JP3623854B2 - Aluminum pigment, method for producing the same, and resin composition containing the same - Google Patents
Aluminum pigment, method for producing the same, and resin composition containing the same Download PDFInfo
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- JP3623854B2 JP3623854B2 JP14750296A JP14750296A JP3623854B2 JP 3623854 B2 JP3623854 B2 JP 3623854B2 JP 14750296 A JP14750296 A JP 14750296A JP 14750296 A JP14750296 A JP 14750296A JP 3623854 B2 JP3623854 B2 JP 3623854B2
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- aluminum pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/642—Aluminium treated with inorganic compounds
Description
【０００１】
【発明の属する技術分野】
本発明は、水性メタリック塗料あるいは水性メタリックインキ等に用いられる、アルミニウム顔料とその製造方法およびそれを配合してなる樹脂組成物に関する。
【０００２】
【従来の技術および発明が解決しようとする課題】
アルミニウム顔料を水性ワニスに配合すると、ワニスに含まれる水と反応し、水素ガスを発生して貯蔵中に容器が爆発したり、アルミニウム顔料が固まってブツを発生するなどの問題を生じる。
【０００３】
これを解決するため多くの技術が開発されているが、比較的実用に近い最近の技術としては、特公平１−５４３８６、特開昭５９−７４２０１、特公昭６０−８０５７、特開平４−３１８１８１、米国特許５，２９６，０３２、特開平６−５７１７１が公知である。
【０００４】
特公平１−５４３８６号では、アルミニウム顔料をクロム酸で処理する方法が開示されている。この方法によればアルミニウム顔料の化学的安定性は改善されるが、処理液の反応性が強すぎるために細かいアルミニウム顔料の処理ができない、六価クロム化合物を使用するため労働衛生面あるいは環境面での問題が大きい等の難点があり、あまり実用化されていない。
【０００５】
特開昭５９−７４２０１号では、アルミニウム顔料をバナジン酸アンモニウムで処理する方法が開示されている。この方法では、処理によるアルミニウム顔料の色調の変化が大きいことが問題となり、実用化には至っていない。
【０００６】
特公昭６０−８０５７号では、アルミニウム顔料を酸性燐酸エステルで被覆する方法が開示されている。この方法によればアルミニウム顔料の色調や化学的安定性は良好であるが、２コート１ベイクあるいは２コート２ベイク塗膜を作成した場合に、処理剤がアルミニウム顔料と樹脂との密着性に好ましからざる影響を及ぼし、ベースメタリック塗膜層とトップコート層との間の層間剥離が大きな問題となる。
【０００７】
特開平４−３１８１８１号では、アルミニウム顔料をモリブデン酸等の酸化剤と燐酸イオン及びアルカリ土類金属イオンを含有する処理液で処理する方法が開示されている。この方法によれば化学的安定性の優れたアルミニウム顔料が作成できるが、処理液に含まれる燐酸イオンやアルカリ土類金属イオンが塗膜の耐湿性その他の物性を低下させる傾向がある。
【０００８】
米国特許５，２９６，０３２では、アルミニウム顔料を燐モリブデン酸などのヘテロポリアニオンで処理する方法が開示されている。この方法の中で、燐モリブデン酸で処理されたアルミニウム顔料は化学的に安定であるが、処理剤に含まれる燐イオンが塗膜耐湿性等の物性を低下させる。また、その他の処理剤については十分な化学的安定性が得られない。
【０００９】
特開平６−５７１７１号では、アルミニウム顔料をモリブデン酸アンモニウムで処理した後、モリブデン酸塩等を添加して更にアルミニウム顔料を安定化する方法が開示されている。この方法によれば化学的安定性の優れたアルミニウム顔料を得ることが可能であり、塗膜物性についても問題は無いが、製造工程が煩雑であるという問題がある。
【００１０】
【課題を解決するための手段】
本発明のアルミニウム顔料は、その表面に少なくとも一種の過酸化ポリ酸から誘導される皮膜が形成されていることを特徴とする。このような過酸化ポリ酸から誘導される皮膜は緻密で耐食性に優れているため、これをアルミニウム顔料表面に形成することにより水性塗料や水性インキ用ワニスに対し化学的に極めて安定なアルミニウム顔料を得ることができる。また、この皮膜は燐やアルカリ土類金属などの塗膜物性に対し悪影響を及ぼす元素を含まないため、本発明のアルミニウム顔料を配合しても、塗膜の耐湿性や耐候性が低下することが無い。
【００１１】
【発明の実施の形態】
本発明に用いられる過酸化ポリ酸は、組成式ＭｘＯｙ・ｍＨ２Ｏ２・ｎＨ２Ｏ（ただし、Ｍは金属元素、ｘは１または２、ｙは２〜５の整数、ｍおよびｎは任意の正数を示す。）で示される。Ｍで表される金属元素として好ましい元素は周期律表４ａ族、５ａ族、６ａ族に含まれる元素で、その中でもＭｏ、Ｗが特にアルミニウム顔料の防食性に優れ、好適である。これらの元素を含む過酸化ポリ酸により特に化学的に安定な皮膜をアルミニウム顔料表面に形成することができる。
【００１２】
アルミニウム顔料表面に形成された皮膜中の金属元素Ｍの量は、アルミニウム顔料１００重量部に対し、０．０１〜２．０重量部、より好ましくは０．０５〜１．０重量部が好適である。金属元素の量がこれよりも少ない場合には、所望の化学的安定性が得られにくく、多すぎるとアルミニウム顔料の色調の変化が大きくなる、アルミニウム顔料が凝集する、塗膜物性が低下するなどの不都合が生じる。
【００１３】
