JP5249819B2 - Electrodeposition coating composition and electrodeposition coating method - Google Patents

Electrodeposition coating composition and electrodeposition coating method Download PDF

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JP5249819B2
JP5249819B2 JP2009048475A JP2009048475A JP5249819B2 JP 5249819 B2 JP5249819 B2 JP 5249819B2 JP 2009048475 A JP2009048475 A JP 2009048475A JP 2009048475 A JP2009048475 A JP 2009048475A JP 5249819 B2 JP5249819 B2 JP 5249819B2
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electrodeposition coating
resin
parts
composition
cationic
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JP2010202740A (en
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幸誠 屋部
亮助 川越
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Nihon Parkerizing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints

Description

本発明は金属材料、特に形状が複雑な金属構成体に対し、優れた付き廻り性を有する電着塗料組成物および電着塗装方法に関するものである。   The present invention relates to an electrodeposition coating composition and an electrodeposition coating method having excellent throwing power for metal materials, particularly metal structures having complicated shapes.

従来、各種金属材料、特に形状が複雑な金属構成体に対して優れた耐食性を付与するための手法としては、複雑な形状の隅々に均一に塗膜を析出させることが可能な電着塗装が一般的に用いられてきた。   Conventionally, as a method for imparting excellent corrosion resistance to various metal materials, especially metal structures with complicated shapes, electrodeposition coating that can deposit a coating film uniformly on the corners of complicated shapes Has been commonly used.

電着塗装は、アニオン性樹脂エマルジョンを含有する水性塗料中で被塗物をアノード電解することによって塗膜を析出させるアニオン電着塗装と、カチオン樹脂エマルジョンを含有する水性塗料中で被塗物をカソード電解することによって塗膜を析出させるカチオン電着塗装とに大別できる。   Electrodeposition coating consists of an anionic electrodeposition coating in which a coating is deposited by anodic electrolysis in an aqueous paint containing an anionic resin emulsion, and an aqueous coating containing a cationic resin emulsion. It can be roughly classified into cationic electrodeposition coating in which a coating film is deposited by cathodic electrolysis.

アニオン性樹脂エマルジョンはアルカリサイドで分散安定性があり、酸性サイドで分散安定性を失う。カチオン性樹脂エマルジョンは反対に酸性サイドで分散安定性があり、アルカリサイドで分散安定性を失う。アノード電解またはカソード電解で樹脂が析出するのは、こうした性質を利用したものである。よって、反応機構上ノニオン性樹脂エマルジョンは析出不可能である。   The anionic resin emulsion has dispersion stability on the alkali side and loses dispersion stability on the acid side. On the contrary, the cationic resin emulsion has dispersion stability on the acid side and loses dispersion stability on the alkali side. The resin is deposited by anodic electrolysis or cathodic electrolysis because of these properties. Therefore, the nonionic resin emulsion cannot be precipitated due to the reaction mechanism.

鉄系金属材料の耐食性向上に対しては、電解処理中に素地金属が塗料中に溶出する心配の無いカチオン電着塗装が有利であり、鉄系材料を主とする金属構成体である自動車車体、自動車部品、家電製品、建築材料等に対してはカチオン電着塗装が広く適用されている。   In order to improve the corrosion resistance of ferrous metal materials, cationic electrodeposition coating that does not cause the base metal to elute into the paint during electrolytic treatment is advantageous, and the automobile body is a metal component mainly composed of ferrous materials. Cationic electrodeposition coating is widely applied to automobile parts, home appliances, building materials and the like.

前述の如く、電着塗装の最大の特徴は塗装の付き廻り性であるが、近年塗料の使用量低減や耐食性の向上を目的に、より高度な付き廻り性が求められるようになってきた。そして、付き廻り性向上のために種々の検討がされてきた。   As described above, the most important feature of electrodeposition coating is the throwing power of the coating. In recent years, more advanced throwing power has been demanded for the purpose of reducing the amount of paint used and improving the corrosion resistance. Various studies have been made to improve the throwing power.

例えば特許文献１（特開２００２−２９４１４３）には、水性媒体、水性媒体中に分散するか又は溶解した、カチオン性エポキシ樹脂及びブロックイソシアネート硬化剤を含むバインダー樹脂、カチオン性エポキシ樹脂を中和するための中和酸、有機溶媒、金属触媒を含有する無鉛性カチオン電着塗料組成物において、揮発性有機分含有量が１重量％以下であり、金属イオン濃度が５００ｐｐｍ以下であり、中和酸の量がバインダー樹脂固形分１００ｇに対して１０〜３０ｍｇ当量である無鉛性カチオン電着塗料組成物、が開示されており、金属触媒はセリウムイオン、ビスマスイオン、銅イオン、亜鉛イオン、モリブデンイオン、アルミニウムイオンからなる群から選択される一種以上、中和酸は酢酸、乳酸、蟻酸、スルファミン酸からなる群から選択される一種以上であることが好ましいとされている。   For example, Patent Document 1 (Japanese Patent Laid-Open No. 2002-294143) neutralizes an aqueous medium, a binder resin containing a cationic epoxy resin and a blocked isocyanate curing agent, or a cationic epoxy resin dispersed or dissolved in the aqueous medium. In the lead-free cationic electrodeposition coating composition containing a neutralizing acid, an organic solvent, and a metal catalyst, the volatile organic content is 1% by weight or less, the metal ion concentration is 500 ppm or less, and the neutralizing acid Is a lead-free cationic electrodeposition coating composition having an amount of 10 to 30 mg equivalent to 100 g of binder resin solid content, and the metal catalyst is cerium ion, bismuth ion, copper ion, zinc ion, molybdenum ion, One or more selected from the group consisting of aluminum ions, the neutralizing acid is acetic acid, lactic acid, formic acid, sulfamic acid. It is that it is preferably at least one selected from the group.

