンアルコールのエチレンオキサイド付加物、直鎖２級アルコールのエチレンオキサイド付加物、分枝鎖ノニルフェノールのエチレンオキサイド付加物、直鎖アルキルフェノールのエチレンオキサイド付加物、オキソアルコールのエチレンオキサイド付加物、チグラーアルコールのエチレンオキサイド付加物、ポリ（アルキレンオキシド）ブロック共重合物、アルキロールアミド、ショ糖脂肪酸エステルなどのほかジエタノールアミン縮合物、モノカノールアミン縮合物、ポリオキシエチレン脂肪酸アミドなどの脂肪酸とヒドロキシアルキルアミンの縮合生成物であるカルボン酸アミド系ノニオン界面活性剤、ポリアルキレンオキシド系ノニオン界面活性剤などが挙げられる。ノニオン性界面活性剤は各種のものが市販されており、たとえば、Ｔｗｅｅｎ（商品名、ポリオキシエチレンソルビタン脂肪酸エステル、アルタスパウダー（Atlas Powder）社製）、プルロニックまたはプロノン（商品名、ポリエチレングリコールと酸化エチレンとの付加物、Wyandotte Chemical社製）などが挙げられる。界面活性剤は１種を単独で使用できまたは２種以上を併用できる。 Further as surfactants in electrodeposition pre for coating treatment solution of the present invention, the coating film after curing, which is formed by electrodeposition coating considering the possible to uniformly adhere, nonionic surfactants are preferred. Nonionic surfactants include, for example, polyoxyethylene lauric acid ester, polyoxyethylene stearic acid ester, polyoxyethylene glycol stearic acid ester, polyoxyethylene myristic acid ester, polyoxyethylene palmitic acid ester, polyoxyethylene olein Acid ester, polyoxyethylene glycol oleate, polyoxyethylene hydroxy stearate, polyoxyethylene 9,10-dihydroxy stearate, polyoxyethylene phenyl stearate, polyoxyethylene-o-xylyl stearate Such as polyoxyethylene fatty acid ester, polyoxyethylene laurylamine, polyoxyethylene stearylamine, etc. Polyoxyethylene alkyl amides such as ciethylene alkyl amine, polyoxyethylene lauryl amide, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate, polyoxyethylene higher alcohols such as polyoxyethylene lauryl alcohol, polyoxyethylene oleyl alcohol, polyoxyethylene octylphenol, polyoxyethylene Polyoxyethylene alkylphenols such as nonylphenol, polyoxyethylene N-octyl cresol, polyoxyethylene benzyl cresol, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene octadecanol ether, polyoxy Polyoxyethylene nonionic surfactants such as ethylene-polyoxypropylene-polyoxyethylene glycol, polyoxyethylene 9,10-octadecanediol, polyoxyethylene 9,10-dihydrooxystearonitrile, sorbitan monolaurate, sorbitan Monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as trioleate, sorbitan sesquioleate, glycerol sorbitan laurate, glycerol mannitan laurate, polyethylene glycol laurate, polyethylene glycol stearate, polyethylene glycol oleate, polyethylene glycol tall oil derivatives, polyethylene glycol sorbitan laurate, Polyethylene glycol alkylamines such as polyethylene glycol sorbitan stearate, polyethylene glycol sorbitan oleate, polyethylene glycol lauryl ether, polyethylene glycol oleyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol lauryl amine, polyethylene glycol stearyl amine, Adduct of ethylene glycol and ethylene oxide, nonylphenol, octylphenol, monoglyceride, diglyceride, glycerin monolaurate, glycerin ester, glycol ester, ethylene oxide adduct of lanolin and lanolin alcohol, ethylene oxide adduct of linear secondary alcohol, Ethylene oxide adduct of branched chain nonylphenol, ethylene oxide adduct of linear alkylphenol, ethylene oxide adduct of oxo alcohol, ethylene oxide adduct of Ziegler alcohol, poly (alkylene oxide) block copolymer, alkylolamide, Fatty acids such as sugar fatty acid esters, diethanolamine condensate, monocanolamine condensate, polyoxyethylene fatty acid amide Condensation products of hydroxyalkyl amines in which the carboxylic acid amide nonionic surfactant, polyalkylene oxide nonionic surfactant and the like. Various nonionic surfactants are commercially available. For example, Tween (trade name, polyoxyethylene sorbitan fatty acid ester, manufactured by Atlas Powder), Pluronic or Pronon (trade name, oxidized with polyethylene glycol) And an adduct with ethylene, manufactured by Wyandotte Chemical). Surfactant can be used individually by 1 type, or can use 2 or more types together.