本発明に使用される過酸化ポリ酸は燐を含まず、燐の含有量を本発明のアルミニウム顔料１００重量部当たり０．０１重量部以下、好ましくは０．００５重量部以下に抑えることができるため、燐酸イオンの存在に起因する耐湿性等の塗膜物性の低下を回避することができる。
【００１４】
本発明のアルミニウム顔料を製造する方法としては、アルミニウム顔料を組成式ＭｘＯｙ・ｍＨ２Ｏ２・ｎＨ２Ｏで示される少なくとも一種の過酸化ポリ酸を含む溶液とを、スラリー状態またはペースト状態で、撹拌または混練することにより表面に過酸化ポリ酸から誘導される皮膜を形成する方法が好適である。
【００１５】
過酸化ポリ酸を含む溶液の作成方法としては、過酸化水素水に金属元素を単体あるいはアルコキシドの如き化合物として溶解させる方法が好適である。過酸化ポリ酸を含む溶液には、未反応の水あるいは過酸化水素等の不可避不純物が含まれていても良い。具体的な作成方法としては、過酸化ポリ酸を含む溶液として、１〜７０重量％（より好ましくは５〜５０重量％）の過酸化水素を含む過酸化水素水に金属元素を単体あるいは化合物として１〜５０重量％（より好ましくは５〜２０重量％）溶解させる方法が好適である。過酸化水素水の濃度が薄すぎると金属元素を溶解させることが困難となり、多すぎると金属元素を添加したときに激しい反応が起こるため危険である。過酸化水素水に溶解させる金属元素の濃度は、低すぎると所望の効果が得られにくく、多すぎると過酸化水素水に溶解しきれなくなる。
【００１６】
塗料に対する分散性や樹脂との親和性を向上させる目的、あるいは耐食性をさらに向上させる目的で、本発明のアルミニウム顔料の表面にさらに樹脂やカップリング剤（シランカップリング剤、チタネートカップリング剤等）を公知方法にしたがって被覆しても良いし、顔料分散剤（界面活性剤）や腐食抑制剤等を添加しても良い。本発明のアルミニウム顔料に樹脂を被覆する方法としては、アルミニウム顔料をミネラルスピリットなどの溶媒に分散し、アクリル酸エステル、メタクリル酸エステル、スチレン等のモノマーとアゾ化合物や過酸化物等の重合開始剤を添加し、加熱撹拌することにより該モノマーを重合させ、該アルミニウム顔料表面に析出させる方法が好適である。また、添加する腐食抑制剤としてはモリブデン酸の金属塩、酸性燐酸エステル、ダイマー酸等が好適である。
【００１７】
本発明のアルミニウム顔料は、塗料・インキなどに配合された樹脂組成物として使用される。ここで言う樹脂組成物には、例えば塗料およびその塗膜、あるいはインキおよびその印刷物が包含される。塗料およびインキは有機溶剤型、水性のいずれにも使用可能であるが、本発明の目的からして、水性塗料あるいは水性インキに特に好適に使用される。樹脂組成物に用いる場合の着色アルミニウム顔料の配合量は、樹脂組成物の重量に対し０．１〜３０％が適当である。配合量が少ない場合は十分な装飾（メタリック）効果が得られず、多すぎる場合は樹脂組成物の物性（耐候性、耐食性、機械強度など）に悪影響を及ぼす。
【００１８】
塗料・インキについては次のような成分から構成される：
１）樹 脂：アクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリ酢酸ビニル樹脂、ニトロセルロース樹脂、フッ素樹脂；
２）顔 料：本発明による着色フレークの他に、フタロシアニン、キナクリドン、イソインドリノン、ペリレン、アゾレーキ、酸化鉄、黄鉛、カーボンブラック、酸化チタン、パールマイカのような着色顔料あるいは体質顔料もしくは染料を併用しても良い；
３）添加剤：水、有機溶剤、界面活性剤、硬化剤、紫外線吸収剤、静電気除去剤、増粘剤等。
【００１９】
本発明の樹脂組成物による塗膜については、電着塗装等による下塗り層や中塗り層の上に形成されていても良く、また、本発明の塗膜の上にトップコート層が形成されていても良い。
【００２０】
【作用・効果】
本発明によるアルミニウム顔料は化学的に安定で、水性塗料や水性インキに好適に使用することができる。
【００２１】
本発明のアルミニウム顔料の製造方法は、簡便で、しかも得られたアルミニウム顔料は化学的安定性に優れている。
【００２２】
本発明の樹脂組成物は、水性塗料あるいは水性インキとして貯蔵安定性に優れており、貯蔵中に水素ガスが発生したり、アルミニウム顔料が凝集したりすることが無い。また、塗膜や印刷物は耐湿性その他の物性が優れている。
【００２３】
【実施例】
（実施例１）
過酸化水素３０％を含む過酸化水素水１０ｇに、金属モリブデン粉末１．５ｇを少しずつ加え、反応させて得られた溶液６．５ｇをイソプロピルアルコール１７５ｇに溶解させた後、市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇに添加してニーダーミキサーで１時間混練し、ペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＭｏおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｍｏは０．１３重量部、Ｐは０．００５重量部以下であった。
【００２４】
（実施例２）
過酸化水素１５％を含む過酸化水素水１０ｇに、金属タングステン粉末１ｇを少しずつ加え、反応させて得られた溶液８ｇをイソプロピルアルコール２０００ｍｌに溶解し、アルミニウム顔料の処理液を作成した。この処理液に市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇを入れてスターラーで攪拌混合し、温度を５０℃に保って４時間反応させた。次いで、このスラリーを加圧フィルターで固液分離し、固形分５０％のペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＷおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｗは０．０８重量部、Ｐは０．００５重量部以下であった。
【００２５】
（実施例３）