また、この電着塗料組成物に類似した組成物を用いて付き廻り性を向上させる技術も多々開示されている。
特許文献２（特開２００２−２８５３９１）は電着浴の温度制御を特徴としており、特許文献３（特開２００２−２８５３９２）は塗膜のガラス転移温度の異なる２種の電着工程を有することを特徴としており、特許文献４（特開２００２−２９４１４４）は不揮発固形分を特定することを特徴としており、特許文献５（特開２００２−２９４１４５）および特許文献６（特開２００２−２９４１４６）はカチオン性エポキシ樹脂のガラス転移温度と分子量を特定することを特徴としており、特許文献７（特開２００２−２９４１４７）は塗膜の最低造膜温度を特定することを特徴としており、特許文献８（特開２００５−１９４３８９）はカチオン性エポキシ樹脂の基体樹脂骨格、膜抵抗、硬化剤および硬化剤のガラス転移温度を特定することを特徴としており、特許文献９（特開２００８−１５６６５５）はやはり膜抵抗を特定することを特徴としている。 In addition, many techniques for improving the throwing power using a composition similar to this electrodeposition coating composition have been disclosed.
Patent Document 2 (Japanese Patent Laid-Open No. 2002-285391) is characterized by temperature control of the electrodeposition bath, and Patent Document 3 (Japanese Patent Laid-Open No. 2002-285392) has two types of electrodeposition processes having different glass transition temperatures of the coating film. Patent Document 4 (Japanese Patent Laid-Open No. 2002-294144) is characterized by specifying a non-volatile solid content, and Patent Document 5 (Japanese Patent Laid-Open No. 2002-294145) and Patent Document 6 (Japanese Patent Laid-Open No. 2002-294146) are characterized by It is characterized by specifying the glass transition temperature and molecular weight of the cationic epoxy resin, and Patent Document 7 (Japanese Patent Application Laid-Open No. 2002-294147) is characterized by specifying the minimum film-forming temperature of the coating film. JP 2005-194389) specifies the base resin skeleton of the cationic epoxy resin, the film resistance, the curing agent, and the glass transition temperature of the curing agent. DOO is characterized by, Patent Document 9 (JP-2008-156655) is characterized in that also identifies the film resistance.

特開２００２−２９４１４３号公報JP 2002-294143 A 特開２００２−２８５３９１号公報JP 2002-285391 A 特開２００２−２８５３９２号公報JP 2002-285392 A 特開２００２−２９４１４４号公報JP 2002-294144 A 特開２００２−２９４１４５号公報JP 2002-294145 A 特開２００２−２９４１４６号公報JP 2002-294146 A 特開２００２−２９４１４７号公報JP 2002-294147 A 特開２００５−１９４３８９号公報JP 2005-194389 A 特開２００８−１５６６５５号公報JP 2008-156655 A 特開２００７−３１４６９０号公報JP 2007-314690 A 特開２００８−５３８３８３号公報JP 2008-538383 A

前田重義，浅井恒敏，岡田秀弥防食技術：３１，２６８（１９８２）Maeda Shigeyoshi, Asai Tsunetoshi, Okada Hideya Anti-corrosion technology: 31,268 (1982)

上記従来技術は、確かに付き廻り性に対する効果を有するが、市場ニーズは更なる付き廻り性の向上を求めていることも確かである。そこで本発明者らは、カチオン電着塗装の析出メカニズムそのものを再考することとした。   Although the above prior art certainly has an effect on the throwing power, it is also certain that the market needs to further improve the throwing power. Therefore, the present inventors have reconsidered the deposition mechanism itself of the cationic electrodeposition coating.

カチオン電着塗装に使用される樹脂エマルジョンは多くの場合アミン基の導入によりカチオン性を付与している。カチオン性樹脂エマルジョンは酸性サイドで分散安定性があり、アルカリサイドで分散安定性を失うわけであるが、実際のカソード電解によりエマルジョンが電荷を失って塗膜を形成するｐＨは１２前後に達することが文献１に掲載されている。   Resin emulsions used for cationic electrodeposition coating are often imparted with cationic properties by introduction of amine groups. The cationic resin emulsion has dispersion stability on the acidic side and loses dispersion stability on the alkali side. However, the pH at which the emulsion loses electric charge and forms a coating film due to actual cathode electrolysis reaches around 12. Is published in Document 1.

もちろん塗膜が析出するｐＨは樹脂エマルジョンの性状、例えばエマルジョン分子量、導入するアミン基の種類や導入率によって変化するが、少なくともｐＨ１０を超える領域にならないと析出は開始しない。よって、カソード電解によるｐＨ上昇の際、出発ｐＨである塗料組成物のｐＨは、樹脂エマルジョンが安定化している範囲でできるだけ高いｐＨであることが、塗膜の析出性に対して有利であると言える。   Of course, the pH at which the coating film precipitates varies depending on the properties of the resin emulsion, such as the molecular weight of the emulsion, the type of amine groups to be introduced, and the introduction rate, but the deposition does not start unless the pH exceeds 10. Therefore, when the pH is increased by cathodic electrolysis, the pH of the coating composition, which is the starting pH, is advantageously as high as possible within the range where the resin emulsion is stabilized, which is advantageous for the deposition properties of the coating film. I can say that.

従来技術である特許文献１０（特開２００７−３１４６９０）および特許文献１１（特開２００８−５３８３８３）は、やはり電着塗料組成物に関するものであるが、水性塗料組成物のｐＨは、５〜７であることが好ましく、５．５〜６．５であることが更に好ましいとされている。ｐＨが５未満の場合の弊害は、電着塗装効率や膜外観が低下することを挙げている。   Patent Document 10 (Japanese Patent Application Laid-Open No. 2007-314690) and Patent Document 11 (Japanese Patent Application Laid-Open No. 2008-538383), which are related arts, also relate to electrodeposition coating compositions, but the pH of aqueous coating compositions is 5-7. It is preferable that it is preferably 5.5 to 6.5. An adverse effect when the pH is less than 5 is that electrodeposition coating efficiency and film appearance are reduced.

特許文献１〜９については、具体的なｐＨの記述は無いものの、電着塗料の付き廻り性を改良するためには、塗料組成物に含有させる中和酸の量を減らしてカチオン性エポキシ樹脂の中和率を低レベルに抑えること、すなわちできる限りｐＨを高く保持することが好ましいとしている。事実、中和酸の量がバインダー樹脂固形分１００ｇに対して１０〜３０ｍｇ当量であることから、ｐＨは必然的に特許文献１０および１１と同様の範囲になることは明らかである。   In Patent Documents 1 to 9, although there is no specific pH description, in order to improve the throwing power of the electrodeposition paint, the amount of the neutralizing acid contained in the paint composition is reduced and the cationic epoxy resin is used. It is said that it is preferable to keep the neutralization rate of the resin at a low level, that is, to maintain the pH as high as possible. In fact, since the amount of the neutralizing acid is 10 to 30 mg equivalent to 100 g of binder resin solid content, it is clear that the pH inevitably falls within the same range as in Patent Documents 10 and 11.

つまり、電着塗料組成物そのもののｐＨを高くすることも、樹脂エマルジョンの改質によって析出ｐＨを低下することも、もはや限界にきており、それ以外の手法を用いないと付き廻り性の改善は望めないのである。   In other words, increasing the pH of the electrodeposition coating composition itself and lowering the precipitation pH by modifying the resin emulsion are already at the limits. Cannot be expected.

そこで本発明者らは、新たな手法として凝集剤によって塗膜析出ｐＨを低下させることを検討した。そして、種々の凝集剤の中でもＡｌが最も効果的であることを見出した。   Therefore, the present inventors examined reducing the coating film deposition pH with a flocculant as a new technique. And it discovered that Al was the most effective among various flocculants.