本発明の電着塗装前処理用組成物における界面活性剤の含有量は電着塗装前処理用組成物全量の０．１〜２．０重量％、さらに好ましくは０．１〜０．５重量％である。界面活性剤の含有量が０．１重量％未満では、電着塗装によって形成される硬化後の塗膜を被塗装体に均一にかつ密着性良く塗装できないおそれがある。２．０重量％を超えても、やはり、電着塗装によって形成される硬化後の塗膜を被塗装体に均一にかつ密着性良く塗装できないおそれがある。 The content of the surfactant in the composition for electrodeposition coating pretreatment of the present invention is 0.1 to 2.0% by weight, more preferably 0.1 to 0.5% by weight of the total amount of the composition for electrodeposition coating pretreatment. %. If the content of the surfactant is less than 0.1% by weight, the cured coating film formed by electrodeposition coating may not be applied uniformly and with good adhesion to the substrate. Even if it exceeds 2.0% by weight, there is a possibility that the cured coating film formed by electrodeposition coating cannot be applied uniformly and with good adhesion to the substrate.
本発明の電着塗装前処理用組成物は、たとえば、シランカップリング剤の適量および必要に応じて界面活性剤の適量を水に溶解または分散させることによって製造できる。ここで使用する水には特に制限はないけれども、蒸留水、イオン交換水、活性炭処理水などが好ましい。 The composition for electrodeposition coating pretreatment of the present invention can be produced, for example, by dissolving or dispersing an appropriate amount of a silane coupling agent and, if necessary, an appropriate amount of a surfactant in water. Although there is no restriction | limiting in particular in the water used here, Distilled water, ion-exchange water, activated carbon treatment water, etc. are preferable.
本発明の電着塗装前処理用組成物は、少なくとも表面の一部または全面が金属からなる被処理品（以後特に断らない限り単に「被処理品」と称す）の金属表面に電着塗装を施すに際し、前処理剤として好適に使用できる。少なくとも表面が金属からなる被処理品としては、たとえば、めっき素材の表面に各種めっきを施して金属層を形成した被処理品、ダイカストなどが挙げられる。めっき素材としてはこの分野で常用されるものをいずれも使用でき、たとえば、純鉄、炭素鋼、高抗張力鋼（低合金鋼、マルエージング鋼）、磁性鋼、非磁性鋼、高マンガン鋼、ステンレス鋼（マルテンサイト系ステンレス、フェライト系ステンレス、オーステナイト系ステンレス、オーステナイト・フェライト系ステンレス、析出硬化型ステンレスなど）、超合金鋼などの鉄系金属、銅および銅合金（無酸素銅、りん青銅、タフピッチ銅、アルミ青銅、ベリリウム銅、高力黄銅、丹銅、洋白、黄銅、快削黄銅、ネバール黄銅など）、鉄・ニッケル合金、ニッケル・クロム合金、ニッケル、クロム、アルミニウムおよびアルミニウム合金、マグネシウムおよびマグネシウム合金、チタン、ジルコニウム、ハフニウムおよびこれらの合金、モリブデン、タングステンおよびこれらの合金、ニオブ、タンタルおよびこれらの合金、合成樹脂類（繊維強化プラスチック（ＦＲＰ）、繊維強化金属（ＦＲＭ）、エンジニアリングプラスチックなど）、セラミックス類（アルミナ、ジルコア、ガラス、ソーダガラス、石英ガラス、硼ケイ酸ガラスなど）などが挙げられる。めっき素材は、複数の材質（金属、プラスチック、セラミックス）の部品が組合わされて形成される組成品であってもよい。めっき素材表面に施されるめっきの種類も特に制限されず、この分野で常用されるめっきをいずれも採用できる。たとえば、銅・ニッケル・クロムめっき、ニッケル・ボロン・タングステンめっき、ニッケル・ボロンめっき、黄銅めっき、ブロンズめっき、銅・錫めっきなどの各種合金めっき、金めっき、銀めっき、銅めっき、錫めっき、ロジウムめっき、パラジウムめっき、白金めっき、カドミウムめっき、ニッケルめっき、クロムめっき（特に三価クロムめっき）、黒色クロムめっき、亜鉛めっき、黒色ニッケルめっき、黒色ロジウムめっき、亜鉛めっき、工業用（硬質）クロムめっきなどが挙げられる。また、ダイカストとしては、亜鉛ダイカスト、アルミニウムダイカスト、マグネシウムダイカスト、焼結合金ダイカストなどが挙げられる。 The composition for pretreatment of electrodeposition coating according to the present invention is an electrodeposition coating on a metal surface of an article to be treated (hereinafter, simply referred to as “object to be treated” unless otherwise specified). When applied, it can be suitably used as a pretreatment agent. Examples of the article to be treated having at least a surface made of metal include an article to be treated, a die casting and the like, in which various plating is performed on the surface of the plating material to form a metal layer. Any material commonly used in this field can be used as the plating material. For example, pure iron, carbon steel, high tensile strength steel (low alloy steel, maraging steel), magnetic steel, nonmagnetic steel, high manganese steel, stainless steel Steels (martensitic stainless steel, ferritic stainless steel, austenitic stainless steel, austenitic / ferritic stainless steel, precipitation hardened stainless steel, etc.), ferrous metals such as superalloy steel, copper and copper alloys (oxygen-free copper, phosphor bronze, tough pitch) Copper, aluminum bronze, beryllium copper, high-strength brass, red brass, western white, brass, free-cutting brass, Nevlar brass, etc.), iron-nickel alloy, nickel-chromium alloy, nickel, chromium, aluminum and aluminum alloy, magnesium and Magnesium alloys, titanium, zirconium, hafnium and their alloys, moly Den, tungsten and alloys thereof, niobium, tantalum and alloys thereof, synthetic resins (fiber reinforced plastic (FRP), fiber reinforced metal (FRM), engineering plastic, etc.), ceramics (alumina, zir core, glass, soda glass) , Quartz glass, borosilicate