過酸化水素３０％を含む過酸化水素水１０ｇに、金属チタン粉末１．５ｇを少しずつ加え、反応させて得られた溶液６．５ｇをイソプロピルアルコール１７５ｇに溶解させた後、市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇに添加してニーダーミキサーで１時間混練し、ペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＴｉおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｔｉは０．１３重量部、Ｐは０．００５重量部以下であった。
【００２６】
（実施例４）
過酸化水素３０％を含む過酸化水素水１０ｇに、タンタルテトラエトキシド３ｇを少しずつ加え、反応させて得られた溶液６．５ｇをイソプロピルアルコール１７５ｇに溶解させた後、市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇに添加してニーダーミキサーで１時間混練し、ペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＴａおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｔａは０．１３重量部、Ｐは０．００５重量部以下であった。
【００２７】
（実施例５）
過酸化水素３０％を含む過酸化水素水１０ｇに、金属モリブデン粉末１．５ｇを少しずつ加え、反応させて得られた溶液１．３ｇをメチルプロピレングリコールモノメチルエーテル１７５ｇに溶解させた後、市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇに添加してニーダーミキサーで１時間混練し、ペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＭｏおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｍｏは０．０２重量部、Ｐは０．００５重量部以下であった。
【００２８】
（実施例６）
過酸化水素３０％を含む過酸化水素水３０ｇに、金属モリブデン粉末４．５ｇを少しずつ加え、反応させて得られた溶液２６ｇをイソプロピルアルコール１７５ｇに溶解させた後、市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇに添加してニーダーミキサーで１時間混練し、５５％のペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＭｏおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｍｏは０．５２重量部、Ｐは０．００５重量部以下であった。
【００２９】
（実施例７）
過酸化水素３０％を含む過酸化水素水１００ｇに、金属モリブデン粉末１５ｇを少しずつ加え、反応させて得られた溶液６５ｇをイソプロピルアルコール１７５ｇに溶解させた後、市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇに添加してニーダーミキサーで１時間混練し、ペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＭｏおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｍｏは１．２９重量部、Ｐは０．００５重量部以下であった。
【００３０】
（実施例８）
過酸化水素１５％を含む過酸化水素水１０ｇに、金属バナジウム粉末１ｇを少しずつ加え、反応させて得られた溶液８ｇをイソプロピルアルコール２０００ｍｌに溶解させた後、アルミニウム顔料の処理液を作成した。この処理液に市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇを入れてスターラーで攪拌混合し、温度を５０℃に保って４時間反応させた。次いで、このスラリーを加圧フィルターで固液分離し、固形分５０％のペースト状アルミニウム顔料を得た。このペースト状アルミニウム顔料を乾燥し、パウダー化した試料のＶおよびＰの含有量をプラズマ発光分析により定量した結果、アルミニウム顔料１００重量部に対し、Ｖは０．０７重量部、Ｐは０．００５重量部以下であった。
【００３１】
（比較例１）
比較例１として、実施例に用いたアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）の配合溶剤を単にイソプロピルアルコールに置換し、固形分６５％としたアルミニウム顔料を作成した。
【００３２】
（比較例２）
燐モリブデン酸６５ｇをメチルプロピレンジグリコールモノメチルエーテル２０００ｍｌに溶解し、アルミニウム顔料の処理液を作成した。この処理液に市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）１ｋｇを入れてスターラーで攪拌混合し、温度を８０℃に保って５時間反応させた。次いで、このスラリーを加圧フィルターで固液分離し、固形分５０％のペースト状アルミニウム顔料を得た。このアルミニウム顔料を乾燥し、プラズマ発光分析でＭｏおよびＰの含有量を定量した結果、アルミニウム顔料１００重量部に対し、Ｍｏは２．１重量部、Ｐは０．０７重量部であった。
【００３３】
（比較例３）
市販のアルミニウム顔料（東洋アルミニウム（株）７６４０ＮＳ−−固形分６５％）５００ｇをメチルプロピレンジグリコールモノメチルエーテル２０００ｍｌに分散したスラリーを撹拌しながら、パラモリブデン酸アンモニウム１．６３ｇを脱イオン水４００ｍｌに溶解した溶液を徐々に加え、スラリー温度を１８℃に保ちながら１時間反応させた。得られたスラリーを固液分離し、固形分５０％のペースト状アルミニウム顔料を得た。このアルミニウム顔料を乾燥し、プラズマ発光分析でＭｏおよびＰの含有量を定量した結果、アルミニウム顔料１００重量部に対し、Ｍｏは１．２重量部、Ｐは０．００５重量部以下であった。
【００３４】
（実施例９〜１６）
実施例１〜８で得られたアルミニウム顔料を使用し、下記の組成：
水溶性アクリル樹脂 ２８．２ｇ
（三井東圧化学（株）アルマテックス ＷＡ９１１）
メラミン樹脂 ４．４ｇ
（三井東圧化学（株）サイメル ３５０）
トリエタノールアミン １．１ｇ
脱イオン水 ４４．８ｇ
イソプロピルアルコール ３．０ｇ
透明酸化鉄 ５．０ｇ
（ＢＡＳＦ社 ＳＩＣＯＴＲＡＮＳ ＲＥＤ Ｌ２１７５Ｄ）