しかし、Ａｌ化合物を従来の電着塗料組成物中に添加しても、瞬時に加水分解によって水酸化物に変化してしまい、かつ水酸化物は経時によって凝集していってしまうため、凝集剤としての効果を失ってしまう。   However, even when an Al compound is added to a conventional electrodeposition coating composition, it is instantly changed into a hydroxide by hydrolysis, and the hydroxide aggregates over time. Will lose its effect.

特許文献１〜９には、金属触媒としてアルミニウムイオンを含むことが好ましいとしているが、上記の理由で実際の電着塗料組成物の中では、瞬時に加水分解し水酸化物が形成されているものと推定される。実施例での検証はなされていないが、水酸化物は触媒としての作用は維持するものの、凝集剤としての効果はもはや望めないものと考えられる。   In Patent Documents 1 to 9, it is said that it is preferable to contain aluminum ions as a metal catalyst. However, in the actual electrodeposition coating composition for the above reason, a hydroxide is formed by instantaneous hydrolysis. Estimated. Although it has not been verified in the examples, it is considered that although the hydroxide maintains its action as a catalyst, the effect as a flocculant can no longer be expected.

そこで本発明者らは、電着塗料組成物の常識であった中性付近のｐＨを、Ａｌが継続的にイオン状態で存在できる範囲まであえて低下させ、Ａｌイオンの付き廻り性に対する効果を評価した結果、組成物のｐＨを低下させたにもかかわらず、極めて良好な付き廻り性が得られることを発見した。   Therefore, the present inventors have lowered the pH near neutrality, which was common knowledge of electrodeposition coating compositions, to a range where Al can be continuously present in an ionic state, and evaluated the effect on the circulation property of Al ions. As a result, it has been found that very good throwing power can be obtained even though the pH of the composition is lowered.

そして、このＡｌイオンの効果は、電解析出不可能だったノニオン性樹脂エマルジョンに対しても有効であり、同じくカソード電解によって析出可能になることを発見し、本発明の完成に至った。   And it discovered that the effect of this Al ion was effective also for the nonionic resin emulsion which could not be electrolytically deposited, and also became possible to deposit by cathode electrolysis, and it came to the completion of this invention.

すなわち、本発明は次に示す（１）および（２）である。
（１） ノニオン性および／またはカチオン性の水系樹脂およびＡｌイオン２０〜５００ｐｐｍを含有し、ｐＨがＡｌイオン濃度をＡ［ｐｐｍ］としたとき次の計算式を満足することを特徴とする電着塗料組成物。
３．５≦ｐＨ≦−Ｌｏｇ（Ａ×１．９３×１０−１５）１／３
（２） 前記（１）の組成物を用いて金属材料をカソード電解法にて塗膜を析出せしめることを特徴とする電着塗装方法。 That is, the present invention includes the following (1) and (2).
(1) Electrodeposition containing a nonionic and / or cationic water-based resin and Al ions of 20 to 500 ppm, and satisfying the following calculation formula when the pH is Al concentration of A [ppm] Paint composition.
3.5 ≦ pH ≦ −Log (A × 1.93 × 10 −15 ) 1/3
(2) An electrodeposition coating method comprising depositing a coating film of a metal material by a cathode electrolysis method using the composition of (1).

第１図は、Ａｌイオン濃度およびｐＨの適正範囲を示した図である。FIG. 1 is a diagram showing appropriate ranges of Al ion concentration and pH. 第２図は、付き廻り性試験に用いる「４枚ボックス付き廻り性試験用治具」のモデル図である。FIG. 2 is a model diagram of a “four-box with-around test jig” used in the in-around test. 第３図は、付き廻り性試験における電着塗装状態を示す。FIG. 3 shows the electrodeposition coating state in the throwing power test.

１．直径８ｍｍの穴
２．４枚ボックス法の付き廻り性試験用治具における外板（Ａ面）
３．４枚ボックス法の付き廻り性試験用治具における内板（Ｇ面）
４．電着塗料浴 1. Outer plate (surface A) in a jig for testing the throwing power of a 2.4-sheet box method with an 8 mm diameter hole
3. Inner plate for G
4). Electrodeposition paint bath

本発明の電着塗料組成物にはノニオン性および／またはカチオン性の水系樹脂が含有されている。ここで、ノニオン性樹脂及びカチオン性樹脂のいずれも特に限定されるものではない。基体樹脂はいずれのタイプを用いても、本発明の効果を損なうものではないが、エポキシ、ウレタン、アクリルがより好ましい。ここで、本発明の一特徴が、新規作用機序（ｐＨ上昇に伴ってＡｌイオンが水酸化コロイドとなり凝集するが、この際に回りの樹脂を巻き込むという作用機序）に基づき、従来は電解析出不能であったノニオン性樹脂もが使用可能となった点である。このようにノニオン系樹脂も使用可能となったことにより選択の幅が広がり、これまで持たせることができなかった各種性質を皮膜に付与することが可能となる。更に、カチオン性樹脂を使用した場合についても、ｐＨ上昇に伴って樹脂自体が分散安定性を失う公知作用機序に加え、前述した新規作用機序に基づき、従来よりも低いｐＨでの電析が可能となる。   The electrodeposition coating composition of the present invention contains a nonionic and / or cationic aqueous resin. Here, neither a nonionic resin nor a cationic resin is particularly limited. Whichever type of base resin is used, the effect of the present invention is not impaired, but epoxy, urethane, and acrylic are more preferable. Here, one feature of the present invention is based on a novel action mechanism (an action mechanism in which Al ions become a hydroxide colloid and aggregate as the pH rises, but the surrounding resin is involved at this time). Nonionic resins that could not be analyzed can now be used. Since nonionic resins can be used in this way, the range of selection is widened, and various properties that could not be obtained can be imparted to the film. Furthermore, in the case of using a cationic resin, in addition to the known action mechanism in which the resin itself loses dispersion stability as the pH increases, electrodeposition at a lower pH than the conventional one is based on the above-mentioned novel action mechanism. Is possible.

樹脂エマルジョンの濃度も特に規定されないが、電着塗料組成物の全重量を基準として、５〜３０重量％含有することが好ましい。７〜２５重量％が更に好ましく、１０〜２０重量％が最も好ましい。樹脂含有量が低過ぎると皮膜析出量が不足し、含有量が高過ぎると経済的に不利である。   The concentration of the resin emulsion is not particularly specified, but it is preferably 5 to 30% by weight based on the total weight of the electrodeposition coating composition. It is more preferably 7 to 25% by weight, and most preferably 10 to 20% by weight. If the resin content is too low, the amount of film deposition is insufficient, and if the content is too high, it is economically disadvantageous.