glass, etc.). The plating material may be a composition formed by combining parts of a plurality of materials (metal, plastic, ceramics). The type of plating applied to the surface of the plating material is not particularly limited, and any plating commonly used in this field can be adopted. For example, copper / nickel / chrome plating, nickel / boron / tungsten plating, nickel / boron plating, brass plating, bronze plating, copper / tin plating and other alloy plating, gold plating, silver plating, copper plating, tin plating, rhodium Plating, palladium plating, platinum plating, cadmium plating, nickel plating, chromium plating (especially trivalent chromium plating), black chromium plating, zinc plating, black nickel plating, black rhodium plating, zinc plating, industrial (hard) chromium plating, etc. Is mentioned. Examples of the die casting include zinc die casting, aluminum die casting, magnesium die casting, sintered alloy die casting and the like.
本発明の電着塗装前処理用組成物を用いる本発明の電着塗装方法は、一般的な電着塗装方法において、化成処理工程と電着塗装工程との間に、電着塗装前処理用組成物による前処理工程を施す以外は従来の電着塗装方法と同様に実施できる。図１は、本発明電着塗装方法の一実施形態を概略的に示すフローチャートである。たとえば、本発明の電着塗装方法は、脱脂工程ａ１、酸中和工程ａ２、化成処理工程ａ３、電着塗装前処理用組成物による前処理工程ａ４、電着塗装工程ａ５および塗膜硬化工程ａ６を含む。 The electrodeposition coating method of the present invention using the composition for electrodeposition coating pretreatment of the present invention is an electrodeposition coating pretreatment between a chemical conversion treatment step and an electrodeposition coating step in a general electrodeposition coating method. It can be carried out in the same manner as the conventional electrodeposition coating method except that the pretreatment step with the composition is performed. FIG. 1 is a flowchart schematically showing one embodiment of the electrodeposition coating method of the present invention. For example, the electrodeposition coating method of the present invention includes a degreasing step a1, an acid neutralization step a2, a chemical conversion treatment step a3, a pretreatment step a4 with an electrodeposition coating pretreatment composition, an electrodeposition coating step a5, and a coating film curing step. a6 is included.
ステップａ１の脱脂工程では、ステップａ０で用意される電着塗装の対象になる被処理品を脱脂する。脱脂は公知の方法に従って実施できる。たとえば、被処理品の表面とアルカリ水溶液とを接触させることによって実施できる。アルカリ水溶液の接触とは、具体的には、被処理品へのアルカリ水溶液の噴霧、被処理品のアルカリ水溶液への浸漬などである。アルカリとしては金属の脱脂に常用されるものを使用でき、たとえば、リン酸ナトリウム、リン酸カリウムなどのアルカリ金属のリン酸塩などが挙げられる。アルカリ水溶液中のアルカリ濃度は、たとえば、処理する金属の種類、被処理金属の汚れの度合いなどに応じて適宜決定される。さらにアルカリ水溶液には、陰イオン性界面活性剤、非イオン性界面活性剤などの界面活性剤の適量が含まれていてもよい。脱脂は、２０〜５０℃程度の温度（アルカリ水溶液の液温）下に行われ、１〜５分程度で終了する。脱脂後、被処理品は水洗され、次の酸洗工程に供される。その他、酸性浴に浸漬する脱脂、気泡性浸漬脱脂、電解脱脂などを適宜組み合わせて実施することもできる。 In the degreasing process of step a1, the article to be processed that is the object of electrodeposition coating prepared in step a0 is degreased. Degreasing can be performed according to a known method. For example, it can be carried out by bringing the surface of the article to be treated into contact with an alkaline aqueous solution. Specifically, the contact with the aqueous alkali solution includes spraying the aqueous alkali solution onto the article to be treated, immersing the article to be treated in the aqueous alkali solution, and the like. As the alkali, those commonly used for metal degreasing can be used, and examples include alkali metal phosphates such as sodium phosphate and potassium phosphate. The alkali concentration in the aqueous alkali solution is appropriately determined according to, for example, the type of metal to be treated and the degree of contamination of the metal to be treated. Furthermore, the alkaline aqueous solution may contain an appropriate amount of a surfactant such as an anionic surfactant and a nonionic surfactant. Degreasing is performed at a temperature of about 20 to 50 ° C. (liquid temperature of the alkaline aqueous solution) and is completed in about 1 to 5 minutes. After degreasing, the product to be treated is washed with water and subjected to the next pickling process. In addition, degreasing to be immersed in an acidic bath, bubbling immersion degreasing, electrolytic degreasing, and the like can be appropriately combined.