アルミニウム顔料（実施例１〜８） ３．０ｇ（固形分として）
を有する水性メタリックベース塗料を作成した。
【００３５】
（比較例４〜６）
比較例１〜３で得られたアルミニウム顔料を使用し、実施例９〜１６と同様の組成で水性メタリックベース塗料を作成した。
【００３６】
−テスト１−
実施例９〜１６、比較例４〜６で作成した水性メタリックベース塗料８０ｇを採取し、これらを５０℃に調整した湯煎器内で７日間保管した場合の累積水素ガス発生量を測定した。
【００３７】
（実施例１７〜２４）
実施例９〜１６で作成した水性メタリックベース塗料をあらかじめ一次防錆塗料を電着塗装したテスト用鋼板に乾燥膜厚１３μｍとなるようにエアースプレー塗装し、９０℃で１０分間予備乾燥した後、下記の組成：
アクリル樹脂 １４０ｇ
（三井東圧化学（株） アルマテックス １１０）
メラミン樹脂 ５０ｇ
（三井東圧化学（株） ユーバン ２０ＳＥ６０）
ソルベッソ１００ ６０ｇ
の有機溶剤型トップコート用塗料を、乾燥膜厚４０μｍとなるようにエアースプレー塗装し、メタリック塗装塗板を作成した。
【００３８】
（比較例７〜９）
比較例４〜６で作成した水性メタリックベース塗料を使用し、実施例１７〜２４と同様の方法でメタリック塗装塗板を作成した。
【００３９】
−テスト２−
実施例１７〜２４、比較例７〜９で得られたメタリック塗装塗板およびそれらを５０℃、相対湿度９８％以上の雰囲気に１０日間曝した塗板について、ＡＳＴＭ Ｄ３３５９Ｂに記載の方法により密着性テストを行い、六段階評価を行った。実用的には、このテストによる評価が４Ｂ以上であることが望ましい。
【００４０】
テスト１、テスト２の結果を表１に示す。
【００４１】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum pigment, a method for producing the same, and a resin composition obtained by blending the same, which are used in water-based metallic paints or water-based metallic inks.
[0002]
[Background Art and Problems to be Solved by the Invention]
When an aluminum pigment is blended with an aqueous varnish, it reacts with the water contained in the varnish to generate hydrogen gas, causing the container to explode during storage, or the aluminum pigment to solidify and generate problems.
[0003]
Many techniques have been developed to solve this, but as recent techniques that are relatively practical, Japanese Patent Publication No. 1-54386, Japanese Patent Publication No. Sho 59-74201, Japanese Patent Publication No. Sho 60-8057, Japanese Patent Publication No. Hei 4-318181. U.S. Pat. No. 5,296,032 and JP-A-6-57171 are known.
[0004]
Japanese Patent Publication No. 1-54386 discloses a method of treating an aluminum pigment with chromic acid. Although this method improves the chemical stability of aluminum pigments, it cannot treat fine aluminum pigments because the treatment solution is too reactive. However, it has not been put to practical use.
[0005]
JP 59-74201 discloses a method of treating aluminum pigments with ammonium vanadate. This method has a problem in that the change in the color tone of the aluminum pigment due to the treatment is large, and has not been put into practical use.
[0006]
Japanese Patent Publication No. 60-8057 discloses a method of coating an aluminum pigment with an acidic phosphate ester. According to this method, the color tone and chemical stability of the aluminum pigment are good, but when a 2-coat 1-bake or 2-coat 2-bake coating film is prepared, the treatment agent is preferred for adhesion between the aluminum pigment and the resin. It has a significant effect, and delamination between the base metallic coating layer and the topcoat layer becomes a major problem.