ノニオン性樹脂エマルジョンについては基体樹脂にエチレンオキサイドのようなノニオン性官能基を導入させる方法、すなわち自己乳化法、およびノニオン界面活性剤を用いて乳化させる方法、すなわち強制乳化法のいずれかまたは双方の手法を用いて作製することができる。カチオン性樹脂エマルジョンについては基体樹脂にアミン基のようなカチオン性官能基を導入させる方法、すなわち自己乳化法、およびカチオン界面活性剤を用いて乳化させる方法、すなわち強制乳化法のいずれかまたは双方を同時に用いて作製することができる。更に、カチオン性官能基を導入後、ノニオン界面活性剤を乳化助剤として用いることもできる。また、自己乳化エマルジョンの分子量が小さい場合は、もはや粒子状のエマルジョンではなく水溶性樹脂となるが、水溶性樹脂であっても本発明の効果が損なわれるものではない。本発明における水系樹脂とは、水分散するエマルジョンと水溶性樹脂の総称である。   For the nonionic resin emulsion, either or both of a method of introducing a nonionic functional group such as ethylene oxide into the base resin, that is, a self-emulsification method and a method of emulsification using a nonionic surfactant, that is, a forced emulsification method. It can be produced using a technique. For the cationic resin emulsion, either or both of a method of introducing a cationic functional group such as an amine group into the base resin, that is, a self-emulsification method and a method of emulsification using a cationic surfactant, that is, a forced emulsification method, are used. They can be used at the same time. Furthermore, after introducing a cationic functional group, a nonionic surfactant can also be used as an emulsification aid. Moreover, when the molecular weight of the self-emulsifying emulsion is small, the emulsion is no longer a particulate emulsion but a water-soluble resin, but even the water-soluble resin does not impair the effects of the present invention. The water-based resin in the present invention is a general term for water-dispersed emulsions and water-soluble resins.

また、水系樹脂には、ブロック化ポリイソシアネートをはじめとする硬化剤を任意に配合することもできる。   In addition, a curing agent such as a blocked polyisocyanate can be arbitrarily added to the water-based resin.

本発明の電着塗料組成物にはＡｌイオンを２０〜５００ｐｐｍ含有することが好ましい。５０〜４００ｐｐｍが更に好ましく、１００〜３００ｐｐｍが最も好ましい。下限を下回るとＡｌイオンの塗膜析出向上効果が不充分となり、上限を上回ると組成物の電気伝導度が過剰となり、かえって付き廻り性を低下させる。   The electrodeposition coating composition of the present invention preferably contains 20 to 500 ppm of Al ions. 50 to 400 ppm is more preferable, and 100 to 300 ppm is most preferable. If the lower limit is not reached, the effect of improving the coating deposition of Al ions becomes insufficient, and if the upper limit is exceeded, the electrical conductivity of the composition becomes excessive, and the throwing power is reduced.

組成物中のＡｌイオン濃度は、超遠心機により組成物を固液分離し、液相を高周波誘導結合プラズマ発光分光分析（ＩＣＰ）もしくは原子吸光分光分析（ＡＡ）を用いて定量することができる。   The Al ion concentration in the composition can be determined by solid-liquid separation of the composition using an ultracentrifuge and quantifying the liquid phase using high frequency inductively coupled plasma emission spectrometry (ICP) or atomic absorption spectrometry (AA). .

本発明に係る電着組成物の液体媒体としては、水性媒体が好適であり、水がより好適である。尚、液体媒体が水である場合、液体媒体として水以外の他の水系溶媒（例えば、水溶性のアルコール類）を含有していてもよい。   As the liquid medium of the electrodeposition composition according to the present invention, an aqueous medium is preferable, and water is more preferable. When the liquid medium is water, the liquid medium may contain an aqueous solvent other than water (for example, water-soluble alcohols).

本発明の電着塗料組成物のｐＨはＡｌイオン濃度をＡ［ｐｐｍ］としたとき次の計算式を満足することが好ましい。
３．５≦ｐＨ≦−Ｌｏｇ（（Ａ×１．９３×１０−１５）１／３）
下記式であることが更に好ましい。
３．６≦ｐＨ≦−Ｌｏｇ（（Ａ×１．９３×１０−１５）１／３）
下記式であることが最も好ましい。
３．７≦ｐＨ≦−Ｌｏｇ（（Ａ×１．９３×１０−１５）１／３）
ｐＨが下限を下回ると、析出効率が低下し付き廻り性も低下していく。ｐＨが上限を上回ると、Ａｌイオンが加水分解を起こしてしまうため、好ましくない。 The pH of the electrodeposition coating composition of the present invention preferably satisfies the following formula when the Al ion concentration is A [ppm].
3.5 ≦ pH ≦ −Log ((A × 1.93 × 10 −15 ) 1/3 )
The following formula is more preferable.
3.6 ≦ pH ≦ −Log ((A × 1.93 × 10 −15 ) 1/3 )
The following formula is most preferable.
3.7 ≦ pH ≦ −Log ((A × 1.93 × 10 −15 ) 1/3 )
When the pH is lower than the lower limit, the deposition efficiency is lowered and the throwing power is also lowered. When the pH exceeds the upper limit, Al ions cause hydrolysis, which is not preferable.

−Ｌｏｇ（（Ａ×１．９３×１０−１５）１／３）の項は、水酸化Ａｌの２５℃における溶解度積：１．９２×１０−３２から求められる。つまり、このｐＨ以上になるとＡｌイオンは水酸化物として沈殿析出してしまい、もはやイオンではいられなくなる。ここで、２５℃は、組成物の保存時及び使用時の典型的な温度である。 The term -Log ((A × 1.93 × 10 −15 ) 1/3 ) is obtained from the solubility product of Al hydroxide at 25 ° C .: 1.92 × 10 −32 . That is, when the pH is exceeded, Al ions precipitate as hydroxides and can no longer be ions. Here, 25 ° C. is a typical temperature during storage and use of the composition.

本発明におけるＡｌイオンの作用効果は以下の通りである。つまり、イオン状のＡｌがカソード電解による金属表面ｐＨ上昇により微細な水酸化物コロイドになり、それがｐＨ９前後でゼータ電荷を完全に失い急激に凝集を始める際、周りの樹脂エマルジョンをも巻き込んで析出するものと推定される。   The effects of Al ions in the present invention are as follows. In other words, when ionic Al becomes a fine hydroxide colloid due to the increase in pH of the metal surface due to cathodic electrolysis, when it completely loses the zeta charge at around pH 9 and begins to agglomerate rapidly, the surrounding resin emulsion is also involved. Presumed to be deposited.

カソード電解によってＡｌイオンから水酸化物コロイドの電荷の消失にいたる一連の反応は瞬時に完了する必要がある。あらかじめ水酸化物になっていては、経時で凝集が始まってしまい、ｐＨ９前後での凝集能力が極端に減退する。よって、本発明のＡｌ成分は、組成物中ではあくまでイオンでいなければならないのである。   A series of reactions from cathodic electrolysis to disappearance of the charge of the hydroxide colloid must be completed instantaneously. If it has become a hydroxide in advance, aggregation starts over time, and the aggregation ability around pH 9 is extremely reduced. Therefore, the Al component of the present invention must be only ions in the composition.