ステップａ２の酸洗工程では、ステップａ１で脱脂を施した被処理品を酸洗する。酸洗は公知の方法に従って実施できる。たとえば、被処理品の表面と酸水溶液とを接触させることによって実施できる。酸水溶液の接触とは、脱脂工程におけるアルカリ水溶液の接触と同様であり、被処理品への酸水溶液の噴霧、被処理品の酸水溶液への浸漬などである。酸としては金属の酸洗に常用されるものを使用でき、たとえば、硫酸、硝酸、リン酸などが挙げられる。酸水溶液中の酸濃度は、たとえば、被処理金属の種類などに応じて適宜決定される。酸洗は、２０〜３０℃程度の温度下（酸水溶液の液温）に行われ、１５〜６０秒程度で終了する。酸洗後に、スケール除去などを施してもよい。 In the pickling process of step a2, the article to be treated that has been degreased in step a1 is pickled. Pickling can be performed according to a known method. For example, it can be carried out by bringing the surface of the article to be treated into contact with an acid aqueous solution. The contact with the acid aqueous solution is the same as the contact with the alkaline aqueous solution in the degreasing step, and includes spraying of the acid aqueous solution onto the product to be treated, immersion of the product to be treated in the acid aqueous solution and the like. As the acid, those commonly used for metal pickling can be used, and examples thereof include sulfuric acid, nitric acid, and phosphoric acid. The acid concentration in the acid aqueous solution is appropriately determined according to, for example, the type of metal to be treated. The pickling is performed at a temperature of about 20 to 30 ° C. (liquid temperature of the acid aqueous solution) and is completed in about 15 to 60 seconds. After pickling, scale removal or the like may be performed.
ステップａ３の化成処理工程では、ステップａ２で酸洗を施した被処理品を化成処理する。化成処理は公知の方法に従って実施できる。たとえば、被処理品の表面と化成処理液とを接触させることによって実施できる。化成処理液の接触とは、たとえば、被処理品への化成処理液の噴霧、被処理品の該処理液への浸漬などである。また、噴霧と浸漬とを組み合わせても良い。化成処理液としてはこの分野で常用されるものを使用でき、たとえば、リン酸亜鉛系化成処理液、リン酸鉄系化成処理液、クロメート系化成処理液、有機酸系化成処理液などが挙げられる。化成処理は、化成処理液の液温を好ましくは２５〜４０℃程度に維持しながら、好ましくは１０秒〜３分程度、さらに好ましくは２０秒〜２分程度で終了する。さらに化成処理は通電下に行うのが好ましい。通電条件は特に制限されないけれども、好ましくは０．３〜１．５Ａ程度、さらに好ましくは０．５〜１Ａ程度の電流を流せばよい。 In the chemical conversion treatment step in step a3, the product to be treated that has been pickled in step a2 is subjected to chemical conversion treatment. The chemical conversion treatment can be performed according to a known method. For example, it can be carried out by bringing the surface of the article to be treated into contact with the chemical conversion liquid. The contact of the chemical conversion treatment liquid includes, for example, spraying of the chemical conversion treatment liquid onto the product to be processed, immersion of the product to be processed in the treatment liquid, and the like. Moreover, you may combine spraying and immersion. As the chemical conversion treatment liquid, those commonly used in this field can be used, and examples thereof include zinc phosphate chemical conversion liquid, iron phosphate chemical conversion liquid, chromate chemical conversion liquid, and organic acid chemical conversion liquid. . The chemical conversion treatment is preferably completed in about 10 seconds to 3 minutes, more preferably in about 20 seconds to 2 minutes, while maintaining the liquid temperature of the chemical conversion solution at preferably about 25 to 40 ° C. Further, the chemical conversion treatment is preferably performed under energization. The energization conditions are not particularly limited, but a current of preferably about 0.3 to 1.5 A, more preferably about 0.5 to 1 A may be passed.