[0007]
JP-A-4-318181 discloses a method of treating an aluminum pigment with a treatment liquid containing an oxidizing agent such as molybdic acid, phosphate ions and alkaline earth metal ions. According to this method, an aluminum pigment having excellent chemical stability can be prepared, but phosphate ions and alkaline earth metal ions contained in the treatment liquid tend to lower the moisture resistance and other physical properties of the coating film.
[0008]
US Pat. No. 5,296,032 discloses a method of treating aluminum pigments with heteropolyanions such as phosphomolybdic acid. In this method, the aluminum pigment treated with phosphomolybdic acid is chemically stable, but the phosphorus ions contained in the treating agent lower the physical properties such as moisture resistance of the coating film. Moreover, sufficient chemical stability cannot be obtained for other treatment agents.
[0009]
Japanese Patent Application Laid-Open No. 6-57171 discloses a method in which an aluminum pigment is treated with ammonium molybdate and then molybdate is added to further stabilize the aluminum pigment. According to this method, an aluminum pigment having excellent chemical stability can be obtained, and there is no problem with the physical properties of the coating film, but there is a problem that the production process is complicated.
[0010]
[Means for Solving the Problems]
The aluminum pigment of the present invention is characterized in that a film derived from at least one kind of polyacid peroxide is formed on the surface thereof. Since the coating derived from such peroxide polyacids is dense and excellent in corrosion resistance, it is formed on the surface of the aluminum pigment to form an aluminum pigment that is chemically extremely stable against water-based paints and varnishes for water-based inks. Can be obtained. In addition, since this film does not contain elements that adversely affect the film properties such as phosphorus and alkaline earth metals, even if the aluminum pigment of the present invention is blended, the moisture resistance and weather resistance of the film may be reduced. There is no.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The peroxide polyacid used in the present invention has a composition formula M x O y · mH 2 O 2 · nH 2 O (where M is a metal element, x is 1 or 2, y is an integer of 2 to 5, m and n represents an arbitrary positive number.) Preferable elements as the metal element represented by M are elements contained in groups 4a, 5a, and 6a of the periodic table, and among them, Mo and W are particularly preferable because of excellent corrosion resistance of aluminum pigments. A particularly chemically stable film can be formed on the surface of the aluminum pigment by the peroxide polyacid containing these elements.
[0012]
The amount of the metal element M in the film formed on the surface of the aluminum pigment is preferably 0.01 to 2.0 parts by weight, more preferably 0.05 to 1.0 parts by weight with respect to 100 parts by weight of the aluminum pigment. is there. If the amount of the metal element is less than this, it is difficult to obtain the desired chemical stability, and if it is too much, the change in the color tone of the aluminum pigment increases, the aluminum pigment aggregates, and the physical properties of the coating film deteriorate. Inconvenience occurs.
[0013]
The peroxypolyacid used in the present invention does not contain phosphorus, and the phosphorus content can be suppressed to 0.01 parts by weight or less, preferably 0.005 parts by weight or less per 100 parts by weight of the aluminum pigment of the present invention. Therefore, it is possible to avoid a decrease in coating film properties such as moisture resistance due to the presence of phosphate ions.
[0014]
As a method for producing the aluminum pigment of the present invention, the aluminum pigment is mixed with a solution containing at least one peroxide polyacid represented by the composition formula M x O y · mH 2 O 2 · nH 2 O in a slurry state or a paste. In this state, a method of forming a film derived from peroxide polyacid on the surface by stirring or kneading is preferable.
[0015]
As a method for preparing a solution containing a peroxide polyacid, a method of dissolving a metal element in a hydrogen peroxide solution as a simple substance or a compound such as an alkoxide is suitable. The solution containing the peroxide polyacid may contain unreacted water or inevitable impurities such as hydrogen peroxide. As a specific preparation method, as a solution containing a peroxide polyacid, a metal element as a simple substance or a compound in a hydrogen peroxide solution containing 1 to 70% by weight (more preferably 5 to 50% by weight) of hydrogen peroxide. A method of dissolving 1 to 50% by weight (more preferably 5 to 20% by weight) is suitable. If the concentration of the hydrogen peroxide solution is too low, it becomes difficult to dissolve the metal element, and if it is too high, a severe reaction occurs when the metal element is added, which is dangerous. If the concentration of the metal element dissolved in the hydrogen peroxide solution is too low, it is difficult to obtain a desired effect. If the concentration is too large, the metal element cannot be completely dissolved in the hydrogen peroxide solution.
[0016]
Resin or coupling agent (silane coupling agent, titanate coupling agent, etc.) is further added to the surface of the aluminum pigment of the present invention for the purpose of improving the dispersibility to the paint and the affinity with the resin, or further improving the corrosion resistance. May be coated according to a known method, or a pigment dispersant (surfactant), a corrosion inhibitor or the like may be added. As a method of coating the resin on the aluminum pigment of the present invention, the aluminum pigment is dispersed in a solvent such as mineral spirit, a monomer such as acrylate ester, methacrylate ester or styrene, and a polymerization initiator such as azo compound or peroxide. A method in which the monomer is polymerized by adding and stirring with heating and deposited on the surface of the aluminum pigment is preferable. Further, as the corrosion inhibitor to be added, metal salts of molybdic acid, acidic phosphoric acid esters, dimer acids and the like are suitable.