また、Ａｌイオンは特定のキレート剤によって安定化できるが、安定化させてしまっては、ｐＨ上昇による水酸化物の生成も阻害されるため、好ましくない。なお、電着塗料組成物に通常配合されている、酢酸、蟻酸、スルファミン酸、乳酸等の有機酸には、Ａｌイオンを安定化させるほどのキレート能力はない。   Further, Al ions can be stabilized by a specific chelating agent, but if stabilized, formation of hydroxide due to an increase in pH is also inhibited, which is not preferable. Note that organic acids such as acetic acid, formic acid, sulfamic acid, and lactic acid that are usually blended in electrodeposition coating compositions do not have a chelating ability to stabilize Al ions.

ＡｌイオンはＡｌ化合物を用いて添加することができる。Ａｌ化合物は特に限定されないが、硝酸塩、硫酸塩と言った無機酸塩または乳酸塩、酢酸塩と言った有機酸塩の形で添加することが可能である。
参考のため、Ａｌイオン濃度およびｐＨの適正範囲を第１図に示す。 Al ions can be added using an Al compound. The Al compound is not particularly limited, but can be added in the form of an inorganic acid salt such as nitrate or sulfate, or an organic acid salt such as lactate or acetate.
For reference, the appropriate ranges of Al ion concentration and pH are shown in FIG.

本発明の電着塗料組成物を用いて金属材料表面に塗膜を形成させる方法としては、カソード電解法が好ましい。無電解もしくはアノード電解では塗膜析出は望めない。
カソード電解条件は特に規定されるものではないが、５０〜４００Ｖの電圧を印加することが好ましい。１００〜３００Ｖであることが更に好ましく、１５０〜２５０Ｖであることが最も好ましい。なお、必ずしも定電圧である必要は無く、徐々に電圧を増加させていく方法や、２段通電等の方法も適用可能である。 As a method of forming a coating film on the surface of a metal material using the electrodeposition coating composition of the present invention, a cathode electrolysis method is preferable. Coating deposition cannot be expected with electroless or anodic electrolysis.
Cathodic electrolysis conditions are not particularly defined, but it is preferable to apply a voltage of 50 to 400V. More preferably, it is 100-300V, and most preferably 150-250V. It is not always necessary to use a constant voltage, and a method of gradually increasing the voltage or a method such as two-stage energization is also applicable.

本発明の組成物には、更に必要に応じて顔料、触媒、有機溶剤、顔料分散剤、界面活性剤等、塗料分野で通常使用されている添加剤を適用することもできる。顔料としては、チタン白、カーボンブラック等の着色顔料、クレー、タルク、バリタ等の体質顔料、トリポリリン酸アルミニウム、リン酸亜鉛等の防錆顔料、ジブチル錫オキサイド、ジオクチル錫オキサイド等の有機錫化合物、ジブチル錫ラウレート、ジブチル錫ジベンゾエートなどのジアルキル錫の脂肪酸もしくは芳香族カルボン酸塩などの錫化合物が挙げられる。   In the composition of the present invention, additives usually used in the paint field such as a pigment, a catalyst, an organic solvent, a pigment dispersant, and a surfactant can be further applied as necessary. Examples of pigments include colored pigments such as titanium white and carbon black, extender pigments such as clay, talc and barita, rust preventive pigments such as aluminum tripolyphosphate and zinc phosphate, organic tin compounds such as dibutyltin oxide and dioctyltin oxide, Examples thereof include dialkyltin fatty acids such as dibutyltin laurate and dibutyltin dibenzoate, and tin compounds such as aromatic carboxylates.

本発明の電着塗料組成物は各種金属材料に対して適用される。金属材料は、特に限定されるものではないが、冷延鋼板、熱延鋼板、鋳物材、鋼管等の鉄鋼材料、それらの鉄鋼材料の上に亜鉛系めっき処理および／またはアルミニウム系めっきが施された材料、アルミニウム合金板、アルミニウム系鋳物材、マグネシウム合金版、マグネシウム系鋳物材等が挙げられる。また、あらかじめ塗装下地処理としてリン酸亜鉛系化成処理やジルコニウム系化成処理が施されていても、本発明の効果を損なうものではない。特に形状が複雑な金属構成体、例えば、鉄系材料を主とする金属構成体である自動車車体、自動車部品、家電製品、建築材料等への使用に適している。   The electrodeposition coating composition of the present invention is applied to various metal materials. The metal material is not particularly limited, but steel materials such as cold-rolled steel plates, hot-rolled steel plates, casting materials, steel pipes, etc., and zinc-based plating treatment and / or aluminum-based plating are applied on those steel materials. Materials, aluminum alloy plates, aluminum castings, magnesium alloy plates, magnesium castings, and the like. Moreover, even if the zinc phosphate-based chemical conversion treatment or the zirconium-based chemical conversion treatment is performed in advance as a coating ground treatment, the effect of the present invention is not impaired. It is particularly suitable for use in metal structures having complicated shapes, for example, automobile bodies, automobile parts, home appliances, building materials, etc., which are metal structures mainly composed of iron-based materials.

以下に実施例および比較例を挙げて本発明の内容を具体的に説明する。
実施例中、「部」および「％」は、ことわりのない限り、重量基準による。 The contents of the present invention will be specifically described below with reference to examples and comparative examples.
In the examples, “parts” and “%” are based on weight unless otherwise specified.

カチオン性エポキシ樹脂の合成
攪拌機、冷却管、窒素導入管、温度計および滴下漏斗を装備したフラスコに、２，４−／２，６−トリレンジイソシアネート（重量比＝８／２）９２部、メチルイソブチルケトン（以下、ＭＩＢＫと略す）９５部およびジブチル錫ジラウレート０．５部を仕込んだ。反応混合物を攪拌下、メタノール２１部を滴下した。反応は、室温から始め、発熱により６０℃まで昇温した。 Synthesis of cationic epoxy resin stirrer, cooling tube, nitrogen introduction tube, thermometer and dropping funnel, in a flask equipped with 92 parts of 2,4- / 2,6-tolylene diisocyanate (weight ratio = 8/2), methyl 95 parts of isobutyl ketone (hereinafter abbreviated as MIBK) and 0.5 part of dibutyltin dilaurate were charged. While stirring the reaction mixture, 21 parts of methanol was added dropwise. The reaction was started from room temperature and heated to 60 ° C. due to heat generation.

その後、３０分間反応を継続した後、エチレングリコールモノ−２−エチルヘキシルエーテル５７部を滴下漏斗より滴下した。更に、反応混合物に、ビスフェノールＡ−プロピレンオキシド５モル付加体４２部を添加した。反応は主に、６０〜６５℃の範囲で行い、ＩＲスペクトルの測定において、イソシアネート基に基づく吸収が消失するまで継続した。   Then, after continuing reaction for 30 minutes, 57 parts of ethylene glycol mono-2-ethylhexyl ether was dripped from the dropping funnel. Furthermore, 42 parts of bisphenol A-propylene oxide 5 mol adduct was added to the reaction mixture. The reaction was mainly carried out in the range of 60 to 65 ° C. and continued until absorption based on the isocyanate group disappeared in the measurement of IR spectrum.