ステップａ４の前処理工程では、ステップａ３で化成処理を施した被処理品に、本発明の電着塗装前処理用組成物によって電着塗装前処理を施す。電着塗装前処理は、たとえば、被処理品の表面と本発明の電着塗装前処理用組成物とを接触させることによって実施できる。電着塗装前処理用組成物の接触とは、たとえば、被処理品への電着塗装前処理用組成物の噴霧、被処理品の電着塗装前処理用組成物への浸漬などである。また、噴霧と浸漬とを組み合わせても良い。前処理は、電着塗装前処理用組成物の液温を好ましくは３０〜５０℃程度、さらに好ましくは３５〜４５℃程度に維持しながら、好ましくは５秒〜３分程度、さらに好ましくは１０秒〜２分程度で終了する。前処理終了後の被処理品には乾燥および／または純水洗浄を施しても良い。乾燥は７０〜８０℃の温度下に実施され、１５〜６０分程度で終了する。純水洗浄は、たとえば、被処理品を純水に１０秒〜２分程度浸漬することによって実施できる。 In the pretreatment process of step a4, the electrodeposition coating pretreatment is performed on the article to be treated that has been subjected to the chemical conversion treatment in step a3 by the electrodeposition coating pretreatment composition of the present invention. The electrodeposition coating pretreatment can be carried out, for example, by bringing the surface of the article to be treated into contact with the electrodeposition coating pretreatment composition of the present invention. The contact of the composition for electrodeposition coating pretreatment includes, for example, spraying the composition for electrodeposition coating pretreatment on the article to be processed, immersion of the article to be treated in electrodeposition coating pretreatment. Moreover, you may combine spraying and immersion. The pretreatment is preferably about 5 seconds to 3 minutes, more preferably 10 while maintaining the liquid temperature of the electrodeposition coating pretreatment composition preferably at about 30 to 50 ° C, more preferably about 35 to 45 ° C. It ends in about 2 to 2 minutes. The article to be treated after completion of the pretreatment may be subjected to drying and / or pure water cleaning. Drying is performed at a temperature of 70 to 80 ° C. and is completed in about 15 to 60 minutes. The pure water cleaning can be performed, for example, by immersing the article to be treated in pure water for about 10 seconds to 2 minutes.
ステップａ５の電着塗装工程では、ステップａ４で電着塗装前処理を施した被処理品に、電着塗装を施す。電着塗装は、公知の方法に従い、たとえば、電着塗装用塗料を満たした通電槽中に被処理品を完全にまたは部分的に浸漬し、通電することにより実施される。電着塗装に用いられる塗料は、紫外線硬化型の塗膜形成成分を含むものであれば、公知のカチオン型およびアニオン型の電着塗料を使用できる。紫外線硬化型の塗膜形成成分としては、たとえば、エチレン性不飽和結合基である（メタ）アクリロイル基を有するアクリル樹脂、スルホニウム基およびプロパルギル基を有するエポキシ樹脂などが挙げられ、（メタ）アクリレート化合物、イソシアネート化合物などの光重合性モノマーが含まれてもよい。電着塗装塗料は光重合開始剤を含んでも良い。光重合開始剤としては公知のものを使用でき、たとえば、ベンゾイン類、アセトフェノン類、アミノアセトフェノン類、アントラキノン類、チオキサントン類、ケタール類、ベンゾフェノン類、芳香族のヨードニウム塩、スルホニウム塩およびジアゾニウム塩、ポリシラン化合物、α−アルキルフェノン類などが挙げられる。電着塗装塗料は着色剤を含んでも良い。着色剤としては、たとえば、無機顔料、有機顔料などがある。無機顔料の具体例としては、たとえば、チタンホワイト（酸化チタン）、カーボンブラック、ベンガラなどの着色顔料、カオリン、タルク、ケイ酸アルミニウム、炭酸カルシウム、マイカ、クレー、シリカなどの体質顔料、リン酸亜鉛、リン酸鉄、リン酸アルミニウム、リン酸カルシウム、亜リン酸亜鉛、シアン化亜鉛、酸化亜鉛、トリポリリン酸アルミニウム、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム、リンモリブデン酸アルミニウム、リンモリブデン酸アルミニウム亜鉛などの防錆顔料などが挙げられる。さらに電着塗装塗料は、たとえば、顔料分散剤、界面活性剤、酸化防止剤、紫外線吸収剤などの一般的な添加剤を含んでいても良い。電着塗料は前述の各成分の１種または２種以上を水に分散させたものであることが好ましい。電着塗装条件も特に制限されず、被処理品である金属の種類、電着塗装塗料の種類、通電槽の大きさおよび形状、得られる塗装物品の用途などの各種条件に応じて広い範囲から適宜選択できるけれども、通常は、浴温度（電着塗料温度）１０〜５０℃程度、印加電圧１０〜２５０Ｖ程度、電圧印加時間１〜１０分程度とすればよい。塗装が施された被処理品は、通電槽から取り出され、水洗される。電着塗装後の被処理品には乾燥を施しても良い。乾燥は７０〜８０℃の温度下に実施され、１５〜６０分程度で終了する。 In the electrodeposition coating process of step a5, the electrodeposition coating is applied to the article to be processed that has been subjected to the electrodeposition coating pretreatment in step a4. The electrodeposition coating is carried out according to a known method, for example, by completely immersing the article to be processed in a current-carrying tank filled with the electrodeposition coating paint and energizing it. As the coating material used for electrodeposition coating, known cationic and anionic electrodeposition coating materials can be used as long as they contain an ultraviolet curable coating film forming component. Examples of the ultraviolet curable