[0017]
The aluminum pigment of the present invention is used as a resin composition blended in paints and inks. The resin composition referred to here includes, for example, a paint and its coating film, or ink and its printed matter. The paints and inks can be used in both organic solvent type and water-based, but for the purpose of the present invention, they are particularly preferably used in water-based paints or water-based inks. The blending amount of the colored aluminum pigment when used in the resin composition is suitably 0.1 to 30% with respect to the weight of the resin composition. When the blending amount is small, a sufficient decoration (metallic) effect cannot be obtained, and when it is too large, the physical properties (such as weather resistance, corrosion resistance, and mechanical strength) of the resin composition are adversely affected.
[0018]
Paints and inks are composed of the following components:
1) Resin: Acrylic resin, alkyd resin, polyester resin, polyurethane resin, polyvinyl acetate resin, nitrocellulose resin, fluorine resin;
2) Facial: In addition to the colored flakes according to the present invention, colored pigments or extender pigments or dyes such as phthalocyanine, quinacridone, isoindolinone, perylene, azo lake, iron oxide, yellow lead, carbon black, titanium oxide, pearl mica May be used together;
3) Additives: water, organic solvents, surfactants, curing agents, ultraviolet absorbers, static eliminating agents, thickeners, etc.
[0019]
The coating film of the resin composition of the present invention may be formed on an undercoat layer or an intermediate coating layer by electrodeposition coating or the like, and a topcoat layer is formed on the coating film of the present invention. May be.
[0020]
[Action / Effect]
The aluminum pigment according to the present invention is chemically stable and can be suitably used for water-based paints and water-based inks.
[0021]
The method for producing an aluminum pigment of the present invention is simple, and the obtained aluminum pigment is excellent in chemical stability.
[0022]
The resin composition of the present invention is excellent in storage stability as a water-based paint or water-based ink, and does not generate hydrogen gas or aggregate an aluminum pigment during storage. Moreover, the coating film and the printed material are excellent in moisture resistance and other physical properties.
[0023]
【Example】
(Example 1)
After adding 6.5 g of metal molybdenum powder to 10 g of hydrogen peroxide containing 30% hydrogen peroxide little by little and dissolving the resulting solution in 175 g of isopropyl alcohol, a commercially available aluminum pigment ( Toyo Aluminum Co., Ltd. 7640NS--solid content 65%) was added to 1 kg and kneaded with a kneader mixer for 1 hour to obtain a pasty aluminum pigment. As a result of quantifying the contents of Mo and P in the dried and powdered sample by plasma emission analysis, Mo was 0.13 parts by weight and P was 0.005 parts per 100 parts by weight of the aluminum pigment. It was below part by weight.
[0024]
(Example 2)
1 g of metal tungsten powder was added little by little to 10 g of hydrogen peroxide containing 15% hydrogen peroxide, and 8 g of the resulting solution was dissolved in 2000 ml of isopropyl alcohol to prepare an aluminum pigment treatment solution. 1 kg of a commercially available aluminum pigment (Toyo Aluminum Co., Ltd. 7640 NS--solid content 65%) was added to this treatment solution, and the mixture was stirred and mixed with a stirrer, and the temperature was maintained at 50 ° C. for 4 hours. Subsequently, this slurry was subjected to solid-liquid separation with a pressure filter, and a pasty aluminum pigment having a solid content of 50% was obtained. As a result of quantifying the contents of W and P in the dried aluminum powder powder sample by plasma emission analysis, W was 0.08 parts by weight and P was 0.005 parts by weight with respect to 100 parts by weight of the aluminum pigment. It was below part by weight.
[0025]
(Example 3)
After adding 6.5 g of metal titanium powder little by little to 10 g of hydrogen peroxide containing 30% hydrogen peroxide and reacting it with 175 g of isopropyl alcohol, a commercially available aluminum pigment ( Toyo Aluminum Co., Ltd. 7640NS--solid content 65%) was added to 1 kg and kneaded with a kneader mixer for 1 hour to obtain a pasty aluminum pigment. As a result of quantifying the contents of Ti and P in the dried and powdered sample by plasma emission analysis, 0.13 parts by weight of Ti and 0.005% of P with respect to 100 parts by weight of the aluminum pigment were obtained. It was below part by weight.
[0026]
(Example 4)
3 g of tantalum tetraethoxide was added little by little to 10 g of hydrogen peroxide containing 30% hydrogen peroxide, and 6.5 g of a solution obtained by the reaction was dissolved in 175 g of isopropyl alcohol. Aluminum Co., Ltd. 7640NS--solid content 65%) was added to 1 kg and kneaded for 1 hour with a kneader mixer to obtain a pasty aluminum pigment. As a result of quantifying the contents of Ta and P in the sample obtained by drying and pasting this pasty aluminum pigment by plasma emission analysis, 0.13 parts by weight of Ta and 0.005 parts of P were added to 100 parts by weight of the aluminum pigment. It was below part by weight.