次に、ビスフェノールＡとエピクロルヒドリンから既知の方法で合成したエポキシ当量１８８のエポキシ樹脂３６５部を反応混合物に加えて、１２５℃まで昇温した。その後、ベンジルジメチルアミン１．０部を添加し、エポキシ当量４１０になるまで１３０℃で反応させた。   Next, 365 parts of epoxy resin with an epoxy equivalent of 188 synthesized from bisphenol A and epichlorohydrin by a known method was added to the reaction mixture, and the temperature was raised to 125 ° C. Thereafter, 1.0 part of benzyldimethylamine was added and reacted at 130 ° C. until the epoxy equivalent was 410.

続いて、ビスフェノールＡ８７部を加えて１２０℃で反応させたところ、エポキシ当量は１１９０となった。その後、反応混合物を冷却し、ジエタノールアミン１１部、Ｎ−エチルエタノールアミン２４部およびアミノエチルエタノールアミンのケチミン化物の７９重量％ＭＩＢＫ溶液２５部を加え、１１０℃で２時間反応させた。その後、ＭＩＢＫで不揮発分８０％となるまで希釈し、ガラス転移温度が２２℃のアミン変性エポキシ樹脂（樹脂固形分８０％）を得た。なお、この製造方法は特許文献１（特開２００２−２９４１４３）の実施例における製造例１に準ずる。   Subsequently, when 87 parts of bisphenol A was added and reacted at 120 ° C., the epoxy equivalent was 1190. Thereafter, the reaction mixture was cooled, 11 parts of diethanolamine, 24 parts of N-ethylethanolamine and 25 parts of 79 wt% MIBK solution of ketimine product of aminoethylethanolamine were added and reacted at 110 ° C. for 2 hours. Then, it diluted with MIBK until it became 80% of non volatile matters, and obtained the amine modified epoxy resin (resin solid content 80%) whose glass transition temperature is 22 degreeC. This manufacturing method is based on Manufacturing Example 1 in the embodiment of Patent Document 1 (Japanese Patent Laid-Open No. 2002-294143).

ブロックイソシアネート硬化剤の製造
ジフェニルメタンジイソシアナート１２５０部およびＭＩＢＫ２６６．４部を反応容器に仕込み、これを８０℃まで加熱した後、ジブチル錫ジラウレート２．５部を加えた。ここに、ε−カプロラクタム２２６部をブチルセロソルブ９４４部に溶解させたものを８０℃で２時間かけて滴下した。さらに１００℃で４時間加熱した後、ＩＲスペクトルの測定において、イソシアネート基に基づく吸収が消失したことを確認し、放冷後、ＭＩＢＫ３３６．１部を加えてブロックイソシアネート硬化剤を得た。なお、この製造方法は特許文献１（特開２００２−２９４１４３）の実施例における製造例２に準ずる。 Production of blocked isocyanate curing agent 1250 parts of diphenylmethane diisocyanate and 266.4 parts of MIBK were charged into a reaction vessel, which was heated to 80 ° C., and then 2.5 parts of dibutyltin dilaurate was added. A solution prepared by dissolving 226 parts of ε-caprolactam in 944 parts of butyl cellosolve was added dropwise at 80 ° C. over 2 hours. Furthermore, after heating at 100 degreeC for 4 hours, in the measurement of IR spectrum, it confirmed that the absorption based on an isocyanate group disappeared, and after standing to cool, MIBK 336.1 parts was added and the block isocyanate hardening | curing agent was obtained. This manufacturing method is based on Manufacturing Example 2 in the embodiment of Patent Document 1 (Japanese Patent Laid-Open No. 2002-294143).

顔料分散樹脂の製造
まず、攪拌装置、冷却管、窒素導入管および温度計を装備した反応容器に、イソホロンジイソシアネート（以下、ＩＰＤＩと略す）２２２．０部を入れ、ＭＩＢＫ３９．１部で希釈した後、ここヘジブチル錫ジラウレート０．２部を加えた。その後、これを５０℃に昇温した後、２−エチルヘキサノール１３１．５部を攪拌下、乾燥窒素雰囲気中で２時間かけて滴下した。適宜、冷却することにより、反応温度を５０℃に維持した。その結果、２−エチルヘキサノールハーフブロック化ＩＰＤＩ（樹脂固形分９０．０％）が得られた。 Production of pigment dispersion resin First, 222.0 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI) was placed in a reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe and a thermometer, and diluted with 39.1 parts of MIBK. Here, 0.2 part of hedibutyltin dilaurate was added. Then, after heating this to 50 degreeC, 131.5 parts of 2-ethylhexanol was dripped over 2 hours in dry nitrogen atmosphere, stirring. The reaction temperature was maintained at 50 ° C. by cooling appropriately. As a result, 2-ethylhexanol half-blocked IPDI (resin solid content: 90.0%) was obtained.

次いで、適当な反応容器に、ジメチルエタノールアミン８７．２部、７５％乳酸水溶液１１７．６部およびエチレングリコールモノブチルエーテル３９．２部を順に加え、６５℃で約半時間攪拌して、４級化剤を調製した。   Next, 87.2 parts of dimethylethanolamine, 117.6 parts of 75% aqueous lactic acid solution, and 39.2 parts of ethylene glycol monobutyl ether are added to a suitable reaction vessel in this order, and the mixture is stirred at 65 ° C. for about half an hour to form quaternization. An agent was prepared.

次に、エポン（ＥＰＯＮ）８２９（シェル・ケミカル・カンパニー社製ビスフェノールＡ型エポキシ樹脂、エポキシ当量１９３〜２０３）７１０．０部とビスフェノールＡ２８９．６部とを適当な反応容器に仕込み、窒素雰囲気下、１５０〜１６０℃に加熱したところ、初期発熱反応が生じた。反応混合物を１５０〜１６０℃で約１時間反応させ、次いで、１２０℃に冷却した後、先に調製した２−エチルヘキサノールハーフブロック化ＩＰＤＩ（ＭＩＢＫ溶液）４９８．８部を加えた。   Next, 710.0 parts of EPON 829 (bisphenol A type epoxy resin manufactured by Shell Chemical Company, epoxy equivalent 193 to 203) and 289.6 parts of bisphenol A were charged into a suitable reaction vessel, and the reaction was conducted under a nitrogen atmosphere. When heated to 150 to 160 ° C., an initial exothermic reaction occurred. The reaction mixture was reacted at 150-160 ° C. for about 1 hour, then cooled to 120 ° C., and 498.8 parts of 2-ethylhexanol half-blocked IPDI (MIBK solution) prepared above was added.