film-forming component include acrylic resins having a (meth) acryloyl group which is an ethylenically unsaturated bond group, epoxy resins having a sulfonium group and a propargyl group, and (meth) acrylate compounds Photopolymerizable monomers such as isocyanate compounds may be included. The electrodeposition paint may contain a photopolymerization initiator. Known photopolymerization initiators can be used, such as benzoins, acetophenones, aminoacetophenones, anthraquinones, thioxanthones, ketals, benzophenones, aromatic iodonium salts, sulfonium salts and diazonium salts, polysilanes. Compounds, and α-alkylphenones. The electrodeposition paint may contain a colorant. Examples of the colorant include inorganic pigments and organic pigments. Specific examples of inorganic pigments include, for example, colored pigments such as titanium white (titanium oxide), carbon black, and bengara, extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica, clay, silica, and zinc phosphate. , Iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, aluminum molybdate, calcium molybdate, aluminum phosphomolybdate, zinc aluminum phosphomolybdate, etc. Anticorrosive pigments and the like. Furthermore, the electrodeposition paint may contain general additives such as a pigment dispersant, a surfactant, an antioxidant, and an ultraviolet absorber. The electrodeposition paint is preferably one in which one or more of the aforementioned components are dispersed in water. There are no particular restrictions on the electrodeposition coating conditions, and there is a wide range depending on various conditions such as the type of metal being processed, the type of electrodeposition coating, the size and shape of the current-carrying tank, and the use of the resulting coated article. Usually, the bath temperature (electrodeposition paint temperature) is about 10 to 50 ° C., the applied voltage is about 10 to 250 V, and the voltage application time is about 1 to 10 minutes. The article to be treated is taken out from the energization tank and washed with water. The article to be treated after electrodeposition coating may be dried. Drying is performed at a temperature of 70 to 80 ° C. and is completed in about 15 to 60 minutes.
ステップａ６の塗膜硬化工程では、ステップａ５において被処理品の金属表面に形成される塗膜を硬化させる。塗膜は紫外線の照射によって硬化される。紫外線の照射量は特に制限されず、塗膜形成成分の種類に応じて広い範囲から適宜選択できるけれども、好ましくは４０００〜５０００ｍＪ／ｃｍ２である。照射量は、照射強度（ｍＪ／ｃｍ２・ｓ）と照射時間（ｓ）との積であるから、照射強度と照射時間とを適宜選択することによって、所望の照射量を選択できる。紫外線源としては、たとえば、高圧水銀灯、ケミカルランプ、メタルハライドランプなどの一般的な紫外線源を使用できる。このようにして、被処理品の表面に硬化した電着塗膜が形成される。 In the coating film curing step of step a6, the coating film formed on the metal surface of the article to be processed is cured in step a5. The coating film is cured by irradiation with ultraviolet rays. Although the irradiation amount of an ultraviolet-ray is not restrict | limited in particular, Although it can select suitably from a wide range according to the kind of coating-film formation component, Preferably it is 4000-5000mJ / cm < 2 >. Since the irradiation amount is a product of the irradiation intensity (mJ / cm 2 · s) and the irradiation time (s), a desired irradiation amount can be selected by appropriately selecting the irradiation intensity and the irradiation time. As the ultraviolet ray source, for example, a general ultraviolet ray source such as a high-pressure mercury lamp, a chemical lamp, or a metal halide lamp can be used. In this way, a cured electrodeposition coating film is formed on the surface of the article to be processed.
次いで、ステップａ６のエンドに進み、金属表面に電着塗膜が形成された物品が得られる。 Subsequently, it progresses to the end of step a6 and the article | item with which the electrodeposition coating film was formed on the metal surface is obtained.