[0027]
(Example 5)
After adding 1.5 g of metal molybdenum powder to 10 g of hydrogen peroxide containing 30% hydrogen peroxide little by little and dissolving 1.3 g of the resulting solution in 175 g of methylpropylene glycol monomethyl ether, It was added to 1 kg of aluminum pigment (Toyo Aluminum Co., Ltd. 7640 NS--solid content 65%) and kneaded with a kneader mixer for 1 hour to obtain a pasty aluminum pigment. As a result of quantifying the contents of Mo and P in the dried and powdered sample by plasma emission analysis, 0.02 parts by weight of Mo and 0.005 parts by weight of P are 0.005 parts by weight with respect to 100 parts by weight of the aluminum pigment. It was below part by weight.
[0028]
(Example 6)
To 30 g of hydrogen peroxide containing 30% hydrogen peroxide, 4.5 g of metal molybdenum powder was added little by little, and 26 g of the resulting solution was dissolved in 175 g of isopropyl alcohol, and then commercially available aluminum pigment (Toyo Aluminum) 7640 NS--solid content 65%) was added to 1 kg and kneaded with a kneader mixer for 1 hour to obtain 55% of a pasty aluminum pigment. As a result of quantifying the contents of Mo and P in the dried and powdered sample by plasma emission analysis, Mo was 0.52 parts by weight and P was 0.005 parts per 100 parts by weight of the aluminum pigment. It was below part by weight.
[0029]
(Example 7)
To 100 g of hydrogen peroxide containing 30% hydrogen peroxide, 15 g of metal molybdenum powder was added little by little and 65 g of the resulting solution was dissolved in 175 g of isopropyl alcohol, and then a commercially available aluminum pigment (Toyo Aluminum Co., Ltd.) 7640 NS--65% solid content) 1 kg and kneaded with a kneader mixer for 1 hour to obtain a pasty aluminum pigment. As a result of quantifying the contents of Mo and P in the dried and powdered sample by plasma emission analysis, Mo was 1.29 parts by weight with respect to 100 parts by weight of the aluminum pigment, and P was 0.005. It was below part by weight.
[0030]
(Example 8)
1 g of metal vanadium powder was added little by little to 10 g of hydrogen peroxide containing 15% hydrogen peroxide, and 8 g of the resulting solution was dissolved in 2000 ml of isopropyl alcohol to prepare a treatment solution for aluminum pigment. 1 kg of a commercially available aluminum pigment (Toyo Aluminum Co., Ltd. 7640 NS--solid content 65%) was added to this treatment solution, and the mixture was stirred and mixed with a stirrer, and the temperature was maintained at 50 ° C. for 4 hours. Subsequently, this slurry was subjected to solid-liquid separation with a pressure filter, and a pasty aluminum pigment having a solid content of 50% was obtained. As a result of quantifying the contents of V and P in the dried and powdered sample by plasma emission analysis, V was 0.07 parts by weight and P was 0.005 parts per 100 parts by weight of the aluminum pigment. It was below part by weight.
[0031]
(Comparative Example 1)
As Comparative Example 1, an aluminum pigment having a solid content of 65% was prepared by simply replacing the compounding solvent of the aluminum pigment (Toyo Aluminum Co., Ltd., 7640 NS--solid content of 65%) used in the examples with isopropyl alcohol.
[0032]
(Comparative Example 2)
65 g of phosphomolybdic acid was dissolved in 2000 ml of methylpropylene diglycol monomethyl ether to prepare an aluminum pigment treatment solution. 1 kg of a commercially available aluminum pigment (Toyo Aluminum Co., Ltd. 7640 NS--solid content 65%) was added to this treatment liquid, and the mixture was stirred and mixed with a stirrer, and the temperature was kept at 80 ° C. for 5 hours. Subsequently, this slurry was subjected to solid-liquid separation with a pressure filter, and a pasty aluminum pigment having a solid content of 50% was obtained. The aluminum pigment was dried and the contents of Mo and P were determined by plasma emission analysis. As a result, Mo was 2.1 parts by weight and P was 0.07 parts by weight with respect to 100 parts by weight of the aluminum pigment.
[0033]
(Comparative Example 3)
1.63 g of ammonium paramolybdate is dissolved in 400 ml of deionized water while stirring a slurry of 500 g of commercially available aluminum pigment (Toyo Aluminum Co., Ltd. 7640 NS—solid content 65%) dispersed in 2000 ml of methylpropylene diglycol monomethyl ether. The solution was gradually added and reacted for 1 hour while maintaining the slurry temperature at 18 ° C. The obtained slurry was subjected to solid-liquid separation to obtain a pasty aluminum pigment having a solid content of 50%. The aluminum pigment was dried and the contents of Mo and P were quantified by plasma emission analysis. As a result, Mo was 1.2 parts by weight and P was 0.005 parts by weight or less with respect to 100 parts by weight of the aluminum pigment.