反応混合物を１１０〜１２０℃に約１時間保ち、次いで、エチレングリコールモノブチルエーテル１３９０．２部を加え、混合物を８５〜９５℃に冷却し、均一化した後、先に調製した４級化剤１９６．７部を添加した。酸価が１となるまで反応混合物を８５〜９５℃に保持した後、脱イオン水３７．０部を加えて、エポキシ−ビスフェノールＡ樹脂において４級化を終了させ、４級アンモニウム塩部分を有する顔料分散用樹脂を得た（樹脂固形分５０％）。なお、この製造方法は特許文献１（特開２００２−２９４１４３）の実施例における製造例３に準ずる。   The reaction mixture is kept at 110-120 ° C. for about 1 hour, then 1390.2 parts of ethylene glycol monobutyl ether is added, the mixture is cooled to 85-95 ° C. and homogenized, and then the quaternizing agent 196 prepared above is used. 7 parts were added. After maintaining the reaction mixture at 85-95 ° C. until the acid value is 1, add 37.0 parts deionized water to terminate quaternization in the epoxy-bisphenol A resin and have a quaternary ammonium salt moiety. A pigment dispersing resin was obtained (resin solid content 50%). This manufacturing method is based on Manufacturing Example 3 in the embodiment of Patent Document 1 (Japanese Patent Laid-Open No. 2002-294143).

顔料分散ペーストの製造
サンドグラインドミルに顔料分散用樹脂を１２０部、カーボンブラック２．０部、カオリン１００．０部、二酸化チタン８０．０部、リン酸亜鉛４水和物１８．０部およびイオン交換水２２１．７部を入れ、粒度１０μｍ以下になるまで分散して、顔料分散ペーストを得た（固形分４８％）。なお、この製造方法はリンモリブデン酸アルミニウムの替わりにリン酸亜鉛４水和物を用いた他は、特許文献１（特開２００２−２９４１４３）の実施例における製造例４に準ずる。 Manufacture of pigment dispersion paste 120 parts of resin for pigment dispersion in sand grind mill, 2.0 parts of carbon black, 100.0 parts of kaolin, 80.0 parts of titanium dioxide, 18.0 parts of zinc phosphate tetrahydrate and ions 221.7 parts of exchange water was added and dispersed until the particle size became 10 μm or less to obtain a pigment dispersion paste (solid content 48%). In addition, this manufacturing method is based on the manufacturing example 4 in the Example of patent document 1 (Unexamined-Japanese-Patent No. 2002-294143) except having used the zinc phosphate tetrahydrate instead of the aluminum phosphomolybdate.

カチオン性エポキシ電着塗料組成物の製造
カチオン性エポキシ樹脂とブロックイソシアネート硬化剤とを固形分比で７０／３０で均一になるよう混合した。その後、エチレングリコール−２−エチルヘキシルエーテルを固形分に対して２重量％になるよう添加した。これに樹脂固形分１００ｇ当たり酸のミリグラム当量（MEQ（A））が２４になるよう氷酢酸を添加し、さらにイオン交換水をゆっくりと加えて希釈した。減圧下でＭＩＢＫを除去することにより、固形分が３６％のエマルションを得た。 Production of Cationic Epoxy Electrodeposition Coating Composition A cationic epoxy resin and a blocked isocyanate curing agent were mixed so as to be uniform at a solid content ratio of 70/30. Thereafter, ethylene glycol-2-ethylhexyl ether was added to 2% by weight based on the solid content. Glacial acetic acid was added so that the milligram equivalent (MEQ (A)) of the acid per 100 g of resin solids was 24, and ion-exchanged water was slowly added to dilute. By removing MIBK under reduced pressure, an emulsion having a solid content of 36% was obtained.

このエマルション１９６０部および顔料分散ペースト１９７部とジブチル錫オキサイド１４．５部とイオン交換水１８４３部とを混合して、固形分２０重量％の電着塗料組成物（以下略号「Ｒ１」）を得た。なお、この製造方法は１０％酢酸セリウム水溶液を混合しなかったことを除いて特許文献１（特開２００２−２９４１４３）の実施例における実施例１に準ずる。   1960 parts of this emulsion, 197 parts of pigment dispersion paste, 14.5 parts of dibutyltin oxide and 1843 parts of ion-exchanged water were mixed to obtain an electrodeposition coating composition having a solid content of 20% by weight (hereinafter abbreviated as “R1”). It was. In addition, this manufacturing method is based on Example 1 in the Example of patent document 1 (Unexamined-Japanese-Patent No. 2002-294143) except not having mixed 10% cerium acetate aqueous solution.

カチオン性アクリル電着塗料組成物の製造
神東塗料製カチオン性アクリル樹脂「サクセード＃１０００」（固形分：６５％）を脱イオン水で希釈し、固形分を１８％に調整した（以下略号「Ｒ２」）。 Production of Cationic Acrylic Electrodeposition Coating Composition Cationic acrylic resin “Saxade # 1000” (solid content: 65%) manufactured by Shinto Paint was diluted with deionized water to adjust the solid content to 18% (hereinafter abbreviated as “abbreviation“ R2 ").

ノニオン性ウレタン電着塗料組成物の製造
ＤＩＣ社製ノニオン性ウレタン樹脂「ＶＯＮＤＩＣ２２２０」（固形分：４０％）を脱イオン水で希釈し、固形分を１８％に調整した（以下略号「Ｒ３」）。 Production of Nonionic Urethane Electrodeposition Coating Composition Nonionic urethane resin “VONDIC2220” (solid content: 40%) manufactured by DIC was diluted with deionized water to adjust the solid content to 18% (hereinafter abbreviated as “R3”). .

実施例および比較例にてＡｌイオンを添加する水準については、Ａｌイオンは硝酸アルミニウム９水和物、硫酸アルミニウム１４〜１８水和物または乳酸アルミニウムを用いて添加した。また、必要に応じて組成物のｐＨを硝酸またはアンモニアを用いて調整した。組成物の組成を第１表に示す。   Regarding the level of adding Al ions in Examples and Comparative Examples, Al ions were added using aluminum nitrate nonahydrate, aluminum sulfate 14-18 hydrate, or aluminum lactate. Further, the pH of the composition was adjusted with nitric acid or ammonia as necessary. The composition of the composition is shown in Table 1.