以下に実施例、比較例および試験例を挙げ、本発明を具体的に説明する。
（実施例１）
３−グリシドキシプロピルトリメトキシシラン（商品名：サイラエース５１０、シランカップリング剤、チッソ（株）製）５０ｇおよびアセチレンジオール混合物（商品名：オルフィンＰＤ００１、ノニオン系界面活性剤、日信化学工業（株）製）１ｇに全量が１０００ｇになるようにイオン交換水を加えて混合し、本発明の電着塗装前処理用組成物を製造した。
The present invention will be specifically described below with reference to examples, comparative examples and test examples.
Example 1
50 g of 3-glycidoxypropyltrimethoxysilane (trade name: Silaace 510, silane coupling agent, manufactured by Chisso Corporation) and acetylenic diol mixture (trade name: Orphine PD001, nonionic surfactant, Nisshin Chemical Industry ( Ion-exchanged water was added to 1 g and mixed so that the total amount was 1000 g, and the composition for electrodeposition coating pretreatment of the present invention was produced.
寸法１００×７０×０．３ｍｍの鋼板を、ニッケルめっき浴（商品名：ラスター１，２、（株）シミズ製）を用い、浴温５０℃、めっき時間１０分でめっきを施し、表面に膜厚１５μｍのニッケルめっき皮膜が形成された試料板を作製した。この試料板にリン酸ナトリウム水溶液による脱脂および硫酸による酸洗を施した後、クロム系化成処理液（商品名：エレコートコネクター、（株）シミズ製）に浸漬して通電下に化成処理を施した。化成処理条件は、電流１．６Ａ、浴温４０℃および浸漬時間３０秒であった。化成処理を施した試験板を上記で得られた電着塗装前処理用組成物に浸漬し、電着塗装前処理を施した。電着塗装前処理条件は、浴温４０℃および浸漬時間３０秒であった。電着塗装前処理後の試験板を７０〜８０℃の温度下で３０分間乾燥し、さらにイオン交換水に３０秒間浸漬して純水洗浄を行った。この試験板に、アクリル系カチオン電着塗料（商品名：エレコートＵＣ−２０００、（株）シミズ製）を用い、液温３０℃、塗装時間２分、通電方式：全没通電、電圧６０Ｖ、塗料撹拌：１サイクル／時間の条件下に電着塗装を行った後、試料板を通電槽から取り出し、水洗し、８０℃で３０分間乾燥した。さらに、この試験板に、紫外線照射機（８０Ｗ２灯、メタルハライドランプ、アイグラフィックス（株）製）を２０ｃｍの間隔で設置し、４分間紫外線を照射した。紫外線照射量はおおよそ５０００ｍＪ／ｃｍ２であった。このようにして、表面に電着塗膜を形成した塗装試料板を作製した。 A steel plate having dimensions of 100 × 70 × 0.3 mm is plated using a nickel plating bath (trade name: Raster 1, 2, manufactured by Shimizu Corporation) at a bath temperature of 50 ° C. and a plating time of 10 minutes, and a film is formed on the surface. A sample plate on which a nickel plating film having a thickness of 15 μm was formed was produced. This sample plate was degreased with an aqueous sodium phosphate solution and pickled with sulfuric acid, and then immersed in a chrome-based chemical conversion treatment solution (trade name: Elecoat Connector, manufactured by Shimizu Corporation) and subjected to chemical conversion under energization. did. The chemical conversion treatment conditions were an electric current of 1.6 A, a bath temperature of 40 ° C., and an immersion time of 30 seconds. The test plate subjected to the chemical conversion treatment was immersed in the composition for pretreatment for electrodeposition coating obtained above, and subjected to the pretreatment for electrodeposition coating. The pretreatment conditions for electrodeposition coating were a bath temperature of 40 ° C. and an immersion time of 30 seconds. The test plate after the electrodeposition coating pretreatment was dried at a temperature of 70 to 80 ° C. for 30 minutes, and further immersed in ion exchange water for 30 seconds to perform pure water cleaning. Acrylic cationic electrodeposition paint (trade name: Elecoat UC-2000, manufactured by Shimizu Co., Ltd.) is used for this test plate, liquid temperature is 30 ° C., coating time is 2 minutes, energization method: fully immersed current, voltage 60 V, paint Stirring: After electrodeposition coating was performed under the condition of 1 cycle / hour, the sample plate was taken out of the energizing tank, washed with water, and dried at 80 ° C. for 30 minutes. Furthermore, an ultraviolet irradiator (80W2 lamp, metal halide lamp, manufactured by Eye Graphics Co., Ltd.) was installed on this test plate at an interval of 20 cm, and irradiated with ultraviolet rays for 4 minutes. The amount of ultraviolet irradiation was approximately 5000 mJ / cm 2 . Thus, the coating sample board which formed the electrodeposition coating film on the surface was produced.
（比較例２）
３−グリシドキシプロピルトリメトキシシランに代えて３−アミノプロピルトリメトキシシラン（商品名：サイラエース３３０、シランカップリング剤、チッソ（株）製）を使用する以外は実施例１と同様にして、本発明の電着塗装前処理用組成物を製造した。この電着塗装前処理用組成物を用いる以外は、実施例１と同様にして、塗装試料板を作製した。
( Comparative Example 2)
Except for using 3-aminopropyltrimethoxysilane (trade name: Sila Ace 330, Silane Coupling Agent, manufactured by Chisso Corporation) instead of 3-glycidoxypropyltrimethoxysilane, The electrodeposition coating pretreatment composition of the present invention was produced. A coated sample plate was prepared in the same manner as in Example 1 except that this electrodeposition coating pretreatment composition was used.
（比較例２）
電着塗装前処理を行わない以外は、実施例１と同様にして、塗装試料板を作製した。
(Comparative Example 2 )
A coated sample plate was produced in the same manner as in Example 1 except that the electrodeposition coating pretreatment was not performed.
（試験例１）
実施例１および比較例１、２で得られた塗装試料板を下記の性能試験に供した。結果を表１に示す。
(Test Example 1)
Was subjected to Example 1 Contact and Comparative Example 1, 2 in the resulting coated sample plate to the performance tests described below. The results are shown in Table 1.
［外観］
テストピースの外観を目視により観察し、硬化被膜表面にピンホール、傷などがないものを「○」と評価した。
[appearance]
The appearance of the test piece was visually observed, and a test piece having no pinholes or scratches on the surface of the cured film was evaluated as “◯”.
［密着性試験］
ＡＳＴＭ Ｄ３３５９−９３に準拠し、碁盤目クロスカットテープ剥離を行い、その剥離残渣面積から５Ｂ〜０Ｂの評価を行った。
[Adhesion test]
In accordance with ASTM D3359-93, a cross-cut tape was peeled off, and 5B to 0B were evaluated from the peeled residue area.
［耐摩耗性（ＲＣＡ磨耗）］
ＲＣＡ摩耗試験機（Norman Tool社製）を使用し、温度２５℃、湿度６０％で試験を行い、素地面が露出するまでの回数を求めた。
[Abrasion resistance (RCA wear)]
Using an RCA abrasion tester (manufactured by Norman Tool), the test was performed at a temperature of 25 ° C. and a humidity of 60%, and the number of times until the bare ground was exposed was obtained.
表１から、本発明の電着塗装前処理用組成物を用いて電着塗装前処理を施すことによって、電着塗膜と金属表面との密着性の低下を実用上問題のない程度に抑制しながら、効果後の電着塗膜の耐磨耗性を顕著に向上させ得ることが明らかである。なお、比較例１では外観にムラが発生するが、実用上全く問題がなく、実施例１に比べると相対的にはムラがある。したがって、本発明の電着塗装前処理用組成物による前処理を施した後に電着塗装を施して得られる塗装品は、たとえば、携帯電話、デジタルカメラなどの金属筺体、プラスチックめっき品などの用途に好適に使用できる。 From Table 1, by performing the electrodeposition coating pretreatment using the electrodeposition coating pretreatment composition of the present invention, it is possible to suppress a decrease in the adhesion between the electrodeposition coating film and the metal surface to a practically satisfactory level. However, it is clear that the wear resistance of the electrodeposition coating film after the effect can be remarkably improved. Although the appearance of the comparative example 1 is uneven, there is no problem in practical use, and there is a relative unevenness compared to the first embodiment . Therefore, the coated product obtained by performing the electrodeposition coating after the pretreatment with the composition for the electrodeposition coating pretreatment of the present invention is used, for example, for metal casings such as mobile phones and digital cameras, plastic plating products, etc. Can be suitably used.
Claims (5)
界面活性剤とを含む電着塗装前処理用組成物であって、
前記シランカップリング剤１〜２０重量％と、前記界面活性剤０．１〜２．０重量％とを含み、残部が水であり、
前記シランカップリング剤が、グリシジル基含有アルコキシシラン化合物であり、
前記界面活性剤が、ノニオン系界面活性剤であることを特徴とする電着塗装前処理用組成物。 A silane coupling agent ;
A composition for electrodeposition coating pretreatment comprising a surfactant,
Containing 1 to 20% by weight of the silane coupling agent and 0.1 to 2.0% by weight of the surfactant, the balance being water,
The silane coupling agent is a glycidyl group-containing alkoxysilane compound,
The composition for electrodeposition coating pretreatment , wherein the surfactant is a nonionic surfactant .
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