[0034]
(Examples 9 to 16)
Using the aluminum pigments obtained in Examples 1-8, the following composition:
Water-soluble acrylic resin 28.2g
(Mitsui Toatsu Chemical Co., Ltd. Almatex WA911)
Melamine resin 4.4g
(Mitsui Toatsu Chemical Co., Ltd. Cymel 350)
Triethanolamine 1.1g
44.8g of deionized water
Isopropyl alcohol 3.0g
Transparent iron oxide 5.0g
(BASF company SICOTRANS RED L2175D)
Aluminum pigment (Examples 1-8) 3.0 g (as solids)
A water-based metallic base paint was prepared.
[0035]
(Comparative Examples 4-6)
Using the aluminum pigment obtained in Comparative Examples 1 to 3, water-based metallic base paints were prepared with the same composition as in Examples 9 to 16.
[0036]
-Test 1
80 g of the aqueous metallic base paint prepared in Examples 9 to 16 and Comparative Examples 4 to 6 was collected, and the amount of accumulated hydrogen gas generated when stored in a water bath adjusted to 50 ° C. for 7 days was measured.
[0037]
(Examples 17 to 24)
The water-based metallic base paint prepared in Examples 9 to 16 was air-sprayed on a test steel plate previously electrodeposited with a primary rust preventive paint so as to have a dry film thickness of 13 μm, and pre-dried at 90 ° C. for 10 minutes, The following composition:
Acrylic resin 140g
(Mitsui Toatsu Chemical Co., Ltd. Almatex 110)
Melamine resin 50g
(Mitsui Toatsu Chemicals Co., Ltd. Uban 20SE60)
Solvesso 100 60g
The organic solvent-type top coat paint was applied by air spraying so as to have a dry film thickness of 40 μm to prepare a metallic paint coated plate.
[0038]
(Comparative Examples 7-9)
Using the water-based metallic base paints prepared in Comparative Examples 4 to 6, metallic paint coated plates were prepared in the same manner as in Examples 17 to 24.
[0039]
-Test 2-
The adhesion test was carried out by the method described in ASTM D3359B for the metallic paint plates obtained in Examples 17 to 24 and Comparative Examples 7 to 9 and the coated plates exposed to an atmosphere of 50 ° C. and a relative humidity of 98% or more for 10 days. And performed a six-level evaluation. Practically, it is desirable that the evaluation by this test is 4B or more.
[0040]
The results of Test 1 and Test 2 are shown in Table 1.
[0041]
[Table 1]
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14750296A JP3623854B2 (en) | 1996-06-10 | 1996-06-10 | Aluminum pigment, method for producing the same, and resin composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14750296A JP3623854B2 (en) | 1996-06-10 | 1996-06-10 | Aluminum pigment, method for producing the same, and resin composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09328629A JPH09328629A (en) | 1997-12-22 |
| JP3623854B2 true JP3623854B2 (en) | 2005-02-23 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14750296A Expired - Lifetime JP3623854B2 (en) | 1996-06-10 | 1996-06-10 | Aluminum pigment, method for producing the same, and resin composition containing the same |
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| Country | Link |
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| JP (1) | JP3623854B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1256603B1 (en) * | 2000-10-13 | 2011-12-07 | Toyo Aluminium Kabushiki Kaisha | Aluminum pigment, process for its production and resin compositions containing the same |
| JP3948934B2 (en) * | 2001-11-08 | 2007-07-25 | 東洋アルミニウム株式会社 | Aluminum pigment, method for producing the same, and resin composition |
| KR100772558B1 (en) * | 2002-03-04 | 2007-11-02 | 도요 알루미늄 가부시키가이샤 | aluminium pigment, method for preparing the same and resin composition comprising the same |
| JP2003292825A (en) * | 2002-04-03 | 2003-10-15 | Toyo Aluminium Kk | Colored metallic pigment and resin composition containing the same |
| JP4027938B2 (en) | 2003-04-28 | 2007-12-26 | 東洋アルミニウム株式会社 | Aluminum pigment, method for producing the same, and resin composition |
| EP1990377B1 (en) | 2006-02-14 | 2012-02-08 | Toyo Aluminium Kabushiki Kaisha | Colored metallic pigment, process for producing the same, and coating composition and cosmetic preparation containing said colored metallic pigment |
| JP2008280405A (en) | 2007-05-09 | 2008-11-20 | Toyo Aluminium Kk | Aluminum pigment and production method thereof, as well as aqueous metallic coating composition containing the aluminum pigment |
| JP5177377B2 (en) * | 2007-12-27 | 2013-04-03 | 日本ペイント株式会社 | Water-based base coating composition, metal-type laminated coating film and method for forming the same |
| JP5805921B2 (en) | 2009-03-17 | 2015-11-10 | 東洋アルミニウム株式会社 | Infrared reflective coloring composition, infrared reflective method for applying this colored composition, and coated product |
| JP5532472B2 (en) | 2009-07-06 | 2014-06-25 | 東洋アルミニウム株式会社 | Metal pigment, method for producing the same, and aqueous metallic resin composition containing the same |
| CN101891975B (en) * | 2010-08-10 | 2012-12-05 | 天津碧海蓝天水性高分子材料有限公司 | Nano aluminum oxide with high dispersibility and high ink absorption, preparation method and application thereof |
-
1996
- 1996-06-10 JP JP14750296A patent/JP3623854B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09328629A (en) | 1997-12-22 |
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