試験板の作製
試験板として、冷延鋼板：ＳＰＣＣ（ＪＩＳ３１４１）７０×１５０×０．８ｍｍを用い、あらかじめその表面を日本パーカライジング社製強アルカリ脱脂剤「ＦＣ−Ｅ２００１」を使用して、１２０秒間スプレー処理することにより脱脂処理した。脱脂処理後は３０秒間スプレー水洗し、実施例および比較例に示す組成物に浸漬させ、カソード電解処理を実施した。電解終了後の試験板は直ちに脱イオン水にて３０秒間スプレー水洗し、電気オーブン中で１７０℃にて２０分間焼付けを行った。 Preparation of test plate As a test plate, cold-rolled steel plate: SPCC (JIS 3141) 70 × 150 × 0.8 mm was used, and its surface was used in advance using a strong alkaline degreasing agent “FC-E2001” manufactured by Nihon Parkerizing Co., Ltd. for 120 seconds. A degreasing treatment was performed by spraying. After the degreasing treatment, it was washed with spray water for 30 seconds, immersed in the compositions shown in Examples and Comparative Examples, and subjected to cathode electrolytic treatment. The test plate after completion of electrolysis was immediately spray-washed with deionized water for 30 seconds, and baked at 170 ° C. for 20 minutes in an electric oven.

付き廻り性評価
「４枚ボックス法」にて付き廻り性を評価した。試験板に直径８ｍｍの穴を空け、４枚の鋼板を２ｃｍ間隔で設置した「４枚ボックス法付き廻り性試験の治具」（第２図参照）を、第３図のように配線した。第３図の４枚の鋼板のうち、最も左側の鋼板に向かって左側の面を「Ａ面」、向かって右側の面を「Ｂ面」とする。同様に、左から２番目の鋼板の左右の面を、それぞれ、「Ｃ面」及び「Ｄ面」、左から３番目の鋼板の左右の面を、それぞれ、「Ｅ面」及び「Ｆ面」、そして最も右側の鋼板の左右の面が、それぞれ、「Ｇ面」と「Ｈ面」となる。第２図の装置において、塗装浴温３０℃、Ａ面と電極との極間距離１０ｃｍ、通電時間３分間にて、Ａ面膜厚２０μｍとなる電圧にて電着塗装した。 Evaluation of throwing power The throwing power was evaluated by the “four-sheet box method”. As shown in FIG. 3, a “four-box testability jig with a box method” (see FIG. 2) in which holes of 8 mm in diameter were formed in the test plate and four steel plates were installed at 2 cm intervals was wired. Of the four steel plates shown in FIG. 3, the left side facing the leftmost steel plate is referred to as “A surface”, and the right side surface toward “B surface”. Similarly, the left and right surfaces of the second steel plate from the left are “C surface” and “D surface”, respectively, and the left and right surfaces of the third steel plate from the left are “E surface” and “F surface”, respectively. The right and left surfaces of the rightmost steel sheet are the “G plane” and the “H plane”, respectively. In the apparatus shown in FIG. 2, electrodeposition was applied at a coating bath temperature of 30 ° C., a distance between the A-side and the electrode of 10 cm, and a current-carrying time of 3 minutes, at a voltage of A-side film thickness of 20 μm.

付き廻り性は、Ｇ面の膜厚にて評価した。Ｇ面膜厚：５μｍ未満を×、５μｍ以上１０μｍ未満を○、１０μｍ以上を◎とした。
但し、Ｒ３については４枚ボックス法ではなく、試験板１枚を２００Ｖにて３分間カソード電解処理し、焼付け後の塗膜厚を評価した。評価結果を第１表に併記する。 The throwing power was evaluated by the film thickness on the G surface. G-plane film thickness: less than 5 μm x, 5 μm or more and less than 10 μm ◯, 10 μm or more as ◎.
However, R3 was not a four-sheet box method, and one test plate was subjected to cathodic electrolytic treatment at 200 V for 3 minutes, and the coating thickness after baking was evaluated. The evaluation results are also shown in Table 1.

第１表の実施例１〜６より、本発明の電着塗料組成物を用いたことによって、金属材料に対して良好な付き廻り性が得られていることがわかる。   From Examples 1 to 6 in Table 1, it can be seen that by using the electrodeposition coating composition of the present invention, good throwing power is obtained for the metal material.

これに対し、本発明の最大の特徴であるＡｌイオンを配合しない比較例１〜３は、付き廻り性が不充分であるばかりか、ノニオン性樹脂エマルジョンに関しては析出すらしていない。   On the other hand, Comparative Examples 1 to 3, which do not contain Al ions, which is the greatest feature of the present invention, are not sufficient in throwing power and are not even precipitated with respect to the nonionic resin emulsion.

また、比較例４はＡｌイオン濃度下限下であり、比較例５はＡｌイオン濃度過剰およびｐＨ下限下であり、いずれも付き廻り性は不充分となっている。   Further, Comparative Example 4 is under the Al ion concentration lower limit, and Comparative Example 5 is under the Al ion concentration excess and under the pH lower limit.

更に、比較例６は実施例４のｐＨを上昇させた組成物であり、やはり付き廻り性は不充分であったが、これはｐＨを上昇させる中和工程にて、Ａｌイオンのほとんどが水酸化物として沈殿析出してしまい、もはやＡｌイオンの効果が発揮されなかったためと考えられる。事実、遠心分離後の液分析にてＡｌイオン濃度は０ｐｐｍであることが確認されている。   Further, Comparative Example 6 is a composition in which the pH of Example 4 was raised, and the throwing power was still insufficient, but this is a neutralization step for raising the pH, and most of Al ions are water. This is probably because the precipitates were deposited as oxides, and the effect of Al ions was no longer exhibited. In fact, it has been confirmed by liquid analysis after centrifugation that the Al ion concentration is 0 ppm.

このように、本発明の組成物を用いた、金属材料のカソード電解処理は、従来のカチオン電着塗装では成し得なかった、優れた付き廻り性を得ることができ、かつ従来電解析出不可能であったノニオン性樹脂エマルジョンの電解析出をも可能にする画期的な技術であることがわかる。

Figure 0005249819
As described above, the cathodic electrolysis treatment of a metal material using the composition of the present invention can provide excellent throwing power, which cannot be achieved by conventional cationic electrodeposition coating, and can be obtained by conventional electrolytic deposition. It can be seen that this is an epoch-making technique that enables electrolytic deposition of a nonionic resin emulsion that has been impossible.
Figure 0005249819

Claims (2)

ノニオン性および／またはカチオン性の水系樹脂およびＡｌイオン２０〜５００ｐｐｍを含有し、ｐＨがＡｌイオン濃度をＡ［ｐｐｍ］としたとき次の計算式を満足することを特徴とする電着塗料組成物。
３．５≦ｐＨ≦−Ｌｏｇ（（Ａ×１．９３×１０−１５）１／３） An electrodeposition coating composition comprising a nonionic and / or cationic water-based resin and Al ions of 20 to 500 ppm, wherein the pH satisfies the following formula when the Al ion concentration is A [ppm]: .
3.5 ≦ pH ≦ −Log ((A × 1.93 × 10 −15 ) 1/3 ) 請求項１の組成物を用いて金属材料をカソード電解法にて塗膜を析出せしめることを特徴とする電着塗装方法。

An electrodeposition coating method comprising depositing a coating film of a metal material by a cathode electrolysis method using the composition of claim 